Advances in Oil-Water Separation

ADVANCES IN OIL-WATER SEPARATION
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ADVANCES IN
OIL-WATER
SEPARATION
A Complete Guide for Physical,
Chemical, and Biochemical Processes
Edited by
PAPITA DAS
School of Advanced Studies on Industrial Pollution Control Engineering, Jadavpur University, Kolkata, India;
Department of Chemical Engineering, Jadavpur University, Kolkata, India
SUVENDU MANNA
Department of Health Safety and Environment, University of Petroleum and Energy Studies, Dehradun, India
JITENDRA KUMAR PANDEY
School of Basic and Applied Science, Adamas University, Kolkata, India
Elsevier
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Contents
List of contributors xi
3. Oil pollution and municipal wastewater
treatment: issues and impact 57
Rwiddhi Sarkhel and Preetha Ganguly
A
3.1 Introduction 57
3.2 Methodology 58
3.3 Treatment methods of wastewater containing
oil 59
3.4 Results 61
3.5 Conclusion 63
Acknowledgements 63
Conflict of interest 63
References 63
Overview on oil pollution and
its effect on environment
1. An overview of
oil pollution and oil-spilling incidents 3
Sangita Bhattacharjee and Trina Dutta
1.1 Introduction 3
1.2 Oil spill incidents 5
1.3 Case studies 6
1.4 Recovery and clean up 10
1.5 Future predictions 12
1.6 Summary 13
References 13
4. An overview of worldwide regulations
on oil pollution control 65
K. Krishna Koundinya, Surajit Mondal and Amarnath Bose
4.1
4.2
4.3
4.4
Introduction 66
International laws on maritime pollution 69
195462 Convention and its amendments 70
International conference on marine pollution,
1973 71
4.5 MARPOL Convention—73/78 73
4.6 Oil Pollution Act, 1990 77
4.7 Conclusions 80
References 82
2. Spatiotemporal distribution of
oil spill effect in the estuarine terrain of
Bhagirathi-Hooghly River,
West Bengal, India 17
Pankaj Kumar Roy, Arnab Ghosh, Malabika Biswas Roy,
Arunabha Majumder, Asis Mazumdar and Siddhartha Datta
5. Technological aspects of different oil
and water separation advanced
techniques 83
2.1 Introduction 18
2.2 Materials and methods 22
2.3 Methodology 24
2.4 Result and discussions 26
2.5 Dissolved heavy metal indices 42
2.6 Conclusion and recommendation 48
Acknowledgment 50
References 50
Vishal Kumar Singh, Sankari Hazarika, Robin V. John Fernandes,
Ankit Dasgotra, Poonam Singh, Abhishek Sharma and
S.M. Tauseef
5.1 Introduction 83
5.2 Advanced filtration materials
v
84
vi
Contents
5.3 Advanced absorption based materials
5.4 Sol-gel based materials 90
5.5 Conclusion 93
References 94
89
6. Impact analysis of oil pollution on
environment, marine, and
soil communities 99
Shipra Jha and Praveen Dahiya
6.1 Introduction 99
6.2 Composition of petroleum hydrocarbon 100
6.3 Sources and fate of oil spill 101
6.4 Oil pollution and its impact analysis 103
6.5 Future prospects and conclusion 109
References 110
7. Impact of oil exploration and
spillage on marine environments 115
Ankita Thakur and Bhupendra Koul
7.1
7.2
7.3
7.4
7.5
7.6
Introduction 116
Types of pollution 116
Types of oils 118
Causes of oil pollution 119
Harmful effects of oil pollution 120
Bioaccumulation and biomagnification:
marine chemistry 127
7.7 Remedies to cope up with oil pollution 128
7.8 Conclusion 132
References 132
B
Physical processes
8. Superhydrophobic polymeric adsorbents
as an efficient oil separator 139
Shubhalakshmi Sengupta, Priya Banerjee, Anil Kumar Nallajarla,
Venkatalakshmi Jakka, Aniruddha Mukhopadhyay and Papita Das
8.1 Introduction 140
8.2 Materials used for oil/water separation 142
8.3 Polymer-based adsorbents for oil/water
separation 145
8.4 Superhydrophobic polymeric adsorbents 148
8.5 Conclusion 152
Acknowledgments 152
References 152
9. Oil spill treatment using
porous materials 157
Prakash Bobde, Ajaya Kumar Behera and Ravi Kumar Patel
9.1 Introduction 157
9.2 Materials and characterization
9.3 Discussion 163
9.4 Conclusion 170
Abbreviations 170
References 170
160
10. Nanotechnological advances for
oil spill management: removal,
recovery and remediation 175
Sougata Ghosh and Thomas J. Webster
10.1 Introduction 175
10.2 Oil pollution 176
10.3 Nanotechnology driven solutions 176
10.4 Conclusions and future perspectives 191
References 192
11. Carbon nanotube-based
oil-water separation 195
Tamanna Khandelia and Bhisma K. Patel
11.1 Introduction 195
11.2 Carbon nanotube-carbon-based sorbent 196
11.3 Principles of oil-water separation by carbon
nanotube 196
11.4 Structure and synthesis of carbon
nanotube 197
11.5 Current applications: carbon nanotube-based
oil-water separation 198
11.6 Future perspective 205
11.7 Summary 205
References 205
12. Nanocoated membranes for
oil/water separation 207
Karun Kumar Jana, Avijit Bhowal and Papita Das
12.1 Introduction
208
vii
Contents
12.2 Nanocoated membrane technology 209
12.3 Fundamental principles behind oil/water
separation behavior 210
12.4 Current application of membranes in oily
wastewater treatment 213
12.5 Morphology and structure 216
12.6 Wetting properties 218
12.7 Mechanical strength 219
12.8 Antifouling method 220
12.9 Separation performance of membranes for
the oil-in-water mixture 220
12.10 Summary 223
12.11 Future perspective 223
Acknowledgement 224
Conflict of interest 224
References 224
C
15. Use of chemical dispersants for
management of oil pollution 263
Sunil Kumar Tiwari, Shashi Upadhyay, Vishal Kumar Singh,
Ankit Dasgotra, Akula Umamaheswararao, Harsh Sharma and
Jitendra Kumar Pandey
15.1 Introduction 264
15.2 Hazardous effect of oil spill and its
emission 265
15.3 Use of chemical dispersant 267
15.4 Principle and mechanism of chemical
dispersants 269
15.5 Effectiveness and adaptability of chemical
dispersants 273
15.6 National and international regulations for
using chemical dispersants 276
15.7 Applications of different chemical
dispersants 277
15.8 Conclusions 278
References 279
Thermo-chemical processes
13. Chemical stabilization of
oil by elastomizers 233
Sankha Chakrabortty, Jayato Nayak and Prasenjit Chakraborty
13.1 Introduction 233
13.2 Characteristics of oil spills 235
13.3 Oil spill stabilization/remediation
techniques 236
13.4 Future perspective for oil stabilization through
chemical process 245
13.5 Conclusions 245
References 245
14. Advances in burning process and
their impact on the environment 249
16. Brief account on the thermochemical
oil-spill management strategies 283
Y. Sivaji Raghav, Poonam Singh, Ankit Dasgotra and
Abhishek Sharma
16.1 Introduction 283
16.2 Major oil spills incidents 284
16.3 Oil spill treating methods 286
16.4 Emulsifying agents 290
16.5 Impact of emulsion on ecosystem
16.6 Conclusion 292
References 292
292
D
Biological processes
Mandira Agarwal and J. Sudharsan
14.1 Introduction 249
14.2 Principles 250
14.3 In situ burningtechniques & current
application 253
14.4 Environmental and health concerns 258
14.5 Summary 260
References 261
17. Use of live microbes for
oil degradation in situ 297
Ragaa A. Hamouda, Dalel Daassi, Hamdy A. Hassan,
Mervat H. Hussein and Mostafa M. El-Sheekh
17.1 Introduction 298
17.2 Bioremediation of oil compounds by
bacteria 299
viii
Contents
17.3 Role of bacterial oxygenases in the oil
biodegradation 300
17.4 Oil-degrading fungi 300
17.5 Marine fungi 301
17.6 Soil fungi 302
17.7 Mycorrhizal fungi 303
17.8 White rot fungi 303
17.9 Fungal enzymes in bioremediation 304
17.10 In situ—mycoremediation 305
17.11 Bioaugmentation 305
17.12 Fungi bacteria consortium 306
17.13 Biostimulation 306
17.14 Biodegradation of crude oil by fresh
algae 307
17.15 Effect of seaweeds (marine algae) in
biodegradation 308
17.16 Cyanobacteria 308
17.17 Algal bacteria consortium 309
17.18 Factor affecting in biodegradations 310
17.19 Summary 311
References 311
18. Metagenomics—an approach for
selection of oil degrading microbes and
its application in remediation of
oil pollution 319
Md Azizur Rahman, Aakanksha Rajput, Anand Prakash and
Vijayaraghavan M. Chariar
18.1 Introduction 320
18.2 Microbes associated with degradation of
oil 320
18.3 Metagenomics in oil degradation 321
18.4 Application 329
18.5 Metagenomics challenges 330
18.6 Conclusion 331
References 331
19. Potentiality of enzymes as a
green tool in degradation of
petroleum hydrocarbons 337
Uttarini Pathak, Aastha Jhunjhunwala, Sneha Singh,
Neel Bajaj and Tamal Mandal
19.3 Role of algae in enzymatic degradation of
petroleum hydrocarbons 343
19.4 Role of fungi in enzymatic degradation of
petroleum hydrocarbons 344
19.5 Feasibility and technical applicability of
enzymes in oil clean up 346
19.6 Conclusion 348
Conflict of interest 349
References 349
20. Bioremediation: an ecofriendly
approach for the treatment of
oil spills 353
Sudipti Arora, Sonika Saxena, Devanshi Sutaria and Jasmine Sethi
20.1
20.2
20.3
20.4
Introduction 354
Catastrophe 355
An approach to eliminate oil spills 357
Factors affecting the biodegradation
efficiency 363
20.5 Role of microorganism 367
20.6 Novel approaches 368
20.7 Case studies 369
20.8 Conclusion and future prospects 370
References 370
21. Bioremediation of black tides:
strategies involving genetically
modified organisms 375
Sonali Mohanty and Subhankar Paul
21.1 Introduction 375
21.2 Conventional bioremediation strategies and
their limitations 377
21.3 Switch to biological methods“bioremediation” 379
21.4 Genetically engineered organisms (GMOS):
an in situ bioremediation approach 381
21.5 Conclusion 388
References 388
22. Microbes and marine oil spills:
oil-eating bugs can cure oily
sea sickness 393
Jayanta Kumar Biswas, Anurupa Banerjee and Soumyajit Biswas
19.1 Introduction 337
19.2 Role of bacteria in enzymatic degradation of
petroleum hydrocarbons 339
22.1 Introduction 394
22.2 Composition of petroleum hydrocarbons
395
ix
Contents
22.3 Impact of oil pollution on marine
ecosystem 398
22.4 Occurrence and distribution of oil degrading
microbial communities 401
22.5 Metabolic versatilities for oil degradation by
microbes 402
22.6 Factors influencing microbial remediation of
oil 405
22.7 Bioremediation/biodegradation strategies for
removal of oil from contaminated sites 409
22.8 Conclusions 414
22.9 Summary 414
References 415
25. Membrane bioreactors for the
treatment of oily wastewater:
pros and cons 469
Shibam Mitra, Riccardo Campo, Subhojit Bhowmick and
Anirban Biswas
25.1 Oily wastewater: the origin and global
trend 470
25.2 Oily wastewater: environmental impact
25.3 Existing oily wastewater treatment
technologies 472
25.4 Conclusions 483
References 483
471
23. Hybrid biological processes for the
treatment of oily wastewater 423
26. Overview on natural materials for
oil water separation 489
Kulbhushan Samal, Sachin Rameshrao Geed and
Kaustubha Mohanty
Somakraj Banerjee, Riddhi Chakraborty, Ranjana Das and
Chiranjib Bhattacharjee
23.1 Introduction 423
23.2 Methods for oily wastewater treatment
23.3 Biological methods 424
23.4 Biological techniques 428
23.5 Hybrid biological processes 428
23.6 Summary 432
References 433
424
E
Miscellaneous
24. Efficient management of oil waste:
chemical and physicochemical
approaches 439
Zhang Xiaojie, Kalisadhan Mukherjee, Suvendu Manna,
Mohit Kumar Das, Jin Kuk Kim and Tridib Kumar Sinha
Body 440
24.1 Introduction 440
24.2 Hazardous effect of waste oil 442
24.3 Chemical constituents of waste oil 445
24.4 Recycling methods of waste oil 448
24.5 Recycling products 456
24.6 Conclusion and future prospect 460
References 461
26.1
26.2
26.3
26.4
26.5
26.6
Introduction 490
Sources of oil/water mixtures 491
Composition of oil/water mixtures 491
Major processes of oil/water separation 493
Natural materials: an alternative 496
Promising natural materials for oil/water
separation 500
26.7 Conclusion and further prospects 505
Acknowledgment 506
References 506
Further reading 510
27. Extraction and separation of oils:
the journey from distillation to
pervaporation 511
Tathagata Adhikary and Piyali Basak
27.1 Introduction 511
27.2 Techniques in the extraction of oils 513
27.3 Emulsification/formation of emulsions 519
27.4 Oil-water separation or demulsification 522
27.5 Conclusion 530
Acknowledgment 531
References 531
Index 537
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List of contributors
Subhojit Bhowmick School of Environmental
Studies, Jadavpur University, Kolkata, India
Tathagata Adhikary School of Bio-Science and
Engineering, Jadavpur University, Kolkata,
India
Anirban Biswas Department of Environmental
Science, Nabadwip Vidyasagar College,
Nabadwip, India
Mandira Agarwal Department of Petroleum
Engineering & Earthsciences, School of
Engineering, UPES, Dehradun, India
Sudipti Arora Dr. B. Lal
Biotechnology, Jaipur, India
Institute
Jayanta
Kumar
Biswas Department
of
Ecological Studies, University of Kalyani,
Kalyani, India; International Centre for
Ecological
Engineering,
University
of
Kalyani, Kalyani, India
of
Neel
Bajaj Department
of
Chemical
Engineering, National Institute of Technology
Durgapur, Durgapur, India
Anurupa Banerjee Department of Ecological
Studies, University of Kalyani, Kalyani, India
Soumyajit
Biswas Department
of
Biochemistry and Biophysics, University of
Kalyani, Kalyani, India
Priya Banerjee Department of Environmental
Studies, Centre for Distance and Online
Education, Rabindra Bharati University,
Kolkata, India
Prakash Bobde Department of Research and
Development, Energy Acres, University of
Petroleum and Energy Studies, Dehradun,
India
Somakraj Banerjee Chemical Engineering
Department, Jadavpur University, Kolkata,
India
Amarnath Bose Department of Health Safety
and Environment Engineering, University of
Petroleum and Energy Studies, Dehradun,
India
Piyali Basak School of Bio-Science and
Engineering, Jadavpur University, Kolkata,
India
Riccardo Campo Department of Civil and
Environmental Engineering, University of
Florence, Florence, Italy
Ajaya
Kumar
Behera Department
of
Chemistry, Utkal University, Bhubaneswar,
India
Sankha
Chakrabortty School
of
BioTechnology and Chemical Technology,
Kalinga Institute of Industrial Technology,
India
Chiranjib Bhattacharjee Chemical Engineering
Department, Jadavpur University, Kolkata,
India
Prasenjit
Chakraborty Agni
College
Technology, Thalambur, Chennai, India
Sangita Bhattacharjee Chemical Engineering
Department,
Heritage
Institute
of
Technology, Kolkata, India
of
Riddhi Chakraborty Chemical Engineering
Department, Jadavpur University, Kolkata,
India
Avijit Bhowal School of Advanced Studies on
Industrial Pollution Control Engineering,
Jadavpur
University,
Kolkata,
India;
Department of Chemical Engineering,
Jadavpur University, Kolkata, India
Vijayaraghavan M. Chariar Centre for Rural
Development
and
Technology,
Indian
Institute of Technology-Delhi, New Delhi,
India
xi
xii
List of contributors
University of Jeddah, Jeddah, Saudi Arabia;
Department of Microbial Biotechnology,
Genetic Engineering and Biotechnology
Research Institute, University of Sadat City,
Sadat City, Egypt
Dalel Daassi Department of Biology, College
of Sciences and Arts, Khulais, University of
Jeddah, Jeddah, Saudi Arabia
Praveen
Dahiya Amity
Institute
of
Biotechnology, Amity University Uttar
Pradesh, Noida, India
Mohit Kumar Das Environment Department,
Tata steel Ltd., India
Papita Das School of Advanced Studies on
Industrial Pollution Control Engineering,
Jadavpur
University,
Kolkata,
India;
Department
of Chemical
Engineering,
Jadavpur University, Kolkata, India
Ranjana
Das Chemical
Engineering
Department, Jadavpur University, Kolkata,
India
Ankit Dasgotra Department of Research and
Development,
School
of
Engineering,
University of Petroleum and Energy Studies,
Dehradun, India; Department of Mechanical
Energy, University of Petroleum and Energy
Studies, Energy Acres, Dehradun, India
Siddhartha Datta Department of Chemical
Engineering, Jadavpur University, Kolkata,
India
Trina Dutta Department of Chemistry, JIS
College of Engineering, Kalyani, India
Hamdy A. Hassan Department of Biological
Science, Faculty of Science and Humanity
Studies at Al-Quwayiyah, Shaqra University,
Al-Quwayiyah, Saudi Arabia; Department of
Environmental
Biotechnology,
Genetic
Engineering, and Biotechnology Research
Institute, University of Sadat City, Sadat City,
Egypt
Sankari Hazarika Department of Petroleum
Engineering and Earth Science, University of
Petroleum and Energy Studies, Dehradun,
India
Mervat H. Hussein Botany Department,
Faculty of Science, Mansoura University,
Mansoura, Egypt
Venkatalakshmi Jakka Department of Sciences
and Humanities, Vignan’s Foundation for
Science, Technology and Research (deemed to
be University), Guntur, India
Karun Kumar Jana School of Advanced
Studies on Industrial Pollution Control
Engineering, Jadavpur University, Kolkata,
India
Mostafa M. El-Sheekh Botany Department,
Faculty of Science, Tanta University,
Tanta, Egypt
Shipra Jha Amity Institute of Biotechnology,
Amity University Uttar Pradesh, Noida,
India
Preetha Ganguly Department of Biochemical
Engineering and Biotechnology, Indian
Institute of Technology Delhi, New Delhi,
India
Aastha
Jhunjhunwala Department
of
Chemical Engineering, National Institute of
Technology Durgapur, Durgapur, India
Sachin Rameshrao Geed Department of
Chemical Engineering, Indian Institute of
Technology (BHU), Varanasi, India
Arnab Ghosh School of Water Resource
Engineering, Jadavpur University, Kolkata,
India
Sougata Ghosh Department of Microbiology,
School of Science, RK University, Rajkot,
India
Ragaa A. Hamouda Department of Biology,
College of Sciences and Arts, Khulais,
Robin V. John Fernandes Department of
Health Safety, Environment and Civil
Engineering,
School
of
Engineering,
University of Petroleum and Energy Studies,
Dehradun, India
Tamanna
Khandelia Department
of
Chemistry, Indian Institute of Technology
Guwahati, Guwahati, India
Jin
Kuk Kim Department of Materials
Engineering and Convergence Technology,
Gyeongsang National University, Jinju, South
Korea
xiii
List of contributors
Bhupendra Koul School of Bioengineering and
Biosciences, Department of Biotechnology,
Lovely Professional University, Phagwara,
India
K.
Krishna
Koundinya Department
of
Electrical and Electronics Engineering,
University of Petroleum and Energy Studies,
Dehradun, India
Arunabha
Majumder School
of
Water
Resource Engineering, Jadavpur University,
Kolkata, India
Tamal Mandal Department of Chemical
Engineering, National Institute of Technology
Durgapur, Durgapur, India
Suvendu Manna Department of Health Safety
and Environment, University of Petroleum
and Energy Studies, India
Asis Mazumdar School of Water Resource
Engineering, Jadavpur University, Kolkata,
India
Shibam Mitra Envirotech
Kolkata, India
East
Pvt.
Ltd.,
Kaustubha Mohanty Department of Chemical
Engineering, Indian Institute of Technology
Guwahati, Guwahati, India
Sonali Mohanty Department of Biotechnology
& Medical Engineering, National Institute of
Technology Rourkela, Rourkela, India
Surajit Mondal Department of Electrical and
Electronics Engineering, University of
Petroleum and Energy Studies, Dehradun,
India
Kalisadhan
Mukherjee Department
of
Chemistry,
Pandit
Deendayal
Energy
University, India
Aniruddha Mukhopadhyay Department of
Environmental
Science,
University
of
Calcutta, Kolkata, India
Anil Kumar Nallajarla Department of Sciences
and Humanities, Vignan’s Foundation for
Science, Technology and Research (deemed
to be University), Guntur, India
Jayato
Nayak Department
of
Chemical
Engineering, School of Bio and Chemical
Engineering, Kalasalingam Academy of
Research and Education, India
Jitendra Kumar Pandey School of Basic and
Applied
Science,
Adamas
University,
Kolkata, India
Bhisma K. Patel Department of Chemistry,
Indian Institute of Technology Guwahati,
Guwahati, India
Ravi
Kumar
Patel UPES
Council
for
Innovation and Entrepreneurship, Energy
Acres, University of Petroleum and Energy
Studies, Dehradun, India
Uttarini Pathak Department of Chemical
Engineering, National Institute of Technology
Durgapur, Durgapur, India
Subhankar Paul Department of Biotechnology
& Medical Engineering, National Institute of
Technology Rourkela, Rourkela, India
Anand Prakash Department of Bioscience and
Biotechnology,
Banasthali
Vidyapith,
Banasthali, India
Y.
Sivaji Raghav CNPC BOHAI Drilling
Company
(BHDC),
Kuwait
City,
KuwaitCNPC BOHAI Drilling Company
(BHDC), Kuwait City, Kuwait
Md Azizur Rahman University Institute of
Engineering, Department of Biotechnology
Engineering
and
Food
Technology,
Chandigarh University, Ludhiana, India
Aakanksha Rajput Department of Bioscience
and Biotechnology, Banasthali Vidyapith,
Banasthali, India
Malabika Biswas
Kolkata, India
Roy
Women’s
College,
Pankaj Kumar Roy School of Water Resource
Engineering, Jadavpur University, Kolkata,
India; Faculty of Interdisciplinary Studies,
Law & Management, Jadavpur University,
Kolkata, India
Kulbhushan Samal Department of Chemical
Engineering,
Ramaiah
Institute
of
Technology, Bangalore, India
Rwiddhi Sarkhel Department of Chemical
Engineering, National Institute of Technology
Durgapur, Durgapur, India
Sonika Saxena Dr. B. Lal
Biotechnology, Jaipur, India
Institute
of
xiv
List of contributors
Shubhalakshmi
Sengupta Department
of
Sciences
and
Humanities,
Vignan’s
Foundation for Science, Technology and
Research (deemed to be University), Guntur,
India
Jasmine Sethi Entrepreneurship and Career
Hub, University of Rajasthan, Jaipur, India
Abhishek Sharma Department of Research
and Development, School of Engineering,
University of Petroleum and Energy Studies,
Dehradun, India
Harsh Sharma Department of Mechanical
Energy, University of Petroleum and Energy
Studies, Energy Acres, Dehradun, India
Poonam Singh Department of Chemistry,
University of Petroleum & Energy Studies
(UPES), Dehradun, India; School of
Engineering, University of Petroleum and
Energy Studies, Dehradun, India
Sneha
Singh Department
of
Chemical
Engineering, National Institute of Technology
Durgapur, Durgapur, India
Vishal
Kumar
Singh Department
of
Mechanical Energy, University of Petroleum
and
Energy
Studies,
Energy
Acres,
Dehradun, India; Department of Health
Safety, Environment and Civil Engineering,
School of Engineering, University of
Petroleum and Energy Studies, Dehradun,
India
Tridib Kumar Sinha Department of Materials
Engineering and Convergence Technology,
Gyeongsang National University, Jinju, South
Korea
J.
Sudharsan Doctoral Research Fellow,
Department of R&D, UPES, Dehradun, India
Devanshi Sutaria Dr. B. Lal Institute of
Biotechnology, Jaipur, India
S.M. Tauseef Centre for Interdisciplinary
Research and Innovation (CIDRI), UPES,
India and Sustainability Cluster, School of
Engineering, UPES, India
Ankita Thakur School of Bioengineering and
Biosciences, Department of Biotechnology,
Lovely Professional University, Phagwara,
India
Sunil
Kumar
Tiwari Department
of
Mechanical Energy, University of Petroleum
and
Energy
Studies,
Energy
Acres,
Dehradun, India; Department of Research
and Development, School of Engineering,
University of Petroleum and Energy Studies,
Dehradun, India
Akula
Umamaheswararao Department
of
Mechanical Energy, University of Petroleum
and
Energy
Studies,
Energy
Acres,
Dehradun, India
Shashi
Upadhyay Department
of
Microbiology, University of Petroleum and
Energy Studies, Energy Acres, Dehradun,
India
Thomas J. Webster Department of Chemical
Engineering,
Northeastern
University,
Boston, MA, United States
Zhang Xiaojie Department of Materials
Engineering and Convergence Technology,
Gyeongsang National University, Jinju, South
Korea; School of Material Science and
Engineering,
Nanchang
Hangkong
University, Nanchang, P.R. China
S E C T I O N
A
Overview on oil pollution and
its effect on environment
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C H A P T E R
1
An overview of oil pollution and
oil-spilling incidents
Sangita Bhattacharjee1 and Trina Dutta2
1
Chemical Engineering Department, Heritage Institute of Technology, Kolkata, India
2
Department of Chemistry, JIS College of Engineering, Kalyani, India
O U T L I N E
1.1 Introduction
3
1.5 Future predictions
12
1.2 Oil spill incidents
5
1.6 Summary
13
1.3 Case studies
6
References
13
1.4 Recovery and clean up
10
1.1 Introduction
The risk of accidental oil spill is associated with the transportation of crude petroleum
or petroleum derived oil from production sources to consumption locations. Spilled oil
causes severe damage to terrestrial as well as marine ecosystems and also loss to human
society. Though the occurrences of major oil spills are occasional, these lead to obvious
environmental damage and hence receive considerable public attention.
The most significant variables those affect the dispersal and residence time of the contaminants following oil spillage in marine environment are the prevailing hydrodynamic
conditions and location of spillage. The wave exposure and prevailing tides and currents
during spillage affect the dispersal of oil spilt. With increasing wave exposure, the availability of mechanical mixing energy required for natural dispersal of oil increases.
Increased wave exposure also increases the effectiveness of chemical dispersants (Carls
et al., 2001; Owens, Robson, & Foget, 1987).
Advances in Oil-Water Separation
DOI: https://doi.org/10.1016/B978-0-323-89978-9.00014-8
3
© 2022 Elsevier Inc. All rights reserved.
4
1. An overview of oil pollution and oil-spilling incidents
Depending upon timing and duration of oil spill, the effects of oil pollution can be
divided into acute impact for a short duration or impact for prolonged period. The impact
also depends on the number and types of organisms affected. Oil spills become an immediate source of fire hazards. Organisms get continuously exposed to different components
of oil when small amounts of oil are released into sea water over long periods. These can
contaminate drinking water supplies and thus may cause waterborne diseases. Point
sources including leaking pipelines, natural seepages, production discharges at offshore,
and nonpoint runoff from various facilities based on lands are the sources of chronic exposures. In most of the cases, there exists a strong gradient of oil concentration against
distance. In the case of oil spillage from a nonpoint source for example, with land-based
run-off and natural input, weak concentration gradients of oil compounds are found in the
environment.
More so often spilled oil gets incorporated into sediments and due to this weathering of
oil is retarded. This causes a release of nearlyfresh oil to the water body for a prolonged
period. Currently the prolonged impacts of acute and chronic contamination are receiving
increased attention (https://www.ncbi.nlm.nih.gov/books/NBK220710/).
The extent and severity of damage on the environment following crude oil spillage
varies on the particular properties of the crude oil and the type of surrounding. Owing
to easy absorption, these light oils act at the cellular level and cause immediate toxicity
to the plants. Plants experience asphyxia as well as hindrance to gaseous exchange after
getting covered by heavy oils (Pezeshki, Hester, Lin, & Nyman, 2000). In case of oil spillage in terrestrial environment, the ecosystem gets affected due to contamination of soil;
in aquatic surroundings, in the littoral zone, the wind and wave action disperse floating
oil on the surface of water, which affects the shoreline environment and vegetation
(Pezeshki et al., 2000).
Among vegetation, mangroves are highly vulnerable to oil spills. These salt-tolerant trees
and shrubs breed in muddy anaerobic sediments. These plants take air through tiny pores on
aerial roots. Mangroves in those areas may die due to lack of oxygen supply owing to heavy
oil inundation of the root systems. However, in open aerated sediments, the toxic components
mostly the light refined products of oil, interfere with the plants’ salt balance maintenance system and thus significantly affect their tolerance toward salt water (https://www.itopf.org/
knowledge-resources/documents-guides/document/tip-13-effects-of-oil-pollution-on-the-marineenvironment/#:B:text 5 Oil%20spills%20can%20seriously%20affect,their%20habitats%20to
%20the%20oil).
Some biological traits such as habitat/depth of the species make them more prone to be
exposed to oil compared to other species; Species with canopies such as kelp and seagrass
reach the water surface. Generally, as spilled oil floats along the surface of the water, most
subtidal species are likely to get much less exposure to oil.
In general, animals and plants are affected by oil spill either directly from the spilled
oil or during cleanup operations. Owing to the presence of poisonous chemicals, spilled
oil can be harmful to living things. Organisms become internally exposed to oil either by
ingestion or inhalation, externally exposed via skin and eye. Following spillage, small
species of fish or invertebrates get damped by oil, oil can coat feathers and fur of birds.
All these lower the natural ability of birds’ and mammals’ to maintain their body
temperatures.
A. Overview on oil pollution and its effect on environment
1.2 Oil spill incidents
5
There are certain sea animals as well as birds those need to traverse air-water interface
intermittently to respire and hence make themselves more vulnerable to oil exposure
(Peterson et al., 2003). However pelagic fish species, due to their habitat, remain minimally
exposed to spilled oil (Paine et al., 1996). During oil spill disasters the intertidal zone
experiences the greatest exposure as the species are brought in direct contact with the oil
during regular rising and falling of tides,. Cetaceans such as whales, dolphins etc. get
affected when they come to surface for breathing purpose. The floating oil may cause
harm to their eyes and nasal tissues. Marine mammals like seals, otters, etc. are more
prone to get damaged by floating oil as they spend time on shore.
Sea birds such as sea ducks, alcids, etc. are severely affected by oil spills. The spilled
area becomes uninhabitable for many bird species as their sources of food such as fishes
are killed off. As their plumage gets coated, the alignment of feathers gets damaged and
can provide neither waterproofing nor thermal insulation. The birds may die due to hypothermia or overheating depending upon the season as their fur matted with oil. Besides
being smothered by oil the natural buoyancy gets lost and these species ultimately end up
their lives into watery grave. The birds while trying to clean themselves by preening out
of natural instinct, take in the sticky, toxic petroleum hydrocarbons, which damage their
internal organs including lungs, livers, and intestines.
Oil spillage may have severe effect on human health and society. Inhalation of crude oil
vapor or ingestion of contaminated seafood may cause immediate effects including dizziness, nausea to long term effects such as development of cancers or ailment of central nervous system (Davidson, Phalen, & Solomon, 2005; Major & Wang, 2012).
The tourism industry can be negatively impacted as oil spills cause harm to beaches
and waterfront properties. The media coverage on oil spilling incidents causes much
reduced trade activities and disruption of activities including swimming, boating, diving
angling, etc. United States Department of Commerce (1983; Oxford Economics, 2010).
Other subsectors of tourism such as accommodations, transportation, guides, and activities also experience economical loss (McDowell Group, 1990; United States Department
of Commerce, 1983). Shopping outlets and eateries catering to the tourism industry suffers substantial economic losses (Loureiro, Ribas, López, & Ojea, 2005; United States
Department of Commerce, 1983).
1.2 Oil spill incidents
Petroleum has been used by humans for a few thousand years. However the use of
petroleum and its refined products had surged after industrial revolution. Due to various
reasons including old and worn out equipment, manmade error and bad fortune, incidents
of oil spillage occurred over years during extraction oil from underground and transportation it to petroleum refineries or other destinations.
A detailed study of oil spilling incidents would reveal that a major fraction of the oil
split had resulted from a few very large oil spills. In the 1990s there were 358 oil spilling
incidents, each causing spillage of 7 tons or higher, which resulted in an oil loss of
1.134 3 106 tons. Only ten of such oil spilling incidents caused loss of about 73% of the
total quantity of oil lost. In the 2000s, 181 oil spills each with spillage of 7 tons or higher
A. Overview on oil pollution and its effect on environment
6
1. An overview of oil pollution and oil-spilling incidents
were reported, causing a cumulative loss of 1.96 3 105 tons. Only 10 incidents are to be
blamed for 75% of the total oil lost in 2000s.
In the last decade, a loss of 1.64 3 105 tons of oil was reported, the loss had arisen from
a number of oil spilling incidents out of which there have been 62 spills of 7 tons and
over, 91% of the total quantity was lost only in ten incidents. About 70% of the total
spilled quantity occurred only in one incident (https://www.itopf.org/knowledgeresources/data-statistics/statistics/).
A single large incident of oil spillage in a particular year may significantly change the
figures with respect to the total volume of spillage. This can be witnessed by considering
incidents such as Atlantic Empress, in 1979, causing oil spillage of 2.87 3 105 tons; Castillo
De Bellver, in 1983, 2.52 3 105 tons spillage; ABT Summer in 1991, 2.60 3 105 tons spillage
(https://www.itopf.org/knowledge-resources/data-statistics/statistics/) etc.
Tens of millions of gallons of oil have been released into the marine environment in
largest oil spills which caused pollution of fisheries, fouling of coastlines, death and
injury of wildlife, and loss of tourism revenue (https://www.britannica.com/list/9-ofthe-biggest-oil-spills-in-history; How BP’s Blowout Ranks among Top 5 Oil Spills in 1
Graphic, 2015).
Accidents of tanker ships carrying crude oil and refined fuel have severely affected vulnerable ecosystems in various parts of the Earth. Smaller spills even sometimes cause a
severe impact on ecosystems as the remote location of the site may hamper the emergency
environmental response required to protect the surrounding ecosystem.
Following spill at sea, oil forms a thin oil slick which can spread over about few hundreds nautical miles, hence the spillages are more disastrous for the sea than those on
land. The beaches are generally covered by a thin oil coating by the oil slick. In the case
of spillage on land, the oil can be effectively contained by construction of a makeshift
earthen dam. This can effectively prevent the land animals from the undesirable, toxic
exposure of oil.
The Indian coast is also vulnerable to oil spilling incidents. On January 27, 2018, an
oil spill took place on the outer Kamarajar Port in Ennore near Chennai in TamilNadu,
India (The Hindu, 2017). On the day of the accident, a tanker BW Maple suddenly
made a collision with an inbound tanker namely Dawn Kanchipuram. In 2010,
Mumbai oil spill happened when the outbound ship MV MSC Chitra from Nava Seva
port of south Mumbai collided off with the inbound KhalijaIII. Due to this incident
about 200 cargo containers were thrown into the Arabian Sea (https://en.wikipedia.
org/wiki/2010_Mumbai_oil_spill).
1.3 Case studies
Oil spilling incidents are severe environmental catastrophes, which often lead to significant, continuing impacts on the surrounding, ecology, and socioeconomic activities of the
affected area. The major oil spilling incidents are summarized in Table 1.1.
The most disastrous, inadvertent oil spill was caused by an explosion on the Deepwater
Horizon oil rig. The incident took place following a gush of natural gas occurred through
a newly installed cement wall cap, built to seal a drilled oil well. Due to the explosion,
A. Overview on oil pollution and its effect on environment
7
1.3 Case studies
TABLE 1.1 Major oil-spilling incidents.
Month & year of
occurrence
Name of vessel/
platform/incident
Location
References
March, 1910
Lakeview Well
California, USA
https://www.idealresponse.co.uk/blog/
the-10-biggest-oil-spills-in-history/
March, 1978
The Amoco Cadiz,
Brittany, France
https://www.britannica.com/list/9-ofthe-biggest-oil-spills-in-history
June 1979- March,
1980
The Ixtoc 1
Bay of Campeche
https://www.britannica.com/list/9-ofthe-biggest-oil-spills-in-history
July, 1979
Atlantic Empress
Trinidad and Tobago
islands in Atlantic Ocean
https://www.britannica.com/list/9-ofthe-biggest-oil-spills-in-history
February, 1983
Nowruz oil field
https://www.britannica.com/list/9-ofthe-biggest-oil-spills-in-history
August, 1983
Castillo de Bellver
Cape Town, South Africa
https://www.britannica.com/list/9-ofthe-biggest-oil-spills-in-history
March, 1989
Exxon Valdez
Alaska, USA
https://www.idealresponse.co.uk/blog/
the-10-biggest-oil-spills-in-history/
JanuaryFebruary,
1991
Persian Gulf war
Northern Persian Gulf
near Kuwait
https://www.britannica.com/list/9-ofthe-biggest-oil-spills-in-history
April, 1991
Motor Tanker
Haven
Genoa, Italy
https://www.idealresponse.co.uk/blog/
the-10-biggest-oil-spills-in-history/
March, 1992
The Mingbulak oil
spill
Fergana valley,
Uzbekistan
https://www.britannica.com/list/9-ofthe-biggest-oil-spills-in-history
1994
Kolva river spill
Russian Arctic
https://www.britannica.com/list/9-ofthe-biggest-oil-spills-in-history
2010
Deepwater
Horizon oil
platform
Gulf of Mexico
https://www.britannica.com/list/9-ofthe-biggest-oil-spills-in-history
huge volumes of oil spilt into the gulf of Mexico resulting in very adverse damage to the
marine environment and ecology. This incident took 11 human lives and caused injury to
17 people. Approximately 1100 miles of coastline and thousands of animals including sea
turtles, mammals, and birds were killed. Among endangered species, brown pelicans, and
Kemp’s ridley sea turtles (critically endangered) were included. According to some studies
conducted in 2014, almost 65,000 turtles were found dead and about 800,000 birds were
thought to have died due to the catastrophic oil spill (https://www.idealresponse.co.uk/
blog/the-10-biggest-oil-spills-in-history/). After this incident, oil, and soot persistently
rained down on seafloor for months.
In 1910, a massive disaster related to oil spill occurred when the Lakeview well of
California, USA erupted releasing huge geyser of crude oil continuously spilling almost
40,00050,000 barrels/day. In spite the workers’ effort to contain the flow of oil, it continued to spill over. Finally, after elapse of 18 months the leak got sealed as the oil caved in
A. Overview on oil pollution and its effect on environment
8
1. An overview of oil pollution and oil-spilling incidents
on itself. Over 378 million crude oil was lost, however the adverse effect on environment
was significantly reduced due to the work carried out by the workers and volunteers.
Workers built dikes to prevent the oil to contaminate the Buena Vista lake, most of the
spilled oil got evaporated or got soaked into the soil (https://www.idealresponse.co.uk/
blog/the-10-biggest-oil-spills-in-history/).
One of the largest oil spill occurred when on March 16, 1978, a very large crude carrier
Amoco Cadiz, stocked with approximately 69 3 106 gallons of lighter crude, suddenly
touched the ground below water on shallow rocks off the coast of Brittany, France. As the
ship was steering through the rough seas of the English Channel, a large wave broke its
rudder and hydraulic system. Inclement weather hampered the rescue operation. Despite
all efforts, the vessel broke by the afternoon of March 17th, following that, the oil slicks
quickly reached the coast. Unfavorable weather conditions, such as strong breeze and heavy seas, disturbed cleanup operations, causing contamination of some of the channel
islands. This was the worst and largest oil spill from a tanker until that time and caused
severe harm to marine ecosystem. Two weeks after the accident, numerous sea urchins,
dead mollusks, and various benthic species were washed toward the shore. This spill
adversely affected oyster cultivation. About 9000 tons of oysters were destroyed in order
to protect market confidence. From some regions, small crustacean and echinoderm species were almost totally vanished, however fortunately many other species were found to
be recovered within a year. Approximately 20,000 dead birds were recovered, most of
them were diving birds. Amoco Corporation, in 1990, decided to pay $120 3 106 to French
claimants, also another compensation amounting to about $35 million towards Royal
Dutch Shell against lost oil was agreed upon by Amoco Corporation (https://en.wikipedia.org/wiki/2010_Mumbai_oil_spill).
During the month of June, 1979, an occurrence of oil spillage from Ixtoc oil well took
place in the Mexican gulf. This accident released up to 140 3 106 gallons of crude oil into
the Bay of Campeche till March 1980. An explosion followed by oil spill occurred when
drilling of exploration wells was taking place at a depth of about 50 m below water surface. The explosion started with an accumulation of oil and gas in pipe due to failure of
circulation of drilling mud. This incident ultimately ruined the rig followed by sinking of
the same. Initially approximately 30 3 103 barrels of oil/day was leaking. Rigorous efforts
were made to reduce the flow and by August, 1979, the flow was reduced to about 10,000
barrels per day. It was reported by Pemex that about 50% of oil spilt got burnt upon reaching the surface, about one third of original spilled oil evaporated, and the remaining was
contained or dispersed in the gulf of Mexico.
In July 1979, another big oil spill known as Atlantic Empress oil spill occurred when
collision took place between two fully loaded very large crude carriers-Atlantic Empress
and Aegean Captain, during rainstorm while navigating in the Caribbean Sea. Leaking
of oil started from the vessels after the collision. An estimated 88.3 million gallons oil
spill took place. Fire broke in both the vessels and 27 crew members died. Though most
of the crude oil was burnt in the fire, an oil slick of 30 miles by 60 miles was found.
Though huge volume of oil spilt during the accident, very small environmental damage
was observed to the beaches on nearby islands; as most of the oil was pushed out to sea.
The VLCC Atlantic Empress, after burning for two weeks, finally sank in the sea on
August 3, 1979.
A. Overview on oil pollution and its effect on environment
1.3 Case studies
9
On August 6, 1983, another major and disastrous oil spill took place at Saldanha bay,
South Africa when Castillo de Bellver, a Spanish tanker was caught fire on board which
resulted in the explosion and burning of the ship. The crew members left the ship, the
ship subsequently got broken down dumping an estimated 78.5 million gallons into the
South Atlantic ocean. An oil slick of approximately 20 miles long was formed. The spill
could have created a major environmental danger by causing destruction to the seabirds
rookeries and damaging productive fisheries. But as the strong wind blew the oil out to
sea rather than shore, much less environmental impact could be prevented. However,
more than 1500 seabirds got either injured or killed due to this spill (https://www.idealresponse.co.uk/blog/the-10-biggest-oil-spills-in-history/).
Several incidents of oil spill occurred in the Nowruz oil field in the Persian Gulf. During
early 1980s, the northern Persian Gulf had become a contested zone of as part of the Iran-Iraq
War. In one such contest an oil spill incident took place when one Iraqi helicopter attacked a
local platform of the same oil-field in March, 1983. Initially one platform above the oilfield
was hit by a tanker on February, 10, 1983. In March, 1983 when Iraqi helicopters charge the
platform, the spill caught fire. Due to the IranIraq war, the technicians could not be able to
carry out the capping operation of the well until 18 September 1983. Ultimately capping was
done with cement (“Nowruz—Cedre,” 2016; Ottaway, 1983). The lives of eleven people were
lost during the operation. Up to September 1983, each day after the spill, the well leaked
about 1500 barrels of oil in Persian Gulf. As a result, about 733,000 barrels of oil got spilled
from this platform until Iran’s capping and repair operation could get completed by May,
1983. Nine people had died during capping operation as they had to work under the fire
from the Iraqis. The Norwuz oil field incidents in 1983 caused a total spill of over 80 million
gallons of oil (https://www.britannica.com/list/9-of-the-biggest-oil-spills-in-history).
The Gulf War oil spill, arising due to the Gulf War in 1991 was recorded as one of the largest
oil spilling incident in history. The war was initiated by the aggression and invasion of Iraq
under leadership of Saddam Hussein against the oil rich country Kuwait. The Persian Gulf War
started by allied coalition with a massive United States-led air offensive known as Operation
Desert Storm when Hussein defied United Nations Security Council demands to withdraw
from Kuwait by mid-January 1991. As a strategy, the Iraqi troops deliberately open valves at
the Sea Island oil terminal in Kuwait and discharged oil from few tankers into the Persian Gulf
with an objective to prevent potential landing by United States Marines. An estimated 240336
million gallons of oil have spilled in this incident. Following the spill, an oil slick of 160 km was
observed, the thickness of the same was up to 13 cm. in some areas. This oil spill caused detrimental effect of surroundings and local marine ecosystems. It is evident from some study conducted after 10 years of this incident, that the ecosystem of salt marshes was still far from
complete recovery. Some centuries will certainly be needed for full recovery of the salt marshes.
On April, 11, 1991 a major explosion followed by spillage of oil occurred when MT
Haven had been unloading a huge cargo carrying oil at the Multedo oil platform adjacent
to Genoa of Italy. Five crew members were died from the violent fire resulted from the
explosion. The motor tanker finally sank into the Mediterranean sea after burning continuously for three days, spilling an approximate quantity of 45 3 106 gallons of crude into seawater. The Italian authority significantly limited the scale of disaster by carrying out large
cleanup operation. However, the environmental damage due to pollution seriously
affected the fisheries along both the French and Italian coast.
A. Overview on oil pollution and its effect on environment
10
1. An overview of oil pollution and oil-spilling incidents
1.4 Recovery and clean up
Clean-up of oil spills from the marine environment is a challenging task. After the
oil spill phenomena, the discharged petroleum hydrocarbons may be transported, may
be dispersed in the water or distributed in form of surface slick. The submerged part of
hydrocarbons can also be accumulated in the sediments (Liu, Wang, Zou, Wei, & Tong,
2012; Reddy et al., 2002).The characteristics of spilled oil changed owing to weathering
processes like evaporation, dissolution, dispersion, photo-oxidation and microbial degradation. Due to evaporation of light hydrocarbons, the density and viscosity of spilled
oil increases in marine environment (Hussein, Amer, & Sawsan, 2009; Karana,
Rengasamy, & Das, 2011).
There are different clean-up strategies from shorelines, water, and sediments. For oil
spills disaster management first step is very crucial to contain oil spills immediately to
keep down the damage on human health, marine ecosystem and natural resources. So in
oil spill clean-up, first critical step is containment which is followed by recovery.
Booms are used as containment equipment to restrict spread of oil spills to shoreline
and other resources as soon as possible, to protect the environment and assist in recovery.
Booms concentrate oil on surface and channelize for recovery and dispersal. These are
basically floating barriers either fixed structure or towed behind or alongside the vessel.
These are designed to have four basic features: (1) “Freeboard” above the water surface,
(2) “Floating device,” (3) “Skirt” below the water surface and (4) “Longitudinal support”
at the bottom of the skirt (USEPA archive document).
In situ burning can remove thick oil layers above the water surface. Its hourly cleaning
capacity is around 100300 tons (Asadpour et al., 2013). This technique should be done
very quickly before remarkable evaporation takes place and minimum 23 mm of oil spill
thickness is required for better efficacy.
The recovery based oil spill treatment are broadly categorized as physical, chemical,
and biological techniques (EPA, 2017). For recovery using physical technique, skimmers
are used. These can recover oil films from the water surface. Skimmers may be selfpropelled, can be operated from vessels or shore. The floating oil spills above the dam and
trapped inside a well, carrying least amount of water. The oil recovery can be enhanced
with meshes made up of water repelling materials which keep away water and permit
more oil to cross through it. Three types of skimmers are available. In case of “Weir” skimmers, the enclosure is used to trap oil from oil- water interface. It recovers fluids at a fast
rate, but prone to clog by the debris floating in the water. In case of oleophilic skimmers,
the oil is scrapped using disks, belts, or continuous mop chains manufactured from oleophilic materials. It is efficient to attract oil and flexible on spill irrespective of its thickness.
The “suction” skimmers runs similar with a vacuum cleaner used for household purpose.
It is highly efficient, but vulnerable to chocking by debris and requires continuous maintenance (USEPA archive document; https://www.bsee.gov/site-page/mechanical-containment-and-recovery).
Sorbents are used to recover small-scale oil spills either by the mechanism of
absorption or adsorption. It is used to remove final trace of oil after collection from
skimmer or from the areas inaccessible by skimmers very efficiently. For oil recovery,
sorbent should be oleophilic and hydrophobic both. Hydrophobicity prevents water
A. Overview on oil pollution and its effect on environment
1.4 Recovery and clean up
11
sorption and increases oil recovery yield. During the selection of sorbent, the characteristics like rate of absorption, oil retention and ease of application need to be considered. Whenever the sorbents are used, these require proper disposal or can be
recycled.
There are different types of sorbents. Natural organics sorbents are cheaper, abundant
and eco-friendly. They soak up three to fifteen times of the weight of sorbents in oil but
sometimes also absorb water. The examples of organic sorbents are rice straw, peat moss,
hay, wood fiber, wool fiber, fibers from kapok and kenaf etc. Other examples are cotton,
rice husk, bagasse, sawdust, ground corncobs, feathers, and other carbon-based products.
Collection is a difficult task as few materials may sink after water absorption or dust particle may spread on water surface. The flotation device aids collection and the problem of
sinking is resolved.
Naturally available inorganic adsorbents are wool, sand, clay, perlite and vermiculite. They absorb oil ranging from four to twenty times of the weight of sorbents.
These are also cheap and abundantly available. The synthetically produced sorbents
like polyurethane, polyethylene, and nylon fibers etc. have high absorption capacity,
seventy times of the weight of sorbents in oil. Sorbents cleaning is easy process and
these can be used multiple times. But disposal is a major issue (USEPA archive
document).
In comparison among different sorbents, the cheaper, biodegradable biomass like cattail
fiber, kapok fiber, bagasse, Salvinia sp., rice husk, woodchip, coconut husk have 70%
greater removal efficiency than synthetic polymer-based fiber sorbents due to enough void
spaces in surface structure and hydrophobicity (Khan, Virojnagud, & Ratpukdi, 2004).
Different treatment methods can enhance the sorption capacity. The pyrolysis of rice
husk increases adsorption capacity by breaking bonds in organic materials and silicon.
The white ash obtained from pyrolysis of rice husk adsorb diesel 5.02 g/g (Vlaev, Petkov,
Dimitrov, & Genieva, 2011). Alkaline treatment of rice husk removes silica.
Waste from Silkworm cocoon can remove 30% more motor oil as well as vegetable oil
compared to natural wool fibers. The adsorption capacity is 42 to 52 (g/g) (51%) in case of
motor oil and 37 to 60 (g/g) (54%) in the case of vegetable oil (Moriwaki et al., 2009).
Banana peel along with Orange peel waste enriched with cellulose removes heavy oil
more efficiently than lighter oil. Hybridized peels waste adsorbs 38% lubricant oil, 32%
petrol oil but only 0.58 g/g of vegetable oil (Abdullah et al., 2016). Luffa, one of the microporous agricultural wastes adsorb .85% diesel oil after treatment (Abdelwahab, 2014) and
become a part for waste management.
There are different particles like chitosan flakes, cellulose nanofibril and polyvinyl alcohol based aerogel microspheres show excellent absorption efficiencies in case of floating
oil clean-up (Barros, Vasconcellos, Carvalho, & Ferreira do Nascimento, 2014; Zhai, Zeng,
Cai, Zia, & Gong, 2016).
Currently the blending of nanoparticles and polymer-based materials are getting importance for better surface property, reusability, biodegradability, and simple recovery
(Fouad, Aljohani, & Shoueir, 2016). The Nanofibers acquired by blending electro-spinning
process from polystyrene and polyvinyl chloride have five to nine times higher sorption
capacity compared to commercial polypropylene. The comparison studied in case of peanut oil, diesel oil and motor oils (Zhu et al., 2011) (Fig. 1.1).
A. Overview on oil pollution and its effect on environment
12
1. An overview of oil pollution and oil-spilling incidents
FIGURE 1.1 Oil recovery and clean-up.
Nowadays, the external magnetic field is being used for oil separation. Magnetic nanoparticles coated quaternized chitosan reported as excellent oil-water separator at different
pH values (Zhang et al., 2017).
For open and deep-water oil spills, the dispersants, making up surfactant, the amphiphilic
surface-active molecules are sprayed on the oil spills and breaks into smaller droplet size of
,100 μm (NOAA, 2017b). Dispersants reduce the tension of oil-water interface, also reduce coalescence with formation of stable micro-emulsions. In addition, the dispersants increase surface
to volume ratio which helps in further treatment like bioremediation. Dioctyl sodium sulfosuccinate, one of the anionic surfactants used in dispersants named Corexit 9527 and Corexit 9500A
during response the Deepwater Horizon oil spill (Belore, Trudel, Mullin, & Guarino, 2009).
In recent trend the green surfactants or herders are getting focus as the existing chemicals are non-biodegradable and stable to stay for long time in marine environment and
create toxicity effect (Place et al., 2016).
The dispersants/chemicals are non-biodegradable, remains in the marine environment for
long years and create further pollution. To resolve this issue the biopolymer based low-cost
sorbents, different advanced materials like aerogels, inorganic meshes, foam membranes, and
surface modified fabrics are getting more weightage for oil separation in the recent years.
In case of bioremediation, the microorganisms and green plants are used to degrade
hydrocarbons. The toxic heavy metals, and volatile organic compounds present within fossil fuels are also sequestered in this process. It is less labor-intensive, also avoids chemical
or mechanical damage. It is a green way of oil spills treatment.
1.5 Future predictions
Future unintentional oil spilling incidents may be prevented by adopting various methods including deployment of trained and experienced crew members, by ensuring strict
A. Overview on oil pollution and its effect on environment
References
13
fire safety regulation on board, limiting the size of individual tanks in ship to ensure smaller spill, by using vessel traffic control in congested areas to reduce risk of collision.
Unintentional oil spilling incidences may also be avoided by ensuring proper mechanical
maintenance of vessel including tightening of bolts which may become loose with shaking
during engine use, by changing damaged hydraulic lines and fittings prior to mechanical
failure. Care must be undertaken during fueling of tank at pump to avoid overflow and
also to leave some room for fuel expansion.
Considering the harmful impact of oil spilt on marine ecosystem, on coastlines and seafloors as well as on environment, preventive measures are to be keenly adopted to minimize future oil spilling incidents. Oil wells are to be carefully designed and maintained.
Care is to be taken while carrying out various phases of work for example, drilling operation, production followed by workover and lastly abandonment.
Impact on human particularly the social and economic harm of the spillage are to be
properly identified. Practice of prevention of offshore oil spill and response lowers frequency of oil spilling incidents at offshore and this practice also reduces the quantity of
spilled oil. In the United States, prevention contingency plans for offshore oil spilling and
emergency response plans are federally mandated requirements, for all offshore oil facilities in United States In many countries, various International treaties take actions towards
prevention of pollution from ships by implementing mandatory control, recording, and
punishments for oil spillage from ships (American Petroleum Institute, 2010).
1.6 Summary
Key variables that have influences on the severity of the consequences of oil spill are to
be found out and their interactions are to be clearly defined. That framework can then be
effectively utilized to understand the impact of oil spilling incidents, to identify lessons
those can be transferable from other oil spills, can be used to plan properly, and perform
risk analysis and policy debates with objectives to develop understanding so as to lower
their vulnerability to oil spill catastrophe.
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C H A P T E R
2
Spatiotemporal distribution of oil spill
effect in the estuarine terrain of
Bhagirathi-Hooghly River, West
Bengal, India
Pankaj Kumar Roy1,2, Arnab Ghosh1, Malabika Biswas Roy3,
Arunabha Majumder1, Asis Mazumdar1 and Siddhartha Datta4
1
School of Water Resource Engineering, Jadavpur University, Kolkata, India 2Faculty of
Interdisciplinary Studies, Law & Management, Jadavpur University, Kolkata, India 3Women’s
College, Kolkata, India 4Department of Chemical Engineering, Jadavpur University, Kolkata, India
O U T L I N E
2.1 Introduction
18
2.2 Materials and methods
2.2.1 Study area
2.2.2 Data used
22
22
22
2.4.2 Spatiotemporal analysis of dissolved
heavy metal parameter
33
2.4.3 Changes in the parameter
effecting oil spill
41
2.5 Dissolved heavy metal indices
42
2.5.1 Enrichment factor
42
2.5.2 Contamination factor
43
2.5.3 Pollution load index and degree of
contamination
43
2.5.4 Geo accumulation index
44
2.5.5 Changes in heavy metal indices
45
2.5.6 Quantitative variation with
increased oil spill
45
2.5.7 Ecological impacts through BOPA
index
47
2.3 Methodology
24
2.3.1 Spatiotemporal analysis in water
quality and heavy metal
concentration
24
2.3.2 Heavy metal indices analysis
24
2.3.3 Ecological impact through BOPA
index
26
2.4 Result and discussions
2.4.1 Spatiotemporal analysis of water
quality parameter
Advances in Oil-Water Separation
DOI: https://doi.org/10.1016/B978-0-323-89978-9.00002-1
26
26
17
© 2022 Elsevier Inc. All rights reserved.
18
2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India
2.6 Conclusion and recommendation
48
Acknowledgment
50
References
50
2.1 Introduction
Oil spill is usually called the leaking process of crude natural liquid petroleum with
hydro carbon from a ship, fishing boat or vessel and mixed with the water of sea, river and
estuary portion (Chen, Ye, Zhang, Jing, & Lee, 2019; Wang et al., 2011). Organic compounds
derived from the thousand organic materials have long been converted beneath the soil surface by pressure, heat, and chemical reactions to form a complex mixture of crude mineral
oil. In addition to hydrogen and carbon, crude oil contains small amounts of metals such as
sulfur, oxygen, nitrogen and nickel, iron, and vanadium (Onwurah, Ogugua, Onyike,
Ochonogor, & Otitoju, 2007). When this unrefined oil is refined, these compounds retain
their properties and functions, even if they are no longer there. When crude oil comes out of
large ships or vessels it pollutes the environment, while various fishing vessels or trawlers
accidentally throw refined oil into the water and pollute the environment. Until World War
II (Campbell, Ed, & Dean, 1942), sea or water transport was dependent on coal. But since
then, the use of mineral oil in water transport has been steadily increasing, and with it also
the level of water pollution. Not only vehicles, but also various oil rigs, offshore platforms,
from the crude oil extraction sites, crude oil leaks into the sea and pollutes the ocean environment. It can be said that human actions are entirely responsible for oil spills. Also, oil
spills are often seen in ports for fishing and conservation (Mirajkar, Shinde, Sini, Nikam, &
Verma, 2019). About 5 million tons of crude oil is exported to various countries by sea every
year. During these exports, oil spills occur mainly due to technical problems, human nuisance, and carelessness. Oil spills also occur when the oil drilling machinery fails due to
human error, carelessness, intentional actions or errors, or natural disasters or marine accidents, especially in the case of refineries or tankers carrying any type of petroleum product
(Ishak, Md Arof, & Zoolfakar, 2020; Nelson & Grubesic, 2017). Spillage from refineries,
dams, tankers, storage facilities and pipelines usually release vast quantities of oil into the
water body and inland areas when such activities occur. The oil floats on the water and
spreads rapidly over the water surface, which forms a thin layer (Bender, Shearls, Murray,
& Huggett, 1980; Singh, Bhardwaj, Arya, & Khatri, 2020; Teal & Howarth, 1984). If the oil
begins to disperse across the water surface, the thin coating, also referred to as an oil slick,
becomes thinner and thinner. Eventually, with the appearance of a rainbow, which is often
referred to as sheen, the oil slick becomes a very thin layer. The oil forms a very dense coating on the water surface as it spreads out in situations where there is spillage of large quantities of oil (Ivshina et al., 2015; Reed, Aamo, & Daling, 1995; Board, Board, & Council, 2003;
Onwurah et al., 2007).
Oil spills directly harm the marine animal and plant world and indirectly the human
environment, health and economy (Ansari & Matondkar, 2014). The harmful effects of oil
spills and ways to get rid of them have been discussed in various works before. Oil spills
have the potential to destroy marine habitat, ecosystems (Camus & Smit, 2019) and
A. Overview on oil pollution and its effect on environment
2.1 Introduction
19
accompanying human activities. Since crude oil is made up of a combination of various
toxic hydrocarbons, marine fauna is easily destroyed. Oil spills have a detrimental effect
on various coastal activities and are gradually affecting the various resources of the river
estuarine ecosystem (Murphy & Riley, 1962; Prat et al., 1999). In most cases, crude oil
causes temporary damage, which can lead to future disasters. Different effects on the environment of coastal and estuary areas are seen based on the toxicity of different chemical
components of crude oil (Alexander & Webb, 1987; Baker, 1983; Beeby, 1993; Board et al.,
2003; Gundlach & Hayes, 1978). Various elements of the ecosystem in coastal and estuarine regions are damaged by the physical nature or chemical composition of crude oil.
Plants or animals that come in contact with crude oil during this time become endangered
within a few days or immediately. The entire mammal world, including birds and fish,
are affected by this oil spill. Fish gills and bird feathers, if saturated with oil, normally die.
Owing also to the presence of lethal concentrations of toxic components in oil; at the
spilled site, large-scale marine life mortalities are expected. Due to ingestion of oil polluted
food from the river bed, biological resources on the shallow areas of the BhagirathiHooghly River as well as other benthos that feed on living resources present in the bed of
the river ecosystem are impacted. The digestive system of sedentary animals within river
ecosystem may also get affected due to the consumption of oil contaminated food
(Al-majed, Adebayo, & Hossain, 2012; Almeda, Hyatt, & Buskey, 2014; Berry, Dabrowski,
& Lyons, 2012; Zenetos et al., 2004). Those animals either die due to ingestion of toxic oils
present or if survive, get contaminated with oil. Bioaccumulations of oily compounds
are common in organisms that survive in such oil contaminated environment. The
bio-accumulation of toxic components of the oil are common in different trophic levels of
ecosystem through food chain and food web and can reach the highest trophic levels of
ecosystem including human being. Thus, human beings are affected by toxic properties
of oil by consuming oil contaminated fish (Banerjee, Joshi, & Jayaram, 2006; Bejarano &
Michel, 2010; Je˛drzejczak, 2002). Thus, oil pollution can occur from industrial waste, blow
out, collision, stranding, human failure, failure of equipment’s, or from any other possible
marine accidents which can threaten human and other marine lives in the tidal & intertidal
zones (Beyer, Trannum, Bakke, Hodson, & Collier, 2016). A major oil spill could affect several areas around the coast and effective combating response will call for coordinated and
concerted activities by a large number of agencies. Preparation of an Oil Pollution
Emergency Plan is, therefore necessary to identify the capabilities and resources of the port
as well as all other mutual aid agencies towards establishing an organizational structure to
combat marine pollution (Chang, Stone, Demes, & Piscitelli, 2014; Dawes, 1998).
There has been a lot of work done in different countries on oil spills and their harmful
effects on the environment have been discussed. Oil spills are more common in the USA
(Gulf of Mexico) (Allan, Smith, & Anderson, 2012; Dı́az-Castañeda & Harris, 2004; Eklund,
Knapp, Sandifer, & Colwell, 2019), West Coast of the UK, Canada, Germany, Netherlands,
France (Fattal et al., 2010), Spain (Murphy & Riley, 1962; Prat et al., 1999a) and Portugal.
Also, during the Gulf War, oil spills were observed on the Arabian coast including Iraq,
Iran, Italy (Akoumianaki & Nicolaidou, 2007), South Africa, Niger Delta of Africa (Iduk &
Samson, 2015; Ifelebuegu, Ukpebor, Ahukannah, Nnadi, & Theophilus, 2017), Russian
Arctic (Yamamoto, Nakoka, Komatsu, Kawai, & Ohwada, 2003), Brazil (Borzone & Rosa,
2009), Venezuela, Chile, Australia, etc. The number of oil spills in Asian countries is very
A. Overview on oil pollution and its effect on environment
20
2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India
low and it is limited to China, India, South Korea, Philippines, Thailand (Abdulrazaq &
Kader, 2004), Pakistan etc. In India, oil spills have been seen in Chennai’s Ennore Port
(2016), Mumbai (200205, 2020, 2011), Goa, Andaman and Nicobar Islands (2006) before.
Oil spills have had an impact on the environment in India (Ansari & Ingole, 2002; Gupta,
Dhage, & Kumar, 2009; Han, Nambi, & Clement, 2018; Ingole et al., 2006; Paul, 2017;
Qasim, Sengupra, & Kureishy, 1988; Sharma, 2009; Sukumaran, Mulik, Rokade, & Kamble,
2014; Singh, Pandey, Singh, & Shukla, 2017; Vaas, Mondal, Samanta, Suresh, & Katiha,
2010) and other parts of Asia. Much of the work on oil spills deals with the direct and
indirect effects on ecosystems, fauna, flora and human health. Recognizing the importance
of these effects, various statistical analyzes have been made in different fields to understand the harmful effects of oil spills. Different countries have developed various action
plans based on these models and implemented these environmentally friendly plans over
time. Risk and vulnerability assessment have also been done based on various data
(Dhanakumar, Mani, Murthy, Veeramani, & Mohanraj, 2011; Wang, Fingas, & Page, 1999).
In general, remote sensing and GIS play a much more effective role in determining oil
spills and their effects in the estuarine region. With the change of seasons and time, changes
in water quality and location of heavy metal in the estuary can be detected with the help of
remote sensing and GIS (Abdunaser, 2020; Balogun, Yekeen, Pradhan, & Althuwaynee, 2020;
Dutsenwai, Ahmad, Tanko, & Mijinyawa, 2017; El-Amier, Elnaggar, & Al-Alfy, 2017; Nelson
& Grubesic, 2021). The effect of oil spill can be easily detected based on various parameters
through the isoline. In fact, the effects of oil spills are best understood based on water quality
and the presence of metal in river sediments obtained in estuarine areas. Water quality and
amount of contaminated metal vary depending on the seasonal flow of the river. When crude
oil is mixed with water, the amount of water pollution increases and the water quality
changes. Understanding the matter on a seasonal basis, it can be seen that the water quality is
changing as the flow of water in the river increases during the monsoon. In addition, when
crude oil is dissolved in water, the metals that exist in it accumulate in the sediments at the
bottom of the estuary and increase the presence of heavy metals. In the estuarine region, tide
also plays an important role in controlling the distribution of water quality and heavy metals.
At high tide, water mixed with contaminated and unrefined oil rises up the estuary, but at
low tide it recedes. This changes the position of water quality and heavy metal. Industrial
waste as oil spill is one of the sources for raising metallic elements in waterways (Banerjee
et al., 2006; Bejarano & Michel, 2010; Je˛drzejczak, 2002; Singare, Mishra, & Trivedi, 2012).
These elements are destroying the river ecosystem as well as harming human health. It isn’t
right to think that we are knowingly increasing these pollutants and metals in the river every
day. In India, over the past three or four decades, the level of pollution has accelerated with
increasing population density and industrial habitation (Ajmal, Nomani, & Khan, 1984;
Banerjee, Kumar, Maiti, & Chowdhury, 2016; Biswas, Paul, & Sinha, 2015; Dhanakumar et al.,
2011; Gupta, Yadav, Kumar, & Singh, 2013; Jain, 2004; Kumar, Solanki, & Kumar, 2013;
Hejabi, Basavarajappa, Karbassi, & Monavari, 2011; Marathe, Marathe, Sawant, & Shrivastava,
2011; Pandey & Singh, 2017; Prabha & Selvapathy, 1997). Heavy metals have carried in combination with deposits. Many times, these trace elements change their place with seasons. This
sediment relocation in the Indo-Gangetic floodplain has been perceived from the writings of
many researchers (Joshi, Kumar, & Agrawal, 2009; Rahaman, 2009; Saikia, Mathur, &
Srivastava, 1988; Wang et al., 2011). Toxic substances like arsenic, nickel, copper, cadmium,
A. Overview on oil pollution and its effect on environment
2.1 Introduction
21
zinc, lead, etc. have poisoned the river sediments in estuarine part. Many researchers have
found the amount of sediment toxicity in the Ganges and other rivers in India through contamination, degree of contamination, pollution load index, enrichment factor, and geoaccumulation index (Bender et al., 1980; Chakravarty & Patgiri, 2009; Singh et al., 2020;
Suthar, Nema, Chabukdhara, & Gupta, 2009; Teal & Howarth, 1984). These various parameters not only indicate the toxicity of sediments in the river but also help in understanding
their mobility with the channel. The detrimental effects of oil spills on the estuarine region are
most evident on the ecosystem. Ecological health in the estuarine region largely depends on
the functioning of the river benthic ecosystem. The BOPA index is often used to realize this
effectiveness (Dauvin & Ruellet, 2007; De-la-Ossa-Carretero & Dauvin, 2010; Gesteira &
Dauvin, 2000; Gesteira & Dauvin, 2005; Hir & Hily, 2002).
Bhagirathi-Hooghly river is a distributary channel of River Ganges, flowing from its
bifurcation point Mithipur, Murshidabad district, West Bengal, towards the Bay of Bengal,
encompassing Kolkata (Bera et al., 2019; Ghosh, Biswas Roy, & Roy, 2020). This river system is a lifeline of the southern part of West Bengal, providing irrigation, industrialization,
and human habitation to a large extent (Laha, 2015). The only busiest port in the estuarine
region of the Bhagirathi-Hooghly river is the Kolkata port. This port is visited by over
3000 large sea-going vessels each year which interalia comprises of oil & chemical tankers.
In addition, the Bhagirathi-Hooghly river within the jurisdiction of Kolkata port is also
navigated by a large number of Inland vessels/barges including Barges of Bangladesh origin plying under the Indo-Bangla protocol. Sources of oil pollution within Kolkata Port
Trust jurisdiction may be categorized under four major groups:
1. Collision, fire, explosion or grounding which results in the release of oil from the ship’s
bunkers and/or from the cargo tanks.
2. Industrial wastes containing oil and grease discharged to sea.
3. Accidental spills while transferring bunker or cargo from ship to ship, ship to shore or
shore to ship and accidental spillage resulting from incorrect operation of valves on
shipboard or at oil terminals.
4. Intentional discharge of oil or oily waste from the pumping of bilge, oily ballast water
and tank washings or by any other means.
In the estuarine region (Das & Tamminga, 2012; Mohiuddin, Zakir, Otomo, Sharmin, &
Shikazona, 2010; Nelson-Smith, 1972; Paul and Sinha, 2013) of the Bhagirathi-Hooghly
river (Kidderpore-Haldia stretch), the harmful effects of oil spills are most visible on the
mangrove forests of the Sundarbans. Earlier, oil spills in Bangladesh had an impact on the
Sundarbans. Therefore, it is very important to know the distribution of oil spills to reduce
the impact of oil spills on the ecosystem of the Indian Sundarbans. The stakeholders of
this river have increased over the last few decades with rapid urbanization and industrial
growth. As a result, the amount of pollution in the estuarine part of Bhagirathi-Hooghly
river has also increased. Plenty of water mixes with pesticide which flows into this river
every day. Even small factories, sewage from the city continue to pollute the river. The
abandonment of immersion is one of the causes of river pollution here (Roy, Halder, Nag,
Roy, & Majumder, 2018). Earlier in 2012, a contingency survey was conducted at the mentioned places along this subcatchment basin and its assessment was submitted to the
Environment Department of the Government of West Bengal. The same areas were
A. Overview on oil pollution and its effect on environment
22
2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India
re-surveyed in 2018 and a comparative discussion of past records with current reports is
conducted. The present study tries to investigate the seasonal and spatial distribution of
water quality and sediment with metal constraints on oil spill and compare it with the
tidal character. Thus, the study identifies the spatial and temporal variation of oil spill
effect on the surface and river bed with the help of GIS. The present study is also trying to
identify the ecological significance of oil spill in the estuarine part of lower BhagirathiHooghly river (Kidderpore-Haldia stretch).
2.2 Materials and methods
2.2.1 Study area
The selected subcatchment basin of the lower course of Bhagirathi-Hooghly river is up to
85 km long stretch from Kidderpore (upstream) to Haldia (downstream) comprising a portion
of Kolkata, South 24 Parganas and East Medinipur district of West Bengal, India. Geologically,
this area lies in the delta region, the lower portion of the ctive deltaic part of the Bengal Basin,
and is composed of the recent deposit of the Pleistocene period. Initially, the area was covered
by sandy clay and sand along the course of the river, and fine silt, sandy loam, and loamy soil
have been found in the flat portion of the plain Fig. 2.1. The Bhagirathi-Hooghly river is connected to Bay of Bengal via coastal estuaries. The coastal zones of West Bengal are used for navigational purpose by a considerable number of vessels moorings at Kolkata and Haldia Port.
The Kolkata city is situated on river Bhagirathi-Hooghly and is approximately 85 km upstream
from the sea. The major water source for maintaining municipal water supply for Kolkata city
is the Bhagirathi-Hooghly river’s water. There are many water treatment plants situated along
the bank of river Bhagirathi-Hooghly for example, Palta, Baranagar-Kamarhati, Garden Reach,
Dakhin Raipur Water Works etc. As there is risk of oil spillage in coastal areas of West Bengal
as well as the river Bhagirathi-Hooghly, so there is threat of deterioration of river water quality
and chances of disruption of public water supply system.
2.2.2 Data used
Water samples were collected during May, June and October 2018 from fourteen different locations as presented in map from lower Bhagirathi-Hooghly river (KidderporeHaldia stretch) and estuary. A vessel was used for collection of samples for qualitative
analysis. The samples were collected for both low tide and high tide condition. Some parameters were analyzed for the water quality and heavy metal samples on oil spill at the laboratory of School of Water Resources Engineering, Jadavpur University, like, oil and
grease, dissolved oxygen (DO), biological oxygen demand (BOD), chemical oxygen
demand (COD), turbidity, total dissolved solids (TDS) for water quality and Cadmium,
Chromium, Lead, Zinc, Nickel, Mercury for heavy metal residue from sediments. The
river water quality parameters for example, DO and TDS were measured at site by using
Rugged Field Kit. The rest of the parameters were analyzed in the laboratory. The influence of oil pollution must be resulted from handling of crude oil/petroleum oil/diesel etc
in Haldia Port/Kolkata Port and Oil Terminal Stations.
A. Overview on oil pollution and its effect on environment
2.2 Materials and methods
FIGURE 2.1 Study area map with sample points.
A. Overview on oil pollution and its effect on environment
23
24
2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India
2.3 Methodology
2.3.1 Spatiotemporal analysis in water quality and heavy metal concentration
There is a need for spatiotemporal analysis to understand the seasonal changes in
water quality (APHA, 2005) and heavy metal concentration (IOC-UNESCO, 1982; IOCUNESCO, 1984) caused by oil spills. This analysis is done through the spline method
of the Spatial Analyst tool of the Arc GIS 10.4 software and the contouring verification
of the 3D Analyst tool on the year 2018. This contouring has been made possible by
placing data along 14 points. This helps in understanding the variation of water quality and heavy metal in 14 points. These points were previously surveyed by contingency survey in 2012 and we also compare the result of those survey with present one
in later part.
2.3.2 Heavy metal indices analysis
The amount of heavy metal dissolved in water has been analyzed in the water samples taken. Analysis has been done mainly on 6 types of heavy metals. Based on several
factors and their analysis, it has been possible to get an idea about these heavy metals.
These are,
2.3.2.1 Enrichment factor
EF evaluates to assess the level of contamination and differentiates the metal based on
their origin (anthropogenic or geogenic sources). EF value is measured with the help of
conservative tracer elements like iron, aluminum, etc. The EF value of plotted points is
measured through commonly used iron (Fe) as the reference value. The EF is calculated
through (Ajmal et al., 1984; Franco-Uria, Lopez-Mateo, Roca, & Fernandez-Marcos, 2009;
Liaghati, Preda, & Cox, 2003; Turekian & Wedepohl, 1961),
EF 5 ðM=FeÞSample =ðM=FeÞBackground
(2.1)
where (M/Fe) is the ratio of metal and iron concentration in the sample and background of the crust, M is the concentration of metal and background value may be
found in subsurface geological condition. In this discussion, the study only concentrated on the heavy metal concentration except for Fe concentration. The evaluation
has considered Fe as a trace element and a part of EF evaluation for the measurement.
The calculated Fe concentration has not been depicted in the article, but the calculation was made through the Fe concentration. The interpretation of EF values are classified as: , 1 means depletion, $ 1 indicates enrichment, $ 1.5 indicates the delivery
of trace metal from noncrustal material or bank erosion element, and .2 means significant enhancement. In the case of calculating the background concentration, fundamental values are generally used, except in the Indian subcontinent area. So, for
analyzing the background concentration of metal enrichment, the studied point value
is calculated through Singh et al.’s (M. Singh, Ansari, Muller, & Singh, 2003)
parameters.
A. Overview on oil pollution and its effect on environment
2.3 Methodology
25
2.3.2.2 Contamination factor
CF is used to understand the contamination level of heavy metal concentration in a specific area. CF is analyzed through (Ajmal et al., 1984; Franco-Uria et al., 2009; Liaghati
et al., 2003; Turekian & Wedepohl, 1961),
CF 5 C;metal =C;background
(2.2)
where, the ratio of CF understood through the relation between the concentration of metal
(C,metal) and metallic concentration in sub surface element (C,background). CF value has been
classified as, CF , 1 means low contamination, 1 # CF # 3 indicates moderate contamination, 3 # CF # 6 indicates considerable contamination and CF . 6 means very high
contamination.
2.3.2.3 Pollution load index
PLI is used to compare the total metal content of different studied points in the study
area. It also provides the variation of quantity in metal concentration towards public
awareness in the surrounding area. PLI is measured through (Ajmal et al., 1984; FrancoUria et al., 2009; Liaghati et al., 2003; Seshan, Natesan, & Deepthi, 2010; Tomlinson,
Wilson, Harris, & Jeffrey, 1980; Turekian & Wedepohl, 1961),
PLI 5 ðCF1 3 CF2 3 CF3 3 . . . CFnÞ1=n
(2.3)
where, CF is the contamination factor and n is the number of metals (here 4). PLI has been
categorized into two parts that is, . 1 means pollution, ,1 indicates no contamination,
and PLI 5 1 shows only a marginal level of pollutants present in the sample.
2.3.2.4 Degree of contamination
DC is measured through the sum of all contamination factors in the study area. DC is
calculated through (Ajmal et al., 1984; Hökanson, 1980),
DC 5
n
X
CFi
(2.4)
i51
Where, n is the number of metals and CFi is the single contamination factor of metals. DC
is evaluated through 4 categories that is , n indicates low DC, n # DC # 2n indicates
moderate DC, 2n # DC # 4n indicates considerable DC and DC . 4n indicates very
high DC.
2.3.2.5 Geo accumulation index
To assess the anthropogenic impact on heavy metal concentration, we used Igeo, first
introduced by Muller (1969). It can be measured by the following equation (Ajmal et al.,
1984; Buccolieri et al., 2006),
Igeo 5
log2 ðCn Þ
1:5Bn
(2.5)
Cn is the metal concentration in the sediment, Bn is the background concentration of element (Turekian & Wedepohl, 1961), and 1.5 is the compensating factor of background data
A. Overview on oil pollution and its effect on environment
26
2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India
by lithogenic effect (Taylor, 1964). This function has not been compared with the other
indices’ measurement due to involvement in a log function and 1.5 background multiplication. It is categorized into seven grades (06) of metal enrichment that is Igeo # 0 indicates unpolluted, 0 , Igeo # 1 (unpolluted to moderately polluted), 1 , Igeo # 2
(moderately polluted), 2 , Igeo # 3 (moderately to strongly polluted), 3 , Igeo # 4
(strongly polluted) and 4 , Igeo # 5 (strongly to extremely polluted). Class 6 is an open
class and comprises of the pattern of all values from the previous class.
2.3.3 Ecological impact through BOPA index
The effects of oil spills on ecosystems are best understood in the benthic region below the
estuary. Basically, all the heavy metals that are dissolved in water slowly settle to the bottom
of the estuary and cause a lot of damage to other plant species including fish. The BOPA
index is discussed to understand the effects of oil spills on benthic ecosystems (Dauvin &
Ruellet, 2007; De-la-Ossa-Carretero & Dauvin, 2010; Gesteira & Dauvin, 2000; Gesteira &
Dauvin, 2005; Hir & Hily, 2002). This index is formed based on the approximate percentage of
the presence of opportunistic polychaetes and the amount of this index is higher in stressed
zone Table 2.1. This index can be divided into five ecological quality status classes.
2.4 Result and discussions
2.4.1 Spatiotemporal analysis of water quality parameter
Different parameters of water quality affect the environment in different ways. Increasing
the amount of oil and grease in estuary water causes considerable damage to the environment
and ecosystem in 2018. In addition, increasing the amount of BOD and COD reduces the
amount of DO, which in turn harms estuarine ecosystems. Increasing the amount of turbidity
and TDS increases the hardness of water which causes various physical problems in human
and animal body. One thing is to be noted that, all measurements here are based on high and
low tides period. Measurements of water quality have increased from low tide to high tide
period, which indicates the changing course of the river at the estuary. Seasonal position
change of water quality parameters with high and low tide is discussed below (Abdunaser,
2020; Balogun et al., 2020).
TABLE 2.1 BOPA index classes [46].
Quality
Index
High (unpolluted sites)
0.00000 # BOPA # 0.02452
Good (slightly polluted)
0. 02452 # BOPA # 0.13002
Moderate (moderately polluted)
0. 13002 # BOPA # 0.19884
Poor (heavily polluted)
0.19884 # BOPA # 0.25512
Bad (extremely polluted)
0.25512 # BOPA # 0.30103
A. Overview on oil pollution and its effect on environment
2.4 Result and discussions
27
The concentration of oil and grease in river Bhagirathi-Hooghly between Khidirpur and
Falta during low tide and high tide indicated less than 1 mg/L Fig. 2.2. Presence of oil and
grease above 1 mg/L was found between Raichak Public Jetty and Kendamari. The concentration of oil and grease during low tide and high tide between Raichak Public Jetty
and Kendamari ranged between 3.1 mg/L and 1.9 mg/L. The highest amount of oil and
grease are mainly concentrated in the downstream part (Diamond Harbor to Haldia) in
time of low tide. But the concentration is totally altered in time of low tide (downstream
mainly surrounding Nayachar Island).
In case of BOD, maximum permissible limit for discharge of wastewater in inland
waterbody is 30 mg/L Fig. 2.3. As per IS 2296, the tolerance of BOD in Class C waterbody is
3 mg/L. Hence maximum tolerance limit of BOD in Class C waterbody is 10% of maximum
permissible limit of BOD for discharging inland surface water. In IS 2296, there is no tolerance
limit for oil and grease getting discharged in inland surface water. However, as per said IS
code the tolerance limit for mineral oil in Class C waterbody is 0.1 mg/L. Considering similarity with respect to BOD, maximum tolerance limit could be considered as 1 mg/L for oil and
grease. Therefore, presence of oil and grease between 3.1 mg/L and 1.9 mg/L between
Raichak Public Jetty and Kendamari indicated influence of oil spill/pollution. The influence of
oil pollution resulted from handling of crude oil/petroleum oil/diesel etc in Haldia Port/
Kolkata Port and Oil Terminal Stations. The study indicated risk associated with oil spill/
pollution in Hooghly river. Any accidental oil spill due to vessel collision, tanker leakage etc
may cause increasing oil and grease concentration in the river and can spread upstream
between Moyapur/Royapur and Kalyani where many water intakes for water treatment plants
are situated. In all time, the highest amount of BOD concentration is mainly surrounded in
Haldia industrial region.
The COD in river Bhagirathi-Hooghly during May and October, 2018 ranged between
1.9 and 5.9 mg/L Fig. 2.4. As per IS 2296 for Class C category of inland surface water the
maximum tolerance limit of COD is 3 mg/L. There is a need to take up action-oriented
program for abatement of pollution of river Ganga. Higher concentration of COD
(. 3 mg/L) has been recorded downstream of Falta. The number of COD is seasonally
higher around the Nayachar island and Haldia industrial belt.
The DO concentration as studied between May and October, 2018 indicated 4.4 and
7.1 mg/L (Fig. 2.5). Presence of DO below 5 mg/L may have been caused due to higher
organic load getting discharged in the river. In fact, DO saturation around 90% was
recorded between Raichak and Kendamari. But lesser saturation concentration of DO has
been recorded upstream of Raichak and it could be attributed due to the discharge of
untreated and partially treated sewage. Seasonally the concentration of DO is higher in
downstream part (Diamond Harbor to Haldia) with tidal effect.
TDS is considered as an important parameter for assessment of tidal river water quality
(Fig. 2.6). The river Hooghly is a tidal river and it is influenced by the salinity entering from
Bay of Bengal. Since the river Hooghly receives a good amount of discharge from Farakka,
the salinity level in Hooghly around Kolkata Metropolitan Area (KMA) is normally less than
80 mg/L. Thus, TDS becomes less than 300 mg/L in the Hooghly along KMA. The water
quality analysis of river Hooghly indicated lower TDS above Falta whereas downstream of
Falta TDS found to be increasing at a faster rate. The TDS between 10,000 and 20,000 mg/L
was monitored between Kulpi and Kendamari. TDS concentration is seasonally higher in the
downstream part (Diamond Harbor to Haldia) with tidal effect.
A. Overview on oil pollution and its effect on environment
28
2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India
FIGURE 2.2 Spatiotemporal seasonal distribution of oil and grease (with tidal effect).
A. Overview on oil pollution and its effect on environment
2.4 Result and discussions
FIGURE 2.3 Spatiotemporal seasonal distribution of BOD (with tidal effect).
A. Overview on oil pollution and its effect on environment
29
30
2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India
FIGURE 2.4 Spatiotemporal seasonal distribution of COD (with tidal effect).
A. Overview on oil pollution and its effect on environment
2.4 Result and discussions
FIGURE 2.5 Spatiotemporal seasonal distribution of DO (with tidal effect).
A. Overview on oil pollution and its effect on environment
31
32
2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India
FIGURE 2.6 Spatiotemporal seasonal distribution of TDS (with tidal effect).
A. Overview on oil pollution and its effect on environment
2.4 Result and discussions
33
Turbidity is largely calculated as a result of measuring total suspended solids in water
(Fig. 2.7). The more turbid the water, the higher the amount of turbidity. As the water flow is
higher during high tide, the water content is higher and the amount of turbidity increases.
Turbidity increases mainly during monsoon period. Turbidity levels are much higher near the
industrial areas of Diamond Harbor, Kulpi, Haldia and Nayachar (429801 NTU). Basically,
the amount of turbidity is much higher for industrial effluents. This amount of turbid water is
much higher also during the monsoon. The concentration of turbidity is same with TDS but
in the seasonal period of low tide, the story is different. Highest turbidity in low tide section
is found between Budge Budge to Kulpi, due to excessive pollution from urban land.
2.4.2 Spatiotemporal analysis of dissolved heavy metal parameter
The amount of heavy metal concentration in the water varied in different seasons in
2018. As the river belongs to the old stage of the morphometric condition, the accumulation of sand heave is presented elsewhere over the river. Thus, the river’s flow condition
is severely low, but it becomes high during monsoon time. Therefore, river transports all
the sediment heave from upper to lower section, and in postmonsoon, the metallic concentration becomes higher in the lower part. River water quality was also monitored to assess
the presence of metal pollution for example, Cadmium (Cd), Mercury (Hg), Lead (Pb),
Zinc (Zn), Chromium (Cr) and Nickel (Ni). The presence of these metals upstream of Falta
has been found to be within the tolerance limit. However, presence of metal concentrations
for example, Cadmium and Lead has been found beyond permissible limit in downstream
Falta (Fig. 2.8 and Fig. 2.9). In all the water samples between Khidirpur and Kendamari,
Mercury concentration was found to be less than 0.0025 mg/L (Fig. 2.10). The position and
amount of heavy metal dissolved in water varies with the flow of water. Although the
amount of heavy metal is less during the monsoon, the presence of heavy metal can be
noticed as there is no good water flow before and after the monsoon. Basically, the runoff
of industrial areas, factories, sewage system etc., constantly flows into the BhagirathiHooghly river and increases the amount of heavy metal. When these elements are present
in large quantities, they completely damage the estuary ecosystem.
Not only that, it enters the human body through fish and other aquatic animals and
causes overall harm to humans. The amount of heavy metal dissolved in water as a whole
is much higher in Diamond Harbor, Kulpi, Haldia, Nayachar etc. While the amount of
cadmium and mercury is higher in the Diamond Harbor area, the amount of Lead is higher in all points overall. Lead causes various diseases in the human body. In addition, the
amount of Zinc (Fig. 2.11), Chromium (Fig. 2.12) and Nickel (Fig. 2.13) is much higher in
Haldia than in Diamond Harbor. Basically, the location of the natural sandbar has helped
a lot to increase the concentration of this heavy metal.
The concentration of cadmium, zinc, mercury and nickel is higher in upstream
(Kidderpore-Budge Budge) and downstream (Kulpi to Haldia) part of this subcatchment
basin in pre and postmonsoon period with tidal effect. But in the monsoon, the metal
floats due to the heavy flow of water and is concentrated in the lower section around
Nayachar. The concentration of lead is higher in the downstream section (Diamond
Harbor to Haldia) with tidal effect. Seasonally, the concentration of chromium is always
higher in in the downstream section (Kulpi to Haldia) with changing tidal behavior.
A. Overview on oil pollution and its effect on environment
34
2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India
FIGURE 2.7 Spatio-temporal seasonal distribution of Turbidity (with tidal effect).
A. Overview on oil pollution and its effect on environment
2.4 Result and discussions
FIGURE 2.8 Spatiotemporal seasonal distribution of Cadmium (with tidal effect).
A. Overview on oil pollution and its effect on environment
35
36
2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India
FIGURE 2.9 Spatiotemporal seasonal distribution of Lead (with tidal effect).
A. Overview on oil pollution and its effect on environment
2.4 Result and discussions
FIGURE 2.10 Spatiotemporal seasonal distribution of Mercury (with tidal effect).
A. Overview on oil pollution and its effect on environment
37
38
2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India
FIGURE 2.11
Spatiotemporal seasonal distribution of Zinc (with tidal effect).
A. Overview on oil pollution and its effect on environment
2.4 Result and discussions
FIGURE 2.12 Spatiotemporal seasonal distribution of Chromium (with tidal effect).
A. Overview on oil pollution and its effect on environment
39
40
2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India
FIGURE 2.13
Spatiotemporal seasonal distribution of Nickel (with tidal effect).
A. Overview on oil pollution and its effect on environment
2.4 Result and discussions
41
2.4.3 Changes in the parameter effecting oil spill
It is important to compare the current reports with the information obtained since it
makes it possible to understand the rate of change. Because it makes it possible to understand the rate of change. This comparison is based on changes with high and low tides.
The quality of the parameters changed from 2012 to 2018 based on the contamination of
crude oil in the water quality samples. Since 2012, the levels of TDS, Turbidity, BOD and
COD have increased by 12%, 9%, 7.8% and 4.8% respectively in 2018. On the other hand,
pollution of crude oil increased the levels of lead, cadmium, zinc and mercury in heavy
metals dissolved in water by about 7.6%, 5.2%, 4.2%, and 3% in 2018. Due to the increase
in the pollution of crude oil in the estuary area, the amount of these substances in the
water has continuously increased (Fig. 2.14).
FIGURE 2.14 Changes in (A) water quality parameter and (B) heavy metal concentration (201218) by oil
spill.
A. Overview on oil pollution and its effect on environment
42
2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India
2.5 Dissolved heavy metal indices
2.5.1 Enrichment factor
The results of the mean annual enrichment factor in heavy metal concentration in
water has been illustrated in Fig. 2.15. This figure indicates that the EF of lead and cadmium are significantly high in enrichment seasonally during both high and low tide
period. The EF (Ajmal et al., 1984; Franco-Uria et al., 2009; Liaghati et al., 2003;
Turekian & Wedepohl, 1961) variation of other metals is negligible, compared to cadmium and lead during both high and low tide period. According to these results, the
EF value of all six studied metal is highly varied, except chromium and nickel.
Chromium and Nickel are in low enrichment in the study area. Cadmium and lead
enriched in this area comes from surrounding agricultural field and industrial sectors,
and also for river transportation mainly in downstream location (near Haldia and
Nayachar). The EF sequence for heavy metals in sediment of this subcatchment basin is
in following sequencing order: Pb . Cd . Zn . Hg . Cr . Ni, which proves the enrichment of lead was higher in comparison with other metal and nickel had a lower
amount of concentration. The geochemical analysis of sediment concentration depends
upon the measurement of EF. The degree and source of metal contamination have been
analyzed through the EF factor. Among the studied points, cadmium became the most
enriched element in water seasonally in respecting tidal factor.
FIGURE 2.15
Seasonal enrichment factor (EF) with tidal effect.
A. Overview on oil pollution and its effect on environment
2.5 Dissolved heavy metal indices
43
2.5.2 Contamination factor
The illustration in Fig. 2.16 indicated the CF of metal concentration seasonally with tidal
effect. Location wises the CF (Ajmal et al., 1984; Franco-Uria et al., 2009; Liaghati et al.,
2003; Turekian & Wedepohl, 1961) value varied with seasonal effect. In the case of the
industrial sector neighboring and increasing the sewage system, it enhanced the CF value
of concentration in the downstream area. Lead and Cadmium had high CF in most of the
studied locations, which was significantly nearer to urban and industrial sites. The value
of CF varied roughly in rust metal concentration throughout the area. The CF value of
lead is highly significant and ranges from moderate to high variation in Diamond harbor,
Kulpi, Haldia, Falta and Nayachar area.
2.5.3 Pollution load index and degree of contamination
The illustration in Fig. 2.17 represented both seasonal PLI and DC in the study area
within the subcatchment basin of lower Bhagirathi-Hooghly river (Kidderpore-Haldia
stretch) with tidal effect. As the PLI values (Ajmal et al., 1984; Franco-Uria et al., 2009;
Liaghati et al., 2003; Seshan et al., 2010; Tomlinson et al., 1980; Turekian & Wedepohl,
1961) of this area were ,1, so no significant level of pollution was indicated through this.
But the result of DC value (Ajmal et al., 1984; Hökanson, 1980) illustrated low to moderate
degree of contamination, except the upstream and downstream location of the surveyed
area. The degree of contamination was higher there because of industrial effused water
FIGURE 2.16 Seasonal contamination factor (CF) with tidal effect.
A. Overview on oil pollution and its effect on environment
44
2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India
FIGURE 2.17
Seasonal pollution load index (PLI) and degree of contamination (DC) with tidal effect.
and sewage system of the urban area. The concentration value has been gathered in the
downstream area with industrial habitation and upstream area with high river transportation on seasonal basis.
2.5.4 Geo accumulation index
The accumulation of data through Igeo of the seasonal studied samples are illustrated
in both high and low tide period (Ajmal et al., 1984; Buccolieri et al., 2006). According to
the classification by Muller (Muller, 1969), the representation of negative value indicated
no pollution development in the subcatchment basin. For lead and cadmium, the Igeo
values showed moderately toxic pollution in the downstream sections of the basin. The
Igeo benefits also became uncontaminated in all over the basin area seasonally by
Fig. 2.18. The uncontained concentration of rest of heavy metals has also been indicated in
the mid-portion of the basin.
A. Overview on oil pollution and its effect on environment
2.5 Dissolved heavy metal indices
45
FIGURE 2.18 Seasonal Igeo with tidal effect.
2.5.5 Changes in heavy metal indices
When the contingency survey was conducted in 2012, the number of metals that were dissolving in the water due to the contamination of crude oil was determined. There is a big difference between that standard and the heavy metal indices made in 2018. A difference of two
years on that average measurement based on the tidal effect makes a good difference. In the
case of PLI and DC, it can be said that the amount of pollution has increased by 4.2% and 3.5%
in 2018 as compared to 2012. The amount of contamination has increased to increase the
amount of pollution and according to the record, the contamination increased from 2012 to 2018
by about 5.4%. As a result of the increase in the number of contaminants in the water, they
have become enriched rapidly in various aquatic animals and plants and the amount of enrichment has increased by about 5.6%. Due to the low velocity of the river, the pollutants have
accumulated in one place and its measure has increased by about 8.2%. However, the position
of accumulation during the low tide in 2012 has completely changed in 2018. It should be noted
that the location of heavy metals derived from crude oil is highest from Kulpi to Haldia, which
proves that most of the pollution is confined to this region (Fig. 2.19).
2.5.6 Quantitative variation with increased oil spill
Most of the oil spill’s material concentration that is produced through effluent from sewage,
industry, river transport and agricultural land is stored in mud and sand in the downstream
A. Overview on oil pollution and its effect on environment
46
2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India
region of subcatchment basin. Effused water discharge and velocity play an important role in this
storage. Since the overall picture of the whole region has been compared between high and low
tide, the oil spill’s material concentration is shown comparatively with the effused water flow in
estuarine region (Fig. 2.20). The amount of effluent water from urban, industrial and agricultural
areas has increased a lot in high tide than the low tide period. In addition, the polynomial coefficient of determination has been over 90% in two specific years (high and low tide), which shows
an increase in the amount of oil spill in the region and water pollution because of the sewage
from industrial and urban areas and also the residue from river transport amenities.
FIGURE 2.19
Changes in heavy metal indices of (A) PLI and DC, (B) CF, (C) EF and (D) Igeo (201218) by oil
spill.
FIGURE 2.20
Oil spill variation with flow (A) high tide and (B) low tide.
A. Overview on oil pollution and its effect on environment
47
2.5 Dissolved heavy metal indices
TABLE 2.2 Comparison of average seasonal oil spill material concentration and velocity.
High tide
Area
Time
Nature of
flow (m/s)
Oil spill’s material
concentration (mg/L)
Upstream
Pre-Monsoon
0.40.7
120
Monsoon
1.62.7
84
Post-monsoon
0.60.8
216
Pre-Monsoon
0.20.4
105
Monsoon
3.24.7
60
Post-monsoon
12.6
221
Pre-Monsoon
0.30.6
140
Monsoon
1.22.4
68
Post-monsoon
0.40.7
200
Pre-Monsoon
0.30.6
125
Monsoon
2.83.7
22
Post-monsoon
0.81.6
201
Downstream
Low tide
Upstream
Downstream
Also, since the whole discussion is based on seasonal changes, the oil spill’s material
concentration on a seasonal basis is shown in the Table 2.2 in between high and low tide.
Comparison of tidal effect shows that the concentration in the downstream region of the
subcatchment basin increased during the postmonsoon season. From tidal differentiation,
the amount of this concentration is much higher. The velocity of estuarine water flow in
monsoon time is higher than pre and postmonsoon period. As a result, the amount of oil
spill’s material washed out in monsoon time in seasonal scenario. Although flow is higher
during the monsoon, the decrease in velocity in pre and postmonsoon increases the material concentration and adverse effect of oil spill continues.
2.5.7 Ecological impacts through BOPA index
This stretch (Kidderpore-Haldia stretch) is full of various plants and animals, including
a variety of fish and Gangetic dolphins. Oil spills have caused severe damage to the fauna
and are now on the verge of extinction. Oil spills have severely damaged the entire ecosystem, including many plants and animals in the estuary (Dauvin & Ruellet, 2007; De-laOssa-Carretero & Dauvin, 2010; Gesteira & Dauvin, 2000; Gesteira & Dauvin, 2005; Hir &
Hily, 2002). The extent and impact of these losses are determined by the BOPA Index
(Fig. 2.21). The low BOPA index value of the study area above indicates the high ecological value of the region and is organized during or after the oil spill. It is most often organized during the monsoon, when the oil spills are washed away by the water due to the
high-water flow. However, the value of BOPA index is highest before and after monsoon,
when water flow is low and oil spills are not easily removed. The BOPA index is
A. Overview on oil pollution and its effect on environment
48
2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India
FIGURE 2.21
Seasonal BOPA index with tidal effect.
essentially a measure of the ecological quality of a region affected by oil spills, and is considered to be one of the relative means of changing ecosystems in the estuary. The BOPA
index is based on 14 sample taken points. A review of this index based on the season and
tide shows that the BOPA index value from Khidirpur to Falta is quite good. Then the
BOPA value from Raichak to Diamond Harbor is fair but the BOPA index is very poor in
the next part up to Haldia. The condition here is considered to be very bad due to excessive pollution.
2.6 Conclusion and recommendation
Oil spill in river Bhagirathi-Hooghly or oil pollution from coastal zone entering in river
Bhagirathi-Hooghly will have serious effect on a number of activities, such as, bathing, public
A. Overview on oil pollution and its effect on environment
2.6 Conclusion and recommendation
49
water supply, irrigation, fishing, recreation and religious activities. Tourism in coastal areas
including Sundarban, Sagar Islands, Bakkhali, Frazergunge, Geokhali, Haldia, Diamond Harbor
and other important locations will be affected. Livelihood of many people depending on tourism,
fishing etc will also get affected due to oil pollution. Aquatic flora and fauna will be under stress
condition due to emulsifications of oil in the river system. Dolphins, other marine mammals, reptiles, aquatic birds, aquatic life on shorelines will get affected. Oil spills have serious ecological
impact on coastal activities and on those who exploit the resources of the river ecosystem. The
entry of oil pollution in various river connectivity in Sundarban will have serious impact of
aquatic life and mangrove. In most cases damages in coastal areas, estuary and river network are
caused primarily by the physical properties of oil creating nuisance and hazardous conditions.
The location of the oil spill in the estuarine region of Bhagirathi-Hooghly river
(Kidderpore-Haldia stretch) is highlighted with seasonal changes and tidal effect. Remote
sensing (RS) and geographical information systems (GIS) have helped to highlight the
directional change in oil spills. The number of COD (1042 mg/L), TDS (15019300 mg/
L) and turbidity (70810 NTU) in the water quality parameters along the entire stretch is
quite high, which indicates the overall contamination of water in this region. On the other
hand, as the amount of DO decreases, it becomes a barrier to survival for a particular ecosystem. Heavy metals dissolved in water also contain high levels of lead (0.0218.7 mg/L)
and cadmium (0.000812.456 mg/L). Also, compared to the data obtained from the contingency survey in 2012, the amount of TDS, turbidity, BOD, COD, lead, cadmium, mercury
and zinc increased in 2018. At the same time, the contamination and accumulation of contaminants in the water has increased a lot. The effect of oil spill on water quality and heavy metal is most seen during high tide and monsoon. Basically, the higher the flow, the
more oil spills dissolve from one place to another. But when the flow is low, the dissolved
substances start to accumulate in one place. Pollution levels, including oil spills, are much
higher in Falta, Diamond Harbor, Kulpi, Haldia, Nayachar and other areas. Having a
sandbar near Nayachar allows oil spilled heavy metals and contaminants to accumulate
there. Also, in the high tide, substances move from one place to another. The lower the
slope (from Diamond Harbor to Haldia), with lowering velocity of the river, the less likely
it is that oil spills will accumulate. Therefore, the lower part of the stretch is more prone to
contamination than the upper part. Also, in the above oil spill prone areas due to high
amount of water drained from factories, urban areas and urban sewers, the amount of pollution is much higher in this area of estuary. Of course, this part of the estuary is the busiest for river transport and large ships, vessels, fishing boats almost all pass through this
area. All this increases the amount of oil spills from the oil emitted by the vehicle. The biggest impact of this oil spill is on the ecosystem of the region concerned, the amount of
which we measure with the help of BOPA index. The value of the BOPA index is much
higher in the 14 pointers from Diamond Harbor to Haldia, which highlights the maximum
amount of pollution.
This article highlights the spatiotemporal effects of oil spills. GIS mapping of different
parameters has shown which regions are more limited. This will make it easier for policy
makers to measure contaminated areas. It will also be possible for environmentalists to
understand which areas are more prone to oil spills and to prevent the spread of oil spills
by adopting specific policies in those areas. Ships or vessels at the port through the
Kolkata Port Trust need to be inspected so that accidents (fire connection, sinking) do not
A. Overview on oil pollution and its effect on environment
50
2. Spatiotemporal distribution of oil spill effect in the estuarine terrain of Bhagirathi-Hooghly River, West Bengal, India
occur and a special committee has to be formed for that. It is necessary to pay attention to
the issue of purification of water discharged from urban areas and factories. Care must be
taken to ensure that crude oil from large oil-carrying vessels does not accidentally fall into
the estuary.
In case of pollution within the dock the antipollution vessels need to be deployed at the
site to recover oil from the dock waters. Manual cleaning simultaneously will also help to
minimize the problem and accordingly private firms can be engaged by the competent
authorities. Regular water quality monitoring will be needed to ascertain the extent and
magnitude of oil pollution. All oil companies (IOCL, HPCL, BPCL, IBP) must be equipped
with men and machine to fight the oil spillage. The all companies must draw action program for adoptions on regular basis as well as during emergencies to combat the problem
arising out from oil spillage/pollution. The controlling officers of Water Supply authorities
(KMC, KMW&SA, KMDA and PHED) shall be informed regarding instances of oil spillage
in case the same threatens to affect their water intake facility. Under such situation they
should deploy their own means to guard/encircle their intake jetty so that oil slicks do not
enter the water treatment plant. If required, they must stop intake pump till such time the
oils slick moves sufficient distance away from the intake jetty.
Acknowledgment
Preparation of Contingency Plan in 2012 and survey on 2018 for Marine Oil Spill for the Coastal areas of West
Bengal has been provided by the Department of Environment, Govt. of West Bengal. This support is highly
acknowledged by the School of Water Resources Engineering, Jadavpur University for creating an opportunity to
work on such an important issue. The authors are also acknowledging gratitude to the all the workers and Digital
Library of School of Water Resources Engineering, Jadavpur University, for allowing to access all the GIS and statistical software.
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A. Overview on oil pollution and its effect on environment
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C H A P T E R
3
Oil pollution and municipal
wastewater treatment: issues and
impact
Rwiddhi Sarkhel1 and Preetha Ganguly2
1
Department of Chemical Engineering, National Institute of Technology Durgapur, Durgapur,
India 2Department of Biochemical Engineering and Biotechnology, Indian Institute of
Technology Delhi, New Delhi, India
O U T L I N E
3.1 Introduction
57
3.2 Methodology
3.2.1 Oil and petroleum sources in
wastewater streams
58
58
3.3 Treatment methods of wastewater
containing oil
3.3.1 Some conventional treatment
methods are as follows
3.3.2 Some new methods for the
wastewater treatment
59
3.4 Results
3.4.1 Future perspectives
61
62
3.5 Conclusion
63
Acknowledgements
63
Conflict of interest
63
References
63
59
60
3.1 Introduction
Commercial wastewater effluent from different petrochemical, chemical, and biorefinery sites has various features in common with the municipal wastewater in term with the
organic contamination content. The removal of such pollutants can be achieved by certain
centralized and biological process. It has been estimated that the degradability of chemical
Advances in Oil-Water Separation
DOI: https://doi.org/10.1016/B978-0-323-89978-9.00016-1
57
© 2022 Elsevier Inc. All rights reserved.
58
3. Oil pollution and municipal wastewater treatment: issues and impact
oxygen demand (COD) in oil-based industrial wastewater is always less than that of the
municipal wastewater.
Oil and grease polluted wastewater effluent come from enormous resources like petrochemical industries, crude oil generation, and oil refinery (Lan, Gang, & Jinbao, 2009). The
toxic substances contained in the industrial oil-based wastewater effluent are petroleum
hydrocarbons, polyaromatic, and phenol which are carcinogenic and mutagenic to humans
as well as equally inhibitory to animal and plant growth. There is a higher content of COD,
color, and oil content in the oily wastewater (Lan et al., 2009). In the last few decades there
has been an increasing world demand for the edible vegetable oil which has led to enormous increase in the commercial cultivation of different oil seeds such as oil palm and soybean (Yacob, 2008). Therefore, it can be concluded that the vegetable oil production
industries are, equally, related with refining, uses and reuses, extraction and transportation.
Oil containing wastewater are usually categorized as serious hazardous contaminants when
disposed into aquatic bodies, and here they pose higher toxic level to the aquatic life, organisms, and ecology (Mendiola, Achutegui, Sanchez, & San, 1998).
Oil and grease are generally classified as non-polar and hydrophobic compound insoluble in water. Under anaerobic environmental conditions, the hydrolysis of oils and grease
to long chain fatty acids and glycerol takes place.
On the other hand, municipal waste is categorized among one of the most enormous pollutants among other domestic and commercial contaminant currently present. To be precise
municipal wastewater treatment is a process in which the addition of harmful waste pollutant
in the water resources takes place from various resources. The main source of municipal pollutant is the domestic waste. The various methods to treat such waste ware biological, chemical, and physical methods. It is one of the main concerns to effectively treat municipal waste
nowadays. The treated effluent might be utilized for the cultivation of different crops.
In the case of municipal wastewater treatment systems, biological treatment processes
are needed to be installed and operated downstream to the primary treatment plant. The
major difference for the municipal waste effluent, is that in primary treatment comprises
removal of only inert and large size materials and grit, that are very common to inflows,
whereas typical municipal treatment comprises of pretreatment of industrial wastewater
followed by primary treatment.
In this review, the study focuses on both the major pollutants of wastewater that are oil
based and municipal waste. The sources of waste are mentioned along with the treatment
methodology. The impact of the wastewater on the environment and challenges is discussed in detail in this review paper. The SWOT analysis for the oil pollution and municipal wastewater is done.
3.2 Methodology
3.2.1 Oil and petroleum sources in wastewater streams
Due to the large concentrations of oil, grease, petroleum, and crude oil around (4000 to
6000 mg/L) from the oil mills, factories, effluents, and petroleum refining industries, the
wastewater streams get highly polluted. This results in its largest source of producing oily
A. Overview on oil pollution and its effect on environment
3.3 Treatment methods of wastewater containing oil
59
wastewater (Ahmad, Bhatia, Ibrahim, & Sumathi, 2005). Because of highly contaminated oily
wastewater and the human shelf life, the aquatic life also gets hampered due to the accumulation of toxic products persists destructing the stability of the environment (Techobanglus &
Franklin, 1995). This greywater can be utilized for the irrigation and agricultural purposes
due to the presence of oil and grease present in it (Friedler, 2004). Various industries like
dairy, meat, and food producing products produce high quantities of effluents containing oil
and grease (Vidal, Carvalho, Mendez, & Lema, 2000; Cammarota & Annajr, 1998; El-Bestawy,
El-Masry, & El-Adl, 2005). Also, some oil containing wastewater streams contain oil produced
from the non-vegetable oil manufacturing industries such as the petroleum refining, metal
forming, and textile industries (Wake, 2005). Large volumes of effluent are produced from different countries like the United Kingdom, Italy, etc. (Busca, 2004). The bilge water usually contains fuel oils, lubricating oils, hydraulic oils, and detergents (Karakulski, Morawski, &
Crzechulska, 1998). Thus, a huge quantity of domestic and sewage wastewater contains oil
and grease as emerging pollutants.
3.3 Treatment methods of wastewater containing oil
There are different treatment methods for the separation of oil from the wastewater
streams. This includes conventional as well as new emergent processes like floatation,
coagulation, membrane separation, and biological treatment (Fig. 3.1).
3.3.1 Some conventional treatment methods are as follows
3.3.1.1 Floatation
Flotation may be defined as the process of bubble formation due to the suspension of
oil particles in water since the density for oil because of floatation is less than water
(Moosai & Dawe, 2003). The process produces less sludge and high efficiency in the treatment of wastewater containing oil (Rubio, Souza, & Smith, 2002). Dissolved air flotation
and flotation impeller has been widely used since its longevity time is more, but it has
FIGURE 3.1 Schematic representation for
the treatment methods of wastewater containing oil.
A. Overview on oil pollution and its effect on environment
60
3. Oil pollution and municipal wastewater treatment: issues and impact
disadvantages of repairing and manufacturing problems because of its large energy consumption. In comparison, the jet flotation method not only saves energy, but also have
advantages for application features like, easy installation, operation and safety features,
which creates a new development for the research. Flotation agents are used to improve
flotation. These agents are used to bridge adsorptivity of the colloidal suspensions (Wang,
2007). Methods like dissolved air flotation and column flotation were applied to obtain
high water oil separation efficiency (Li, Liu, Wang, Wang, & Zhou, 2007). The dissolved
air flotation treatment was investigated after the addition of activated carbon (Hamia, AlHashimi, & Al-Doori, 2007). The results revealed that when the carbon content was
of 50150 mg/L, there was an increase in the removal rate of COD from 16%64% to
72%92.5% rise, and also a significant increase in the BOD removal rate from 27%70% to
76%94% (Painmanakul, Sastaravet, Lersjintanakarn, & Khaodhiar, 2010). The study
inferred from the drawn with respect to the COD concentration varying the parameters.
The velocity gradient (G) and a/G ratio provides the efficiency of floatation increasing the
costs.
3.3.1.2 Coagulation
Coagulation procedure is an eminent treatment process to remove the oil and other biodegradable polymers from wastewater containing oil (Ahmad, Sumathi, & Hameed, 2006).
A coagulant composite CAX has been established for the treatment of wastewater streams
containing oil, grease, and petroleum when the original oil in water concentration was
207 mg/L, COD concentration was 600 mg/L (Lin & Wen, 2003). Zeng, Yang, Zhang, and
Pu (2007) studied the process of flocculation and coagulation treatments using zinc silicate
(PISS) composite. This composite acts as an efficient flocculent for the oily wastewater
treatment with an oil removal efficiency 99%, with suspended solids concentration less
than 5 mg/L (Zeng et al., 2007). These methods progressively lead to high costs with the
new trend of developing cost-effective composite materials. Cong, Liu, and Hao (2011)
used the best flocculation condition with an optimal dosage of 35 mL, and a suitable range
of pH is 78 (Cong et al., 2011).
3.3.2 Some new methods for the wastewater treatment
3.3.2.1 Membrane separation
Membrane separation technology involves the utilization of a membrane as a porous
material for the physical removal of contaminants (Lin, Liu, Liu, & Zhang, 2006). The pressure driven membrane separation processes have been classified into various treatment
methods for the treatment of oily wastewater using membranes such as microfiltration
(MF), ultrafiltration (UF), nanofiltration, and reverse osmosis (RO). Song, Wang, and Pan
(2006) used the carbonization techniques involving activated carbon and membrane separation methods like MF to obtain a tubular carbon matrix with low cost, and high efficiency which has been suitable for the treatment of oily wastewater. The operating
conditions require a pore size of 1.0 m, pressure of 0.10 MPa, and flow rate of about
0.1 m/s for the treatment of oily wastewater with oil removal efficiency 97%. The
A. Overview on oil pollution and its effect on environment
3.4 Results
61
membrane was stable at a high permeation flux rate of about 99% in neutral or alkaline
environments. It has been noticed from the recent literature surveys that as the temperature increased from 283 to 313K, the steady retention ratio decreased from 99.9% to 98.2%
and the steady permeate fluxes increased from 120.1 to 153 L. Crossflow MF processes
with oily wastewater with effects of variation in the parameters by the permeate flux was
investigated by (Hua et al., 2007). A sensitivity analysis (SA) was also conducted to enumerate the influence of the parameters on the permeate volume. NaA zeolite MF membranes incorporated with in situ hydrothermal synthesis process for the separation and
recovery from oily water were studied by (Cui, Zhang, Liu, Liu, & Yeung, 2008). It was
inferred that more than 99% oil rejection was obtained. Salahi, Noshadi, Badrnezhad,
Kanjilal, and Mohammadi (2013) developed a model named nanoporous membrane
(PAN). It has been inferred from the results that nanoporous membrane is efficient for the
treatment of petroleum refinery wastewater. The treated water can be utilized for the discharge to the environment and can be reused as agricultural water. Tomaszewska, Orecki,
and Karakulski (2005) investigated the oily wastewater treatment in the hybrid technique
of UF/RO system with maximum purification. The new methods with hybrid technique of
membrane separations add into the emergence of different techniques better than the conventional methods to separate the oil from wastewater at a high efficiency.
3.3.2.2 Biological treatment
Microorganisms play an interim part in the biological treatment process for the
decontamination of the wastewater containing oil (Kriipsalu, Marques, Nammari, &
William, 2007; Sirianuntapiboon & Ungkaprasatcha, 2007). Treatment methods involving activated sludge and biologically use filtration techniques. Aeration tank utilizes
the method of activated sludge for the decomposition of the microorganisms on the
surface of lagoons. The biological filter method is used where the microorganisms are
attached to the filter, and the oily wastewater gets filtrated out thus separating the
micropollutants and oil from water (Li, Tian, & Xie, 2006). Fungi effectively takes
place for the high COD removal from the wastewater. Studies show (Li, Kang, &
Zhang, 2005). Scholz and Fuchs (2000) assessed the oil removal rate with higher efficacy. Liu, Ye, Tong, and Zhang (2013) treated heavy oil wastewater with low nutrient
of nitrogen and phosphorus by an up flow anaerobic sludge blanket (UASB) coupled
with immobilized biological aerated filters (IBAFs). The ability to degrade the oil and
to remove the COD was observed utilizing Yarrowia lipolytica W29 immobilized by
calcium alginate (Wu, Ge, & Wan, 2009). The results inferred that the microorganisms
Y. lipolytica have a great thermostability degrading the immobilized cells and can be
applied to a wastewater treatment system.
3.4 Results
Table 3.1
A. Overview on oil pollution and its effect on environment
62
3. Oil pollution and municipal wastewater treatment: issues and impact
TABLE 3.1 SWOT analysis for the different processes.
Processes
involved
(1)
Floatation
Strengths
Weaknesses
1. Oil removal is more
than 90%.
2. High processing
capacity.
3. Less sludge
production.
1. Maximum allowable
concentration was less
than 10 mg/L.
2. The dissolved air
floatation stays there a
long time.
(2)
1. Can easily remove
Coagulation
dissolved oil and
emulsified oil.
2. High separation
efficiency.
(3)
Membrane
separation
1. Good for removing
dissolved organics.
2. Use of special porous
material for the
physical removal of
contaminants.
(4)
Biological
treatment
1. Elimination of
secondary clarifiers.
2. Reduce the capital
cost.
Opportunities
1. High oil-water
separation
efficiency.
2. COD removal
rate . 5 80%.
3. Activated carbon
treatment can
also be used here.
1. Complex treatment of 1. Oil removal
some biodegradable
efficiency was
organic polymer.
greater than
2. COD removal rate was
99%.
very less.
2. Composite
flocculants can
be used.
1. May lead to scaling
1. Less pollution.
and corrosive issues.
2. Very cost2. Pretreatment is needed
effective process.
to reduce the
3. Separation
concentration of
process has less
suspended solids.
energy
consumption.
1. Complex control
systems.
2. Total organic carbon
degradation efficiency
was very less.
1. Biological filters
and activated
carbon are
widely used.
2. Better treatment
effects.
3. UASB filters can
be used.
Threats
1. Repairing
problems.
2. High energy
consumption.
1. The oily
wastewater
composition was
complex.
2. Suspended solid
concentration was
very low.
1. Treated water will
be contaminated if
there is no
backwash.
2. Hybrid membrane
separation is better
than single
membrane.
1. Extensive use may
lead to high level
of maintenance.
2. A very timeconsuming process.
3.4.1 Future perspectives
3.4.1.1 Environmental impact of wastewater containing oil
The water bodies worldwide have been increasingly polluted with oily water which creates an indispensable effect on the ecosystem and destruct the shelf life of marine and
human life. Formation of a layer of oil due to the presence of oil, petroleum, crude oil, and
grease causes significant pollution problems such as reduction of light penetration and photosynthesis (Mohammadi & Esmaelifar, 2005). Effects of oil and grease in the wastewater
streams consequently increase the costs of maintenance including in sewers, pipes, pumps,
filters (Stams & Oude, 1997). Oil pollution in the wastewater streams has been a significant
focus of research for the marine environment, and degradation of oil is the major potential
issue for aquatic environment including flora and fauna. This also leads to explosion
hazards in the treatment works (El-Bestawy et al., 2005). Oil and grease cause an offensive
odors and taste for the municipal wastewater treatment (Baig, Mir, & Bhatti, 2003).
A. Overview on oil pollution and its effect on environment
References
63
3.4.1.2 Challenges and issues faced due to oil and municipal solid waste pollutants
The mitigation of challenges for the separation of oil, grease, and petroleum sources from
wastewater harms the industries and human population. For the unsaturated LCFA, it adversely
affects the environment by the toxic products through both methanogenic and acetogenic bacteria
and the application of anaerobic treatment to wastewater containing oil and grease (Rinzema,
Boone, & Lettinga, 1994). The development of a new model UASB has quite improved the efficiency of treatment of wastewater containing sludges and oil (Angelidaki & Ahring, 1992). One of
the challenges that mostly concerns the industrial wastewater is the amount of TDS especially
chloride, sulfate, lead present in water. These can adversely affect treatment plants increasing the
salinity, on the flocculation and coagulation techniques. If the chloride and sulfate concentration is
high, it damages the performance of the plant thus reducing the quality of the effluent.
3.5 Conclusion
Waste effluent which contains oil, grease and domestic waste are increasing sequentially in
volume due to the expansion of the industrialization worldwide. This increasing pollutant
averts immense negative impact on human and aquatic life as well as the ecological environment. Therefore, the treatment of this waste is essential. The traditional method for the treatment of waste effluent mainly comprises of coagulation and floatation, whereas the advance
method includes membrane separation and biological treatment. The biological treatment is the
best treatment plant because is produces a negligible amount of waste. This has identified oil
and municipal waste as emerging contaminants of concern in waterbodies. This research paper
has discussed the sources of the pollutant along with their treatment method. The strengths and
weaknesses of the treatment methods are also discussed in detail.
Acknowledgements
All authors are thankful to Jadavpur University for their sincere guidance and support at each level of the
research. This work was financially supported by Jadavpur University.
Conflict of interest
There is no conflict of interest.
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A. Overview on oil pollution and its effect on environment
C H A P T E R
4
An overview of worldwide regulations
on oil pollution control
K. Krishna Koundinya1, Surajit Mondal1 and Amarnath Bose2
1
Department of Electrical and Electronics Engineering, University of Petroleum and Energy
Studies, Dehradun, India 2Department of Health Safety and Environment Engineering,
University of Petroleum and Energy Studies, Dehradun, India
O U T L I N E
4.1 Introduction
66
4.1.1 Maritime effects of oil spillage
66
4.1.2 Significance of oil pollution control
management
68
4.2 International laws on maritime
pollution
primary provisions of the 1973
convention are summarized below 71
4.4.2 Other conventions and instruments
on the Regional Basis
72
4.5 MARPOL Convention—73/78
4.5.1 Annex I
4.5.2 Annex II
4.5.3 Annex III
4.5.4 Annex IV
4.5.5 Annex V
4.5.6 Annex VI
69
4.3 195462 Convention and its
amendments
70
4.3.1 Origin and establishment of 1954
convention
70
4.3.2 1969 and 1971 Amendments
70
4.6 Oil Pollution Act, 1990
77
4.6.1 Origin of Oil Pollution Act, 1990 77
4.6.2 Progress of Oil Pollution Act,
1990 in oil pollution control
79
4.4 International conference on marine
pollution, 1973
71
4.4.1 Annex I of the convention consists of
the regulations for oil pollution control
and prevention which are primarily
focussed on modifying all the
provisions of 1954/62 convention and
amendments as per requirement. The
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73
73
74
75
76
76
77
65
4.7 Conclusions
80
References
82
© 2022 Elsevier Inc. All rights reserved.
66
4. An overview of worldwide regulations on oil pollution control
4.1 Introduction
Many international organizations such as IMO, WHO, IMCO, UNESCO, IOC and other
pollution control bodies jointly adopted an appropriate definition of marine pollution that
“the hazardous or harmful effects which effect flora and fauna of the marine system from
the causes of direct or indirect inventions of humans into the marine environment including all the marine activities” by considering various social, economic, political, and legal
factors (Schachter, 1971). The global requirement of oil leads to the exploration even from
oceans thus drilling, pipeline installation, and marine transportation got lifted up for
global oil supply and consumption, but oil is one of the most happening forms of marine
pollutants with serious consequences over marine ecosystems, wild life, and resources. Oil
pollution takes place in the form of oil spills/seeps either naturally or by human activities
which in general caused by any crude oil-based liquid products such as hydrocarbons
with higher molecular weights, viscosities and densities and gaseous products such as
non-marshal volatile hydrocarbons, polycyclic aromatic hydro carbons which structure is
shown in Fig. 4.1, produced from the partial oxidation chemical reactions, metals like arsenic, lead, chromium, etc. from various pollutant source inputs (Nriagu, 2019).
Various oil source inputs to the marine environment which lead to oil spill incidents to
take place are reported in Table 4.1 based on offshore sources, transport sources, and
land-based sources such as (National Research Council, 2003)
1. Natural seeps are caused when the underground crude and natural gas spilled into the
oceans through sludge or sediments which contribute the largest proportion of marine
pollution.
2. Extraction, transportation and consumption of crude derives or petroleum products.
3. Functional discharges like cargo oil, grounded vessels, fuel dumping, machineries.
4. Industrial waste water sludge on to the seafloors directly or through inland rivers &
run-offs.
5. Atmospheric depositions of volatile hydrocarbons and pipe line spills.
4.1.1 Maritime effects of oil spillage
The oil pollution can influence both environmental and socioeconomical aspects
which result in loss of marine lives, aqua cultures, seashores, human health, etc. The
oils form slick in various colors based on their properties on the surface of water and
FIGURE 4.1 Polycyclic aromatic structure.
A. Overview on oil pollution and its effect on environment
67
4.1 Introduction
TABLE 4.1 Summary of some major global oil spills and their effects on the marine environment (Ji, Xu,
Huang, & Yang, 2020).
S
No Incident/accident
Location
Oil spilled out
Reasons, results, and losses
1
The Persian Gulf War Oil
Spill (1991, August 2)
Persian Gulf,
Kuwait
380520 million gallons
• Iraq burnt hundreds of Kuwaiti oil wells
which continue to burn for months
2
The BP’s Horizon Oil
Spill (2010, April 20 and
September 17)
Gulf of Mexico
April—natural gas spilled
out,September—134
million gallons
3
The Ixtoc-1 oil spill (1979
June1908 March)
Bay of Campeche
126140 million gallons
4
The Atlantic Empress Oil
Spill (1979, July 19)
Atlantic Ocean, at
the Islands of
Trinidad and
Tobago
90 million gallons
5
The Mingbulak or
Fergana Valley Oil Spill
(1992, March 2)
Uzbekistan
88 million gallons
6
The Kolva River Spill
(1994)
Russian Arctic
84 million gallons
• Natural gas burst out from capsized well
cap
• 11 fatalities and 17 got seriously injured
• 2100 km of United States gulf coast from
Texas to Florida was coated with oil.
• Explosion during drilling under 164 feet
from seafloor which resulted in raising of
mud, oil and natural gas
• Loss of money, lost tourism
• Reduced the commercial fishing for 5 years
• Oil spilled into 16 km off the islands due to
the collision of VLCC’s Atlantic Empress
and Aegean Captain during a tropical
storm
• Ships caught fire and ignited the oil spilled
• 27 sailors died and out of luck there was a
less environmental damage
• A well blow out spewed the oil into the
valley of Fergana
• Continuously burned for 2 months when
fire caught
• More than 88 million gallons of oil was
protected from fire behind the dikes and
berms
• Oil spilled for almost 8 months and 72 sq.
miles of Tundra and Wetlands
7
The Incidents at Nowruz
Oil Filed (1983, February
10 & Iran-Iraq war
period)
Northern Persian
Gulf
In February, 733,000
barrels of oil and in war
period, nearly 80 million
gallons
8
The Castillo de Bellver
Oil Spill (1983, August 6)
South Atlantic
Ocean, South
Africa
110,000 tons of oil
9
The Amoco Oil Spill
(1978, March 16)
Coast of Brittany,
France
69 million gallons
• Iranian Oil Field was struck by the tanker
which resulted in corrosion and toppling of
platform due to waves.
• One month later the tanker collision took
place, Iraqi helicopters attacked the nearby
platforms resulted oil spills
• 20 people died trying to cap the wells and
2/3 rd of oil spilled
• Tanker broke into 2 pieces
• Caught the fire & drifter to 24 miles of
coast before it sank in deep water
• Oil was floated on surface was caught in
Benguela Current
• Hydraulic system and rudder got damaged
• 200 miles of French coast was polluted by
oil slick
• Huge loss of marine lives and
contaminated the oyster beds in the zone
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4. An overview of worldwide regulations on oil pollution control
FIGURE 4.2 (A) Amoco Cadiz oil spill (The Editorial Team, 2019) (B) fire demolished LPG carriers (Maritime
Herald, 2019).
migrates due to the ocean currents. The speed of currents has higher influence on
migration of oil spillage when compared to the rate of oil spillage (Rafferty, 2020). The
oil spillage tends to some serious accidents and two major accidents among them are
shown in Fig. 4.2A and B and environmental impacts such as explosion, firing, capsizing, global warming, greenhouse gases emission, particulate emissions that form a
ground level ozone layer and smog which have carcinogenic effects on the functional
organs such as respiratory system.
4.1.2 Significance of oil pollution control management
Apart from natural occurrence the other sources of oil pollution can be managed in
order to minimize the marine pollution due to the oil seeps as a small amount and constant rate of oil spill into the inland water bodies (seas) can be assimilated to the ocean
environment. From 2010 to 2019 nearly 415 incidents took place and the proportions per
year are represented in Fig. 4.3.
The serious need in marine, ecological, and environmental stabilization puts many
international organizations together to govern the oil pollution control management by setting many laws, rules and regulations in implementation on the national basis and global
basis depending upon the oil management proportions. Every country has its own policies
and regulations to control the oil pollution which are derived from the worldwide regulation to analyze the social, economic, and environmental losses statistics if any maritime
incident/accident occurred and to take some measures to prevent such phenomena to
happen again by implementing various regulations and laws such that every maritime
operation such as exploration, drilling, oil extraction, transportation, as a result the transportation of petroleum products through pipelines minimized the tankers usage as shipping activities are the primary source of marine pollution and hence the existing rules are
mostly related to vessel source pollution. The factors like precautionary methods, polluter
compensation concepts, vigilant technologies, and healthy environmental practices
(OSPAR, 2019) should be adopted along with EPA and FRP rules while plotting a
regulation.
A. Overview on oil pollution and its effect on environment
69
4.2 International laws on maritime pollution
[PERCENTA
[PERCENTA
[PERCENTA
[PERCENTA
GE]
GE]
GE]
GE]
[PERCENTA
GE]
[PERCENTA
GE]
[PERCENTA
GE]
[PERCENTA
GE]
[PERCENTA
GE]
[PERCENTA
GE]
2010
2011
2012
2013
2014
2015
2016
2017
2018
2019
FIGURE 4.3 Total number of global incidents occurred in water from 201019 (PHSMA, 2020).
4.2 International laws on maritime pollution
After World War II, the global concern on maritime safety and security became a primary
focus due to the results of military activities in Atlantic Ocean. In 1972, the Stock Holme
Declaration on Human Environment stated that every required practice must be taken in order
to keep the marine environment away from pollution and to protect the lives of humans, marine
ecosystem, and amenities of seas and oceans in principle 7 and about liabilities & compensations
regarding marine pollution in principle 22. Region wise marine pollution monitoring was implemented by “United National Environment Program” which adopted the regional seas action
plans for monitoring the pollution prone regions and this could solve transboundary problems
like Mediterranean region which was first covered. The general measures taken by the legal field
to protect the marine environment from oil spills especially from ships have four objectives.
1. To reduce the unnecessary oil discharges by the tankers and ships for cleaning, filling
purposes, etc.
2. Preventing accidents to take place as there might be a chance of oil spillage if any of the
ships is carrying oil products.
3. Following various methods and implementing some viable technologies that minimize
the accidents and protect marine environment.
4. To keep the sailors and those who travel through ships safe and to compensate the
victims if suffered by any accident as a result of pollution.
Oil Pollution was not projected as an issue in global conventions on the Law of the Sea
where Geneva Conventions of 1958 focused on oil spill through pipelines and other sea
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4. An overview of worldwide regulations on oil pollution control
bed activities which provoked the coastal states to establish safety zones around the offshore installations to protect the marine living resources from oil pollution.
4.3 195462 Convention and its amendments
4.3.1 Origin and establishment of 1954 convention
In 1954 governments of United Kingdom and United Nations held an international conference in London from April 26th to May 12th 1954 with the aim to regulate the oil discharges
from the tankers and ships which was the first step taken toward the reduction of global oil pollution and the respective regulations were confessed by the convention are described below.
1. The ships or tankers should not discharge any oils and their mixtures into the
prohibited zones established by the convention (Curtis, 1985).
2. The violations of the rules by any ship “shall be an offense punishable under the laws
of territory in which the ship was registered” (Boyle, 1985).
3. Huge penalties are imposed “if the violation of rules is done outside the territories
when compared to the penalties for unlawful oil discharges in the territorial waters of
the states concerned” (Mensah, 1976).
4. The convention also confessed that every ship within its jurisdiction must be well fitted
in order to avoid the unwanted and excess oil spillages or leakages by passing the oils
through oil-water separator (Concerning, 2010).
The convention officially started or came into existence in January 1959. The convention
synchronized the violations and contraventions by providing facilities for unwanted or disposed residue discharge from oil ballast and tankers into the ports by maintaining the regular records to inspect the operational discharges of ships in their territories and ports and
these records followed by laws and other legislative aspects regarding conventional provisions in the state territories were sent to the Bureau of Conventions of the contracting parties. IMCO had become the depositary of this convention and again a conference was held
to review the 1954 convention and adopted the amendments that extended the oil discharge
prohibition zones and also the application of lesser gross tonnage ships. An article that
empowered the IMCO assembly, was revised and with the support of IMCO maritime
safety committee (MSC), was sent to the contracting governments for acceptance and since
June 1957, the convention as amended in 1962, came into force and these provisions are currently followed by 52 states which means over 91% of the ocean ships and 95% of the world
tanker fleet are being run with the provision of 1954 convention.
4.3.2 1969 and 1971 Amendments
By resolving A 172 (VI) the IMCO Assembly adopted some amendments to 1054 convention and its annexes as amended in 1962 (Mensah, 1976), with following limitations.
1. Oil discharge quantity in any ballast voyage should be 1/15000 of the cargo vessel
carrying capacity.
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2. The discharge rate of oil was limited to almost 60 L per mile traveled by the ship.
3. Within 50 miles of the nearest land, oil discharge into the waters is prohibited.
The 1969 amendments introduced new oil record process that had concerned with the
liberal observance of the convention and the ships carrying flags of respective countries
should give a notice to the IMCO for delivering the particulars to other government. These
amendments minimized the quantity of oil discharged into seas and achieved an appreciable progress in reducing the oil pollution.
In 1971, by resolving A 232 (VII) the IMCO Assembly adopted an amendment to the
convention for protecting Great Barrier Reef Area because of its uniqueness in scientific
and environmental significance as by 1969, they came to a conclusion that long vision
development regarding industrial aspects and maritime operations with respect to ships
had introduced some problems which could not be handled with the perspective measures
of 1954/62 Convention which made IMCO to propose another conference in 1973 to adopt
the new international provinces and focus on contamination of not only seas and oceans
but also air and land by ships, vessels, etc that are used for any maritime operation.
4.4 International conference on marine pollution, 1973
This conference aimed at a complete elimination of global intentional oil discharges and
other hazardous toxic substances into water bodies along with regulating the accidental
discharges that happen and this conference work is extended to all shipborne proportions
of oil related pollutants.
4.4.1 Annex I of the convention consists of the regulations for oil pollution
control and prevention which are primarily focussed on modifying all the
provisions of 1954/62 convention and amendments as per requirement. The
primary provisions of the 1973 convention are summarized below
1. The regulations regime of convention is applied both for all types of oils as “Load on
Top” system prevents the unwanted oily mixtures discharge into the waterbodies and
stored at the top of cargoes in the tanks where the non-polluting sediments and parts
are disposed into water and for those ships which could not carry the oils at the top
would be provided the receivers at the ports to discharge such polluting oils by
providing an appropriate fitting with the corresponding equipment like oil discharge
monitoring and control systems, tanks, pipelines and pumps (Mensah, 1976).
2. Two new requirements were added to the tanker construction where the first one was
the limit of dead-weight was 70,000 tons for a new tanker or the ballast tanks are to be
provided to increase the capacity of ships instead of carrying the segregated ballast water
through cargo oil tanks for efficient operation of tankers and the other requirement was
to enable the survival of tankers after collisions or stranding (Mensah, 1976).
3. The other important feature was provision on special areas in which the specified areas
are pollution prone, oil discharges are strictly prohibited. Mediterranean Sea Area,
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4. An overview of worldwide regulations on oil pollution control
Black Sea Area, Baltic Sea Area, Red Sea and Gulf areas come under the prohibited
zones (Mensah, 1976).
4. The 1973 convention also prohibited the violations of requirements and based on the Law
of Administration of the ship irrespective of the region of violation took place, the
sanctions will be established and if the violation takes place in any jurisdiction of any
parties, then the sanctions are established based on the law of that party (Bodansky, 1991).
5. If the evidence regarding or against violation that took place either in jurisdiction of a
party or out of the jurisdiction, can be submitted to the convention to prove the
violation occurrence.
The 1973 conventions did not include some aspects such as direct release of oil during
exploration, exploitation and mineral source processing but covered almost all incidents of
marine pollution and to develop the convention provisions an article was incorporated in
order to provide numerous methods for convention amending and its annexes (Mensah, 1976)
under the guidance of IMCO got circulated to various state parties for acceptance and brought
into force by the “explicit act” of a major number parties. The 1973 convention finally entered
into force after one year of acceptance given by at least 15 states, not less than 50% of global
shipping merchants. The 1973 Convention did not cover the spills arise due to the operations
of some devices such as drilling rigs which are engaged in exploitation and exploration.
There are other conventions that were established with the prime focus in preventing
accidents due to the oil spills in order to promote maritime safety with higher standards.
The important such conventions are
1. The International Convention on Safety of Marine lives, 1960 which adopted the
amendments from 1966 to 1973 (Bleicher, 1972).
2. The international Regulations for preventing Collisions at Sea, 1960.
3. The International Regulations for Preventing Collisions at Sea, 1972 (Mensah, 1976).
4. The International Convention on Load Lines, 1966 (IMCO, 1969).
5. The International Convention on Safety of Life at Sea, 1974 (IMO, 1974).
Some other instruments were designed specifically to eliminate the pollution accidents
such as 1971 amendments to 1954/62 Convention and other amendment was adopted by
IMCO to deal with pollution due to the substantial increase in sizes of tanker (Mensah,
1976) or vessel by giving the limitations as the size of the individual tanks were permitted
to the strength up to 100,000 ton capacity of the “Torrey Canyon” because the level of pollution arise when such large dimensional designed ships involved in collisions or stranding
made IMCO to have a concern on limiting the oil spills in such case of accidents or incidents, hence the 1969 Civil Liability Convention entered into force on June 19, 1975.
4.4.2 Other conventions and instruments on the Regional Basis
These conventions deal with not only oil pollution but also the other pollutants that pollute marine environment to be comprehensive in scope and not confined to the oil exclusively. Some important Conventions and Instruments are;
1. The Convention in 1974 for Nordic Environmental Protection
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4.5 MARPOL Convention—73/78
73
2. The Paris Convention on the Prevention of Land-Based Sources of Pollution.
3. The Convention on the Protection of the Marine Environment of the Baltic Area of 1974.
The “Torrey Canyon” incident was the first major oil pollution which had a strong impact
on the development of the international law and marine environmental legislation to step up
for the formation of “International Maritime Organization” to improve the international liability
and compensation for oil spillage and also established MSC to deal with environmental issues.
4.5 MARPOL Convention—73/78
MARPOL was adopted by IMO on November 2, 1973 and the prime attention of
MARPOL was keen towards maritime pollutants in the form of oils, sewages, chemicals
and other leakages or spills due to operations and accidents. 1978 MARPOL protocol was
adopted and some measures were incorporated to prevent the tankers from polluting the
maritime environment, in a conference on February after the disaster of tankers accidents
in the period of 19761977. The Regulations of MARPOL Convention were aimed on all
types of polluting sources like accidents and routine operations by interpreting six
Annexes for preventing any accidents to take place which are listed in the Table 4.2.
IMO introduced measures through MARPOL Convention which made a major impact
on maritime pollution control by reducing the oil spillages with safe construction and
operational procedures. The persistent spilled oil residues and water-in-oil emulsions will
be the main threat posed to Marine mammals and reptiles, birds that could come into contact with a contaminated sea floors and also effects onshore marine life.
4.5.1 Annex I
4.5.1.1 Measures to control operational discharge of oils according to annex I
Oil discharge either outside or inside the special areas from a 400 tonnage and above
tankers or ships can be permitted when;
1. There must be an installed oil filtering equipment as per the requirement of Annex
2. Oil content of the effluent from the ships or tankers should be diluted at most to 15 ppm.
3. Effluents should not be mixed with the oil cargo residues.
4. Specific in Antarctic zone any kind of oil discharge is strictly prohibited.
5. Oil Record book should be maintained with machinery space operations and Ballast
operations.
4.5.1.2 Shipboard oil pollution emergency plan
Oil tanker of greater than or same as 150 gross tonnage and every ship of 400 gross tonnage and above shall carry on board Shipboard Oil Pollution Emergency Plan governed
by the Administration by reporting any incident or accident if occurred, determining the
statistics of losses, compensations and liabilities including the plan of action to reduce the
oil pollution with the governance of the national authorities in combating the oil pollution.
The special areas focused by this Annex are the Mediterranean Sea area, the Baltic Sea
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TABLE 4.2 List of Annexes of MARPOL Convention (MEPC 58, 2008).
Annex Point of attention and regulations
Entered into force
Revised annex
entered into force
I
Regulations for the Prevention of Oil Pollution
2nd October 1983
1st January 2007
II
Regulations for the Control of Pollution by focusing on
Noxious Liquid Substances in Bulk
2nd October 1983
1st January 2007
III
Prevention of Pollution by Harmful Substances packages
across seas and oceans
1st July 1992
1st October 2010
IV
Prevention of Pollution by Sewage from Ships
27th September 2003
27th September 2003
V
Prevention of Pollution by Garbage from Ships
31st December 1988
1st January 2013
VI
Prevention of Air Pollution from Ships
19th May 2005
1st July 2010
TABLE 4.3 List of various Oils accidental or due to operational spills (Mensah, 1976).
S No
Classification
1
Asphalt oils
Blending stocks, roofer flux, straight run residues
2
Gasoline blending stocks
Alkylates (fuel), reformates, polymers (fuel)
3
Distillates
Straight run residues and flashed feed stocks
4
Gasolines
Automotive, aviation, straight run, kerosene, fuel oil (1-D, 2, 2-D)
5
Jet oils
JP-(1, 3, 4 and 5), Turbo fuel, kerosene, mineral spirit
6
Naphtha
Solvents, petroleum, heart cut distillates
area, the Black Sea area, the Red Sea area, the Gulfs area, the Gulf of Aden area, the
Antarctic area, the Northwest European waters including the North Sea, the Irish Sea,
the Celtic Sea, the English Channel and part of the North East Atlantic near Ireland, the
Arabian Sea near Oman and the Southern South African waters. The list of oils that were
spilled in general are listed in Table 4.3.
4.5.2 Annex II
4.5.2.1 Main features of annex II of MARPOL
The Annex II of MARPOL categorizes the effluents that are discharged into seas as X
which has greatest threat to the marine environment, Y with moderate threat and Z with
the least level of threat carried by the vessels or tankers in bulk based on their threat levels
on the marine environment, amenities and human health. This Annex also interpreted
some standard procedures and regulations that should be either in English or French or
Spanish through the manual with respect to Cargo handling, tank cleaning, slop handling,
ballasting and de-ballasting the cargos and in case if the manual is in other language then
the format should be translated into any of the above three languages according to
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Appendix 4 of Annex II. The record book is the ship’s official log book in the form specified in IBC amendments of Appendix 2 of Annex II and various details such as loading/
unloading the cargo, pre wash/cleaning the cargo according to the manual provided,
internal transfer, ballasting/de-ballasting and accidental or operational discharges of oils
are included in the record book.
4.5.2.2 Shipboard marine pollution emergency plan for noxious liquid substances
Every ship of 150 gross tonnage must have a shipboard marine pollution emergency
plan for Noxious Liquid Substances approved by the Administration to report a Noxious
Liquid Substances pollution incident with a detailed plan of action that to reduce or control the discharge of Noxious Liquid Substances following the incident and this must be
governed by the national authorities to reduce the pollution. Antarctic zone is the special
area for this Annex.
4.5.3 Annex III
4.5.3.1 Main features of annex III of MARPOL
This Annex describes the requirements in detailed such as standards on packing, marking/labeling, documentation, stowage, quantity limitations, exceptions and notifications
for preventing pollution from pollutants by adopting the amendments of International
Maritime Dangerous Goods (IMDG) Code, which has been amended for the transportation
of harmful substances including marine pollutants and every pollutant must be labeled
with the standard marine pollutant mark which was made a mandatory form in May 2002
by IMO and IMDG finally entered into the force on January 1, 2004.
The regulation 7 of this Annex states that “appropriate measures will be taken depending up on the physical, chemical and biological properties of pollutants and regulate the
washing of leakages overboard without impairing the safety of the ships and persons on
board” which has two parts of volume code as described in Table 4.4 and this Annex is
applicable for all types of ships and vessels carrying hazardous materials in packaged
form or road and rail carry wagons.
For every two years, IMO incorporates the changes in IMDG Code with new amendments with the approval of MSC.
TABLE 4.4 Parts of two volume code (MEPC 58, 2008).
Volume 1
First 7 parts of the code
excluding part 3
• Classification of the general-provisions, Packing & Tank Provisions,
Consignment Procedures are described
• Construction and Testing of packages, IBCs, portable tanks, MEGCs
and road tank vehicles and their Operation
Volume 2
Part 3, appendix An and
appendix B
• Harmful packages of goods, provisions including exceptions
• Generic and N.O.S. Proper Shipping Names
• Glossary of terms
• An Index
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4.5.4 Annex IV
4.5.4.1 Main features of annex IV of MARPOL
Many legal requirements are plotted by Marine Environmental Protection Committee in
2011 from the resolution MEPC.200(62) which adopted the amendments that consider the
Baltic Sea as a Special Area and introduced some discharge requirements for passenger
ships in the special areas. A set of regulations are provided for controlling sewage discharge into the seas from ships within a specific distance from the nearest land and also
included a legal model of International Sewage Pollution Prevention Certificate which
should be issued by National Shipping Organizations to ships under the government to
ensure the adequate provision of facilities at ports and terminals for sewage discharge.
4.5.4.2 The revised annex IV
The revised Annex for new ships on December 3, 1976 engaged in the international voyage of gross tonnage should be provided with sewage treatment plant with the international standards while IMO by Resolution MEPC.2(VI) adopted the installation,
construction and calibration of sewage treatment systems is or a sewage holding tanks
which are to be certified by more than 15 persons. Shipboard Sewage Pollution Sources
such as drainages and other waste waters need the regulations but disposal of drainage
from dishwasher, shower, laundry, bath and washbasin drains—gray water don’t require
any regulations as they are not considered as pollutants. The revised Annex can be applicable for all types of passenger ships which includes new standards/tests for sewage treatment plants with the installation of Advanced Waste Sewage Treatment Systems. This
Annex came into force on January 1, 2013 and from January 1, 2018 the sewage discharge
in the Baltic Sea Area was prohibited.
4.5.5 Annex V
4.5.5.1 Legal requirements for the Annex V
This Annex mainly focuses on the garbage that was produced from the ships which
majorly affect the marine lives. Many wastes like plastics that float on water and also nonbiodegradable will be consumed by many fish and mammals of the seas by mistaking the
plastic as food, trapped in the plastic covers, nets, fish gears, incinerated ashes, animal carcasses, and cargo residues. These garbage materials were added to the seas/oceans by the
fishermen who throw away the unwanted and used items, people who throw the waste
onshore and also through rivers and canals from cities/towns. The garbage is also produced from the ships that are passing through the oceans or seas. MARPOL aimed to
eliminate the garbage generation across the seas.
4.5.5.2 Restrictions and garbage management
According to Annex V the garbage includes waste food, domestic and operational waste
produced from the ships by prohibiting the disposal of plastics anywhere into the sea, and
restricts discharges of any garbage (that harm marine lives) from ships into coastal waters
by providing the facilities at ports and terminals for the reception of garbage. IMO
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4.6 Oil Pollution Act, 1990
77
Guidelines MEPC.220(63) describe various garbage management aspects like garbage minimization, storage, collection and processing. The ships of minimum 400 gross tonnage
should be verified and certified by 15 persons of respective jurisdiction.
The prohibition zones for this Annex are the Mediterranean Sea, the Baltic Sea Area, the
Black Sea area, the Red Sea Area, the Gulfs area, the North Sea, the Wider Caribbean
Region and Antarctic Area. MEPC/Circ.317 gives Guidelines for developing the garbage
management plans and an Appendix to Annex V of MARPOL to give a standard form for
a Garbage Record Book.
4.5.6 Annex VI
4.5.6.1 Application
This Annex can be applicable for all ships of 400 gross tons and above which must carry
IAPP Certificate and ships of less than 400 gross tons should comply with legislation
where applicable with appropriate measures and this Annex is complied with the following regulations.
1. Regulation 12: Ozone depleting substances
2. Regulation 13: Nitrogen oxides (NOx)
3. Regulation 14: Sulfur oxides and Particulate Matter (SOx)
4. Regulation 15: Volatile organic compounds
5. Regulation 16: Shipboard incineration
6. Regulation 17: Reception Facilities
7. Regulation 18: Fuel oil quality and availability
The summary on recent and upcoming worldwide regulations are discussed in
Table 4.5. There are various energy efficiency regulations introduced for ships of 400 gross
tons and above. They are (https://www.lr.org/en-in/marpol-international-convention-forthe-prevention-of-pollution/)
1. Energy Efficiency Design Index (EEDI)-to calculate CO2 generated per tonnage to
approach the energy efficiency calculations.
2. Ship Energy Efficiency Management Plan (SEEMP)-to establish a mechanism for the
optimum performance with good energy efficiency of a vessel in a cost-effective
manner
3. International Energy Efficiency Certificate-Certificate that covers both EEDI & SEEMP.
4.6 Oil Pollution Act, 1990
4.6.1 Origin of Oil Pollution Act, 1990
After the spill of Exxon Valdez which carried up to 70,000 barrels of oil on March 24th,
1989 in United States; the Congress voted to pass Oil Pollution Act in 1990 (US Coast
Guard, 1991) which amended the Federal Water Pollution Act and outlines to prevent,
control and respond to the oil spills by introducing additional restrictions by mandating a
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TABLE 4.5 Summary on recent and upcoming regulations of MARPOL Convention (MARPOL, 1973).
Annex Regulation Into force
Applicability
Progress
I
28
1st January Authority of oil tankers, chemical Requirements for oil tankers are introduced
2016
tankers and gas carriers
for stability instruments for intact and
damage stability
VI
13
1st January Authority, labor and other
Tier III requirements are introduced to
2016
shipbuilding-related stakeholders control NOx emissions from diesel engines
VI
13.7
1st March
2016
I
12
1st January All ship owners and managers
2017
Requirements for sludge piping are
introduced into Regulation 12
VI
13
1st
September
2017
Requirements to record when engines are
altered from Tier II operation to Tier III
operation on applicable ships entering Tier
III ECAs.
IV
11 & 13
1st June
2019
All ship owners and operators
Introduction of the Baltic Sea Special
Area requirements until 2019 for new
passenger ships and 2021 for existing
passenger ships by changing the format
of ISPP certificate
VI
22 A
1st March
2018
Authority of ships that are
subject to air emission controls
New requirements for ships of capacity
5000 gt are introduced in order to record
the report of ship fuel-oil consumption data
of 2019
V
1.2
1st March
2018
Ship owners, operators, and
managers
Cargo residues, including the cargo hold
washing water and e-wastes are considered
pollutants.
VI
14.1.3
1st January Authority of vessels subject to
2020
MARPOL VI
Ships when operating outside the existing
ECA for SOx emissions, any fuel oil used
on board should be limited to 0.50% sulfur
content.
VI
14.1
1st March
2020
Authorities of ships that are
subject to air emission controls
under MARPOL Annex VI
Ships when operating outside the existing
ECA for SOx emissions, any fuel oil used or
carried on board should be limited to 0.50%
sulfur content.
VI
13
1st
January,
2021
New ships constructed from 1
January 2021 operated in
European waters
Introduces two new NOx Emission
Control Areas in various areas which
requires Tier III engines for ships
operating, which are constructed from 1 st
January 2021 or have “non-identical”
replacement engines or additional
engines installed.
All ship owners and operators
Modified the IAPP Record of Construction
format.
A. Overview on oil pollution and its effect on environment
4.6 Oil Pollution Act, 1990
79
double hull requirement of United States operating tank barges, newly built tanks and created a phrase out schedule for existed tanks and single hull tankers began to phased out
from 1985.
4.6.2 Progress of Oil Pollution Act, 1990 in oil pollution control
The United States Coast Guard was established by OPA which is supposed to consistently
enforce the law, embrace the businesses and communities to comply with OPA with an effective utilization of resources and training their personnel to handle all OPA related aspects. The
work was extended to authorize the Oil Spill Liability Trust Fund for which the fund was originally established in 1986. Crude oil tax on barrels produced within or imported to the U.S was
the financial factor of OPA and can distribute up to one billion dollars per incident to compensate the victims of oil spills and is governed by the federal government. Various assessments
such as federal, state, etc. oil spill removals and damage could be qualified to use the fund.
OPA laid the penalties for companies responsible for oil spills and gave numerous guidelines
on the perceptions like response and counter measures to be taken for a spill if takes place in
order to minimize the oil spills and the impact of the spill and the amendments are adopted by
taking the present best practices into consideration. OPA introduced the International
Regulation “The Convention on Civil Liability” and other regulations but oil companies have
found loopholes in the system to avoid the penalties. The OPA, promulgated by the United
States Congress, introduced the double hull standards for oil tankers which was called
“Draconian Legislation” which led to an idea concerning the vessel tank was familiar as in 1971
the amendments to the OILPOL have been elaborated which regulated the tank sizes of ships
in order to reduce the pollution. However, ship construction industry at that time opposed this
amendment proposal, hence the Amendments did not enter into force and as OPA was first
enacted, major ship owners proposed only chartered vessels usage to carry oil into the United
States and refused to enter certain ports. Apart from drawbacks, the OPA made a remarkable
impact in United States maritime operations and on oil pollution to decline rapidly. Later many
organizations were established in order to protect the marine environment. Some of such are
discussed in Table 4.6 and some regional conventions are mentioned below.
• Art. 8 of the Abidjan Convention, 1981 focused on protecting and developing the
Marine and Coastal Environment of the West and Central African Region;
• Art. 4 of the Lima Convention, 1981 focused on protecting the Marine Environment and
Coastal Area of the South-East Pacific.
• Art. 8 of the Jeddah Convention, 1982 focused on the conservation of the Red Sea and
Gulf of Aden Environment.
• Art. 8 of the Cartagena de India’s Convention, 1983 focused on protecting and
developing the Marine Environment of the Caribbean Region.
• Art. 8 of the Nairobi Convention mainly focused the of the Eastern African Region’s
protection, management and development of the Marine and Coastal Environment.
• Art. 8 of the Nouméa Convention, 1986 focused for the Protection of the Natural
Resources and Environment of the South Pacific Region and related Protocols.
• Art. 7 of the Barcelona Convention, 1976 focused on protecting the Mediterranean
region from pollution.
A. Overview on oil pollution and its effect on environment
80
4. An overview of worldwide regulations on oil pollution control
TABLE 4.6 Summary of various international organizations for global oil pollution control (International
Spill Control Organization, 2013).
Organization
Established Progress and working
APICOM (Association of Petroleum
Industry Co-operative Managers)
1972
It is an advisory body for introducing and developing new
standards, regulations and policies for preventing oil
pollution in global vision
ISSA (International Social Security
Association)
1997
Provides all the events, expert networks, professional
standards, practical services, innovative appropriates and
supplements the global advocacy for socio-security
IMO (International Maritime
Organization)
1948
Shipping regulations, Plotting MARPOL convention
against the oil pollutions from ships and almost all the
world nations follow MARPOL with some required
modifications if any
IGP&I (International Groups of P&I
Clubs)
Covers all the responsibilities of ocean-going voyages
globally by forming 13 clubs for compensating the
international groups
IOPC (International Oil Pollution
Compensation Funds)
1992
Provides pays, compensations for economic damage from
the oil to tankers if any spill takes place
ISCO (International Spill Control
Organization)
1984
Focuses on prevention and countermeasures for oil spills if
took place
ITOPF (International Tanker Owners
Pollution Federation Limited)
1968
Provides the guidelines, technical information documents,
data and statistics to respond for implementing measures
for spills of oils, chemicals and other harmful pollutants
UNEP (United States Environment
Program)
1972
Focuses on Air, Bio Safety, Climate Change, Water
sustainability develop programs, disasters and conflicts
and serves as an administrative advocate for global
environment
INTERTANKO (International
Association of Independent Tanker
Owners)
1970
Focuses on various amendments to authorities of tanks like
operational and commercial aspects
Fig. 4.4 describes the statistics regarding quantity of oil spill per year after the implementation of these many laws and regulations to protect the marine environments due to oil spills.
4.7 Conclusions
The chemicals carried at sea have a hazardous influence on the marine environment
and the oil spills corrupt its ecosystem in numerous ways as when a few tons of oil spills
into the sea it forms slicks with various thickness based on the viscosities of the oils spilled
on the water surface which mostly damage marine life. Since the middle of the 20th century many global legislative measures were adopted to prevent the oil pollution and protect the marine environment by introducing many national laws and regulations which
A. Overview on oil pollution and its effect on environment
4.7 Conclusions
81
FIGURE 4.4 Plot of Oil spilled and progress of regulations in minimizing the global oil pollution (Roser,
2013).
led to the minimization of oil spills with improved tank construction, and other technological advancements like the load-on-top system in order to reduce onshore and offshore oil
pollution. Oil pollution made to introduce many legal documents for marine environment
protection using viable regulations and principles from international environmental law to
embrace the sustainable development even in the aspect of welfare of victims by providing
liability and compensation such as CLC fund if any accident takes along with the application of measures against oil pollution from ships/vessels by governing various conventions like MARPOL and Oil Pollution Act as even a little oil spilled into seas/oceans can
cause irreparable loss and damage. There are many effective policies and instruments to
prevent the oil pollution by clean-up operations, mechanical containment along with
installation of sewage treatment plants and holding tanks. Other counter measures can be
used in emergency scenarios due to their limitations during burning, sinking, grounding,
etc. depending upon a situation arising in order to protect marine environment and
marine lives, but still some obligations for the oil industry are seen as legislation for oil
pollution which has a slow development.
The international organizations modify the regulations based on the requirements
and these regulations do not need to be followed by all parties around the world
depending on their climate conditions, pollution stats, and many other factors. The
exploration and exploitation in the oceans and seas for energy sources cause oil pollution but they are much needed for the further optimization of global energy efficiency
by avoiding accidents and oil spillages in order to protect the marine environment and
ecosystem.
A. Overview on oil pollution and its effect on environment
82
4. An overview of worldwide regulations on oil pollution control
References
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A. 263264 (VIII) 1973.
Bodansky , D. (1991). International convention for the prevention of pollution of the sea by oil, supra note 6,
at 152.
Boyle, A.E. (1985). International convention for the prevention of pollution of the sea by oil, supra note 5, art III.I
Concerning, C. (2010). International convention for the prevention of pollution of the sea by oil, supra note 5, art.
VIII.
Curtis, J.B. (1985). Cited by 50 — International Convention for the Prevention of Pollution from Ships, No- ...
MARPOL 73/78, supra note 2, annex I, regulations 9, 10.
Herald, M. (2019). https://maritime-zone.com/en/news/view/top-latest-maritime-accidents.
International Spill Control Organization (2013). https://spillcontrol.org/2013/02/04/international-organizations/.
IMCO (1969). IMCO Sales No. 1968-3 with amendments adopted by the resolutions of the IMCO.
IMO (1974). International Convention or the Safety of Life at Sea (SOLAS), 1974.
Ji, H., Xu, M., Huang, W., & Yang, K. (2020). The influence of oil leaking rate and ocean current velocity on the
migration and diffusion of underwater oil spill. Scientific Reports, 10, Article number: 9226.
MARPOL (1973). https://www.lr.org/en-in/marpol-international-convention-for-the-prevention-of-pollution/.
Mensah, T.A. (1976). International convention for the prevention of pollution of the sea by oil, supra note 5,
Regulation 25.
Mensah, T.A. (1976). Text in Int’l Legal Materials 267 (1972).
Mensah, T.M. (1976). IMCO Sales No. 1973-3 with amendments adopted by the resolutions of IMCO.
Mensah, T.A. (1976). The text of the 1954/62 Convention, with the 1969 Amendments appears in 9 Int’l Legal
Materials 1 (1970).
Mensah, T.A. (1976). International convention for the prevention of pollution of the sea by oil, supra note 5, art.
VI & art. VII.
Mensah, T.A. (1976). International convention for the prevention of pollution of the sea by oil, supra note 5,
Regulation 1 of Annex I.
Mensah, T.A. (1976). International convention for the prevention of pollution of the sea by oil, supra note 5,
Regulation 15, 16, 17 & 18.
Mensah, T.A. (1976). International convention for the prevention of pollution of the sea by oil, supra note 5, art XVI.
MEPC 58 (2008). IMO, ANNEX VI of MARPOL 73/78, regulations for the prevention of air pollution from ships
and NOx Technical Code.
National Research Council (2003). Oil in the sea III: Inputs, fates and effects, Chapter 3: Input of oil to the sea;
2003. Washington, DC: The National Academies Press. Available from https://doi.org/10.17226/10388.
Nriagu, J. (2019). Oil industry and the health of communities in the Niger Delta of Nigeria by, School of Public
Health, Encyclopedia of Environmental Health, pp. 758766, published on March 2011.
OSPAR (2019). http://www.ospar.org/html-documents/ospar/html/OSPAR-Convention-e-updated-text-2007.Pdf.
PHSMA (2020). https://portal.phmsa.dot.gov/analytics/saw.dll?PortalPages.
Rafferty, J.P. (2020). 9 of the biggest oil spills in history, https://www.britannica.com/list/9-of-the-biggest-oilspills-in-history.
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The Editorial Team (2019). The Acomo Cadiz Oil Spill, Brittany (March 1978). https://safety4sea.com/cm-amococadiz-oil-spill-the-largest-loss-of-marine-life-ever/.
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mil/Mariners/National-Pollution-Funds-Center/About_NPFC/opa/.
A. Overview on oil pollution and its effect on environment
C H A P T E R
5
Technological aspects of different oil and
water separation advanced techniques
Vishal Kumar Singh1, Sankari Hazarika2,
Robin V. John Fernandes1, Ankit Dasgotra4, Poonam Singh3,
Abhishek Sharma4 and S.M. Tauseef 5
1
Department of Health Safety, Environment and Civil Engineering, School of Engineering,
University of Petroleum and Energy Studies, Dehradun, India 2Department of Petroleum
Engineering and Earth Science, University of Petroleum and Energy Studies, Dehradun, India
3
School of Engineering, University of Petroleum and Energy Studies, Dehradun, India
4
Department of Research and Development, School of Engineering, University of Petroleum
and Energy Studies, Dehradun, India 5Centre for Interdisciplinary Research and Innovation
(CIDRI), UPES, India and Sustainability Cluster, School of Engineering, UPES, India
O U T L I N E
5.1 Introduction
83
5.2 Advanced filtration materials
5.2.1 Metal-based membranes
5.2.2 Polymer-based membranes
5.2.3 Ceramic based membranes
84
85
86
88
5.4.1 Template based materials
5.4.2 Micro nanomaterials
5.4.3 Nanobased materials
5.4.4 Nanocellulose based material
5.3 Advanced absorption based materials 89
5.4 Sol-gel based materials
91
92
92
93
5.5 Conclusion
93
References
94
90
5.1 Introduction
Mining, oil industry, food, textile, and other mass processing units all discharge
traces of oil in wastewater, which pollutes the water bodies if discarded without
Advances in Oil-Water Separation
DOI: https://doi.org/10.1016/B978-0-323-89978-9.00006-9
83
© 2022 Elsevier Inc. All rights reserved.
84
5. Technological aspects of different oil and water separation advanced techniques
proper treatment. The International Convention on the Prevention of Pollution by
Sea Vessels had established strict regulations on marine emissions. To successfully
separate oil from the sea, a petroleum water separator must be installed (United
States E. P. Agency and O. of E. and C. Assurance, 2020). Porous materials like
sponges (Guerin, 2002; Nguyen et al., 2017; Zhu et al., 2013), foam (Calcagnile et al.,
2012; Li et al., 2020), and textiles (Li et al., 2015; Zhang and Seeger, 2011; Zhang,
Zhang, & Wang, 2012) are widely used in the separation of oil from water after accidental use. Some research has recently focused on oil and water separation as it
helps deal with numerous industrial wastewater problem. There are various methods
using the mass transfer phenomenon to separate two distinct mixtures of immiscible
liquid and a stable mixture like suspension. During this separation process, the more
valuable component is collected. For example, the decantation process is used to separate the oil from water which greatly simplifies the purification process, and it is
also used in the production of high-efficiency electrodes and the synthesis of highquality silver nanowire solutions.
All forms of water pollution are not only a threat to our climate but also our ocean’s
ecosystem. Despite technological advancements separation of oil and water poses a significant challenge. With the current technologies, there is demand for more costeffective, environmentally sustainable, and environmentally sound oil/water separation methods which are capable of large volume production. These separation methods
should have efficiencies while dealing with large volumes of oil and water mixtures
(Gupta, Dunderdale, England, & Hozumi, 2017). The materials used for oil water separation can be classified according to their mechanisms for filtration or absorption of oil
and water separation in this chapter.
5.2 Advanced filtration materials
The rapid development of membrane technologies has improved the membrane performance by the wetting phenomenon. Due to fewer complexities and its cost effectiveness,
the functionalized membranes with superwettability have become an important tool for
researchers to separate oil from water and are perfect candidates for practical industrial
applications. However, numerous oil-water separating membranes break out of dependency on transmembrane pressure and have a particular wettability. The oil water separation materials can be classified into films, filters, membranes and meshes which is shown
in Fig. 5.1.
Using porous material with wettability functionality oils can be removed from the
water because oil has lower surface tension than water. The pore size and porosity are
two important parameters for pressure-driven separation membranes where breakthrough pressure is considered in wetting analysis (Mosadegh-Sedghi, Rodrigue,
Brisson, & Iliuta, 2014). The first physical feature is a breakthrough pressure (ΔPc),
defined as the highest pressure applied to a membrane before the moisture is created
on the membrane pores of a liquid. This creates the first drop of liquid on the permeable side of the membrane which has small pores with liquid geometry. The
A. Overview on oil pollution and its effect on environment
85
5.2 Advanced filtration materials
FIGURE 5.1 Filtration materials for
oil-water separation (Gupta et al.,
2017).
breakthrough pressure can be measured as given in Eq. (5.1) using the Laplace young
equation (Kim & Harriott, 1987).
ΔPc 5
2γ L cosθY
rp
(5.1)
where γ L and rp are the surface tension of the radius of the liquid and the maximum membrane pore. These superhydrophobic materials have contact angles of more than 100
degrees. The contact angle of the oil from the water must be more than 160 degrees to
operate (optimum is 175).
4γcos 180 2 θA
(5.2)
P:
Φ
In this equation the interfacial tension is γ, θA is the contact angle of one phase in to the other
and Φ is the square pore’s size (length). The highest resistance to oil will be observed when
passing through a hydrophilic membrane which has a large θA and will be vice versa in small
mesh size (Kwon et al., 2015). These researchers felt that it would only be feasible to generate
the stable Cassie-Baxter state which is shown in Fig. 5.2 if the Young’s contact angle was bigger than the LTA.
The researchers have been increasingly engaged in the identification of liquids in practical
mesh and super-absorbed membranes. The filter media must be very porous for high flow
and high selectivity. Super or ultrafine particles in the filtering surfaces should be light and
larger in weight so that emulsions can be separated more easily (Kim & Harriott, 1987). The
following are different working methods and their advantages and disadvantages.
5.2.1 Metal-based membranes
Membranes are referred to as inorganic membranes, consist of oxides, nonoxides, carbon,
organic metal frames, zeolites, metals, and other components (Abdel Halim, Ramadan,
Shawabkeh, & Abufara, 2013). Inorganic membranes are split into two principal types based
on their structure: porous and nonporous inorganic membranes. The porous membrane has a
metallic surface with a pore size that varies from micro to nano level which is used for water
A. Overview on oil pollution and its effect on environment
86
5. Technological aspects of different oil and water separation advanced techniques
FIGURE 5.2 Cassie- Baxter’s model (Kwon, Post, & Tuteja, 2015).
filtration. For example, a Palladium membrane is a form of dense metallic membranes that
are being considered for hot gas separation (Adhikari & Fernando, 2006).
Bioinspired membranes have lately been produced with porous metallic networks for
the separation of all forms of oil-water mixtures. Although metal mesh substrates are
always bigger than oil droplet sizes, they have a high separation efficiency and flux. These
substrates have raw microstructures and nanostructures that have robust surfaces, hard
environments resistant, and possess unique repeatability which makes them ideal for useful applications in oil-water separation (Ren et al., 2013). These membranes are created
using a variety of surface modification techniques (Sun et al., 2013).
Wang and Song (2006) developed aligned copper mesh membranes which are a good
substrate for oil-water separation and made some electrochemical modification by adding
copper microparticles on the mesh surface. The copper mesh membranes were treated
with in-dodecanoic acid for 12 h. This represented that the substrate has a water contact
angle (WCA) of 158 degrees and a surface angle of 2 degrees when came in contact with
the oil and the contact angle was equivalent to 0 degree. This was developed as a superhydrophobicsuperoleophobic membrane that was found to be an effective solution for oil
and water separation. Guo, Liu, Dang, and Fang (2017) used a similar electrochemical
approach to deposit a 2 mm thick layer of copper nanoparticles on the copper mesh surface. It was a measure that the WCA was 154 degrees and the oil contact angle was 0
degree after treating with n-octadecyl thiol. The prepared mesh membrane could efficiently separate a mixture of chloroform and water using only gravity. Wang et al. (2009)
again experimented to produce a superhydrophobicsuperoleophobic membrane by using
copper mesh surface in addition to electrochemical deposition. The copper mesh was initially treated with nitric acid and modified with 1-hexadecane thiol which was a solution
based immersion process with a WCA of 153 degrees, surface angle of 5 degrees and oil
contact angle equivalent to 0 degree. The membrane did not prove a fast oil-water separator but has shown excellent results in a different medium of solutions.
5.2.2 Polymer-based membranes
These polymer membranes have multiple advantages which include low cost, ease of operation and good processing. These membranes are made of polysulfone (Chakrabarty &
Ghoshal, 2008), polysulfone (Xiong et al., 2018), polyvinylidene fluoride (PVDF) (Zhang et al.,
A. Overview on oil pollution and its effect on environment
87
5.2 Advanced filtration materials
2014) and widely used in oil treatment (Kocherginsky & Tan, 2003) to enhance hydrophilicity
and centrifuge polymeric membrane using either additive or treatment approaches.
Additionally, polymer chemistry offers more advanced approaches such as atom transfer radical polymerization (Zhu & Loo, 2013), in situ polymerization, and interfacial polymerization (Cao et al., 2013).
During the phase inversion process, a polymer matrix can be mixed with additives such as
hydrophilic polymers, amphiphilic copolymers, and inorganic nanoparticles to increase the
resistance from fouling during filtration (Otitoju, Ahmad, & Ooi, 2017). These membranes are
prone to initiate reaction of events such as aggregation, adherence, expansion and agglomeration of fouling agents during treatment of oil wastewater which results in fluidity declination.
The surface properties can be changed by physical or chemical modification using different
additives that improves the antifouling properties as shown in Fig. 5.3. Kim and Van Der
Bruggen (2010). Zhang et al. (2013) used an inert solvent-induced phase-inversion technique
to construct an superhydrophobic-superoleophilic polyvinylidene flouride SHB-SOL PVDF
membrane capable of separating micro and nano stabilized surfactants with composite
particles.
The hydrophilic and hydrophobic segments are present in amphiphilic polymers and
are used as additives in host polymers (Akthakul, Salinaro, & Mayes, 2004). Hester,
Banerjee, and Mayes (1999) employed a comblike copolymer Polymethyl methacrylate
(PMMA) as an additive and mixed with PVDF which forms amphiphilic membranes. This
study indicated that the antifouling capability of the membrane may be significantly
enhanced while maintaining the membrane’s structure. Since then, numerous amphiphilic
copolymers, such as tri-block (Wang et al., 2005), comb-like (Revanur, McCloskey,
Breitenkamp, Freeman, & Emrick, 2007), and branched copolymers (Zhao, Zhu, Kong, &
Xu, 2007), have been employed as additives to increase the antifouling capabilities of host
polymers. Additionally, amphiphilic copolymers containing both hydrolysis lignin (HL)
and hydrophobic (HB) segments are utilized as additives to blend with host polymers.
When the polymer is mixed with additives like hydrophilic polymer, amphiphilic copolymers and composite nanoparticles during the phase inversion process it improves the
fouling resistance and selectivity of polymeric filtration membranes.
FIGURE 5.3 Filler inserted as an additive in polymer membrane (Kim & Van
Der Bruggen, 2010).
A. Overview on oil pollution and its effect on environment
88
5. Technological aspects of different oil and water separation advanced techniques
In comparison to phase-inverted porous membranes, electrospun polymeric membranes
exhibit similar excellent features, including exceptionally high flux at low operating pressure and comparatively controlled pore size and porosity (Chang et al., 2014).
Conventional electrospun membranes with superhydrophobicity were used to separate oil
from the emulsion (Ning, Xu, Wang, & Liu, 2021).
The oil is entirely absorbed when they come into contact with the membrane’s surface
forming an oil layer with a strong water repellent feature because the membrane has an evident attraction for oil due to its loose and porous structure. Where in a similar case Zhang,
Tian, Lv, Na, and Liu (2015) developed a polymer membrane composed of polylactide and
poly (3-hydroxybutyrate-co-4-hydroxybutyrate) using the blend electrospinning method.
Modifying the surface wettability of polymeric membranes by chemical or physical
means is another effective strategy for improving the performance of polymeric membranes
for oil-water separation. Chemical alteration of the membrane surface might be used to
securely introduce HL polymers such as poly(ethylene glycol) methyl ether methacrylate
(Belfer, Purinson, Fainshtein, Radchenko, & Kedem, 1998), poly(2-hydroxy-ethyl methacrylate) (Rahimpour, 2011), zwitterionic polyelectrolyte (Zhu et al., 2013), or small molecules
(Zhao, Su, Chen, Peng, & Jiang, 2012) via formation of covalent bonds. The added hydrophilic materials generate compact hydrated layers that prevent oil droplets from fouling
membrane surfaces. Along with chemical processes, physical absorption may be used to
directly coat hydrophilic polymers and zwitterionic polymers onto membrane surfaces.
Zhao et al. (2012) did research on the grafting method of filtration membranes. He
grafted a low surface free energy molecule, that is, pentadecaflourooctanoic acid on polyacrylonitrile ultrafiltration membrane which has resulted in a good antifouling membrane.
Wang, Zhang, Yang, and Wang (2010) reported on the surface modification of the
hydrophilic layer polyacrylonitrile nanofiber was first deposited onto a nonwoven microfiltration poly (ethylene terephthalate) substrate as a scaffold. To generate high flux for oilwater separation spin coating of chitosan was done on polyacrylonitrile weave as the
hydrophilic layer which resulted in three-tier nanofibrous ultrafiltration membranes.
5.2.3 Ceramic based membranes
The ceramic membranes are originated from alumina, titanium, zirconia, silicon carbide,
etc. Chen et al. (2015) which are made of different porous layers. A substrate layer and
above that a thin division layer, also known as the top layer which sometimes include a
middle layer also which consist of a metal oxide or inorganic powder.
This mixture of layer should be pressed or extruded before sintering process. The
ceramic support surface should be smoothed to produce a ceramic membrane. The flat
ceramic support is then usually dipped by capillary force and then dried for a certain
period with a casting solution (Hyun & Kim, 1997).
The permanent roughness to ceramic membranes was achieved by the coating method
which brings the correct membrane structure and thickness followed by covering and drying of ceramic microcrystals which causes calcination.
The surface roughness is a critical element in membrane weight because it influences membrane performance in oil-water separation. Numerous initiatives have focused heavily on the
development of high-performance microfiltration and ultrafiltration ceramic membranes for
A. Overview on oil pollution and its effect on environment
89
5.3 Advanced absorption based materials
the treatment of oily wastewater (Barbosa, Barbosa, & Rodrigues, 2015). Hu et al. have
reported his research (Hu et al., 2015) research which have focused on oil-water separation
using ceramic membranes with surface wettability. These studies corresponded with roughness control and modifications to the membrane’s HL surface. Since ceramic membranes composed mostly of metal oxides are widely known to be hydrophilic, practically all membrane
researchers have concentrated on developing ceramic membranes for oily water treatment.
Because ceramic membranes composed mostly of metal oxides are widely known to be hydrophilic, practically all membrane researchers have concentrated on developing ceramic membranes for oily water treatment. In addition, the application of Al2O3 MF membrane modified
with hydrophilic HL nanosized ZrO2 for oil-water separation was systematically investigated
by Zhou, Chang, Wang, Wang, and Technology (2010).
5.3 Advanced absorption based materials
Two-dimensional materials such as membranes and meshes have demonstrated success in
a variety of industrial settings. They are less helpful for external environmental pollution treatment such as in lakes, rivers, and the open sea. However, 3D pore materials and particles
avoid some of these drawbacks since they may be easily deposited on polluted regions and
absorb water or oil (Hou et al., 2015; Lu et al., 2021; Wang et al., 2013). As a result, a vast variety of innovative and often hydrophobic three-dimensional porous and particulate systems
with unique surface structures or chemical functions have been discovered.
Separation efficiency is a measuring of the volume of oil or water as compared to that
present in the original mixture by a rejection coefficient R (%), shown in Eq. (5.3):
Vp
R% 5 1 2
3 100
(5.3)
V0
where R% denotes the rejection coefficient in percentage, Vp is the volume of the separated
liquid, and V0 is the volume of the original mixture. There are several ways for functionalizing porous materials for specific applications, including sol-gel functionalization (Zhu &
Guo, 2014; Wu, Li, Li, Zhang, & Wang, 2015), dip-coating (Hou et al., 2015; Zhu & Guo,
2014), and nanoparticle addition as shown in Fig. 5.4.
FIGURE 5.4 Absorption materials for oil-water separation (Wu
et al., 2015; Zhu & Guo, 2014).
A. Overview on oil pollution and its effect on environment
90
5. Technological aspects of different oil and water separation advanced techniques
A simple and cost-effective strategy is to employ preexisting foams and sponges as functional surfaces or as a support framework for further synthesis to create 3D porous oil and
water separation materials. (Du et al., 2015; Wang & Huang, 2015; Zhang, Li, Liu, & Jiang,
2013; Zhu, Pan, & Liu, 2011). Wang et al. described inexpensive superhydrolphlilic sponges
made from melamine which may be temporarily utilized to separate oil/water mixtures using
a simple protonation procedure.
5.4 Sol-gel based materials
The use of a sol-gel synthesis, since such synthesis is easily porous in particular reaction
conditions, is another highly effective approach to the preparation of functional 3D porous
materials. Researchers have also employed foams composed of various metals to boost
resistance to mechanical and thermal damage and to facilitate manipulation using magnetic fields. Cufoams, as revealed by Zang et al., are particularly susceptible to texturing
and functionalization.
Mu et al. demonstrated that the one-pot synthesis of Methyltrimethoxysilane (MTMS),
Dimethyldimethoxysilane, and tetraethoxysilane (TEOS) created an extremely porous,
superhydrophobic silicone sponge of size 6 mm (Mu et al., 2015). The absorbent sponges
preserved 95%98% of their usefulness after 50 cycles and could be maintained at temperatures up to 200 C without losing functionality were 614 g/g for various organic
liquids (Liang, 2013).
Chen et al. presented a new strategy that focused on water-phase absorption. They created Ni-foams covered with a superhydrophilic hydrogel (Chen et al., 2015). The PAM
hydrogel was successfully generated by immersing the Ni-foam in an aqueous solution of
N, N’-methylenebisacrylamide, N, N’, N’-tetramethylethylenediamine, and ammonium
persulfate. The metal foam enabled for magnetic manipulation on a dichloromethane surface to clean up spilt water (Gao, 2014).
Hayase, Kanamori, Fukuchi, Kaji, and Nakanishi (2013) also utilized the same process
to make comparable methyltrimethoxysilane-dimethyldimethoxysilane (MTMS-DMDMS)
gels utilizing a variety of tri- and difunctional alcohoxylic reagents using an aqueous acidcatalytic sol-gel process with an n-hexadecyltrimethylammonium surfactant to increase the
material’s porosity. This material absorbed up to 14 g/g chloroform and preserved its
absorption and flexibility through a temperature range of 270 C320 C (Hayase et al.,
2013). Yu et al. have synthesized a similar “swamplike” aerogel using the surfactant hexadecyltrimethylammonium bromide by polycondensing methyltriethoxysilane (MTES)
dimethyl-diethoxy silane (DMDES) (Yu et al., 2015). These gels exhibited comparable flexibility at room temperature and were also absorbed at a rate of 6.816.9 g/g in a variety of
organic fluids. A polysiloxane aerogel was prepared using environment friendly synthesis
under supercritical CO2 as shown in the Fig. 5.5 (Yu et al., 2015).
Sol-gel synthesis may be utilized to generate materials, structures, and frameworks
that include polymer species. Chen et al. described the preparation of a water-in-oil mixture gel using a specialized low-molecular-weight gelator, tertiary butyl methacrylate, 3aminopropyltriethoxysilanes, 3-isocyanatopropyltriethoxysilanes, and TEOS (Chen et al.,
2014). They discovered that porous monolith architectures may be altered by altering the
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5.4 Sol-gel based materials
91
FIGURE 5.5 Polysiloxane aerogel prepared under supercritical CO2 (Zou et al., 2015).
oil/water phase ratio and silane addition amounts. Wu et al. modified polyurethane
(PU) sponges with commercially available TiO2 to create a sponge with an outstanding
capacity of 80110 g/g for oil/water absorption from a variety of oil/water mixes when
immersed in a n-octadecylthiol solution (Wu et al., 2014). Gao, Shi, Bin Zhang, Zhang,
and Jin (2014) used single-walled carbon nanotubes and porous carbon nanotube (CNT)/
TiO2 porous nanocomposites to induce a self-reinforcing solgel reaction under moderate circumstances. Following calcination at 400 C, TiO2/CNT materials were calculated
to be capable of separating both surfactant-stabilized and unstable oil/water mixtures
from a variety of organic fluids with an efficiency of up to 99.9%, as well as exhibiting
excellent self-cleaning and antifouling properties when exposed to UV light, as organic
material accumulated on the substrate was successfully degraded by UV light.
5.4.1 Template based materials
Template based methods have been used to synthesize porous materials by using existing framework for any material. Zhang (2013) prepared a superhydrophobic copper foam
from a PU sponge using a conductive treatment method which was functionalized by
immersing in n-dodecanethiol solution (Zhang et al., 2013). This foam has shown proved
excellent hydrophobic nature and by absorption of 98% of oil and water mixtures.
Yu et al. adopted a novel strategy by using tiny species to stabilize the emulsion polymerization template (Yu et al., 2015). Amphiphilic carbonaceous microspheres and a trace
amount of surfactant was utilized to stabilize an oil-water emollience comprising dissolved PS, divinylbenzene, and an oil-phase initiator. This was utilized to synthesize two
distinct kinds of very porous hydrophobic PS monoliths that absorbed toluene with a
purity of 98.5% and exhibited absorption capacities of 4,733 g/g for a variety of biofluids,
depending on the precursor proportions utilized in the synthesis. For example, poly
(methyl methacrylate) particles are used as template with different diameters, with a controllable surface ruggedness which has brought a little effect on the water flow of membrane and oil to reject which was used in filtration of oily wastewater.
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92
5. Technological aspects of different oil and water separation advanced techniques
5.4.2 Micro nanomaterials
More advanced methods for oil and water separation employing columns and other
ways have been reported with the use of microparticles or nanoparticles. Okada et al.
employed glass beads ranging in size from 1 to 4 mm to create a bed capable of separating
oil and water (Okada et al., 1985). These micrometer-scale beads were responsible for considerable coalescing, and the increased separation efficiency was noticed following the formation of an oil layer on the surface of the beads at room temperature due to a reaction
between a vinyl-trimethoxy-silane oligomer and fluoroalkyl-capped nanoparticles constituted of vinyl-trimethoxylic/clay. The composition of these components enabled the
encapsulation of guest molecules such as 2-hydroxy-4-methoxybenzophénone, bisphenol
A, propane sulfonic acid 3-(hydroxyalkyl), and perfluoro-2-methyl-3-oxahexanicacid for
application to textiles, glass surfaces, and even to the PS. When utilized in a column, the
composites are employed to separate surfactant-stabilized oil/water mixtures more successfully than typically employed silica gel particles (22 mm diameters) (Oikawa, 2015).
In ternary systems of variable proportions each of the two fluid and solid phases of
hydrophobe, hydrophilic and unmodified glass or SiO2 particles (0.735 mm of diameter)
are used. When the particles are wetted in the fluid the aggregation is promoted by wetting the particles with a single fluid in which they form a suspension, and the fluid and
particles have the same volume fraction. Thus both weight fractions and volume fractions
are to be considered during the seperation of oil and water mixtures.
5.4.3 Nanobased materials
The addition of nanoparticles to a porous material improves surface roughness, hydrophobicity and oleophilicity for oil and water separation. Ge et al. reported a simplified approach
that used polyfluorowax and polysulfone to make a hydrophobic SiO2 nanoparticle dispersion
(1020 nm) which produced sponges with enhanced compressive strain resistance, and the
absorbance capacity for different oils and solvents ranged from 7.5 to 75 g/g, with no significant change for most solvents after 10 cycles (Ge et al., 2015).
Cao et al. also described in situ polymer synthesis using PU sponges containing dopamine
polymerization, which was then functionalized with 1 H, 1 H, 2 H, 2H-perfluorodecanethiol,
to create superhydrophobicity (Cao et al., 2013). These could absorb 1560 g/g of diverse
organic liquids and were not affected by exposure to boiling solvents or high pH solutions
(pH 113). Carbon nanotubes have also been attached to porous surfaces. In systems with
varying ratios of two fluid and solid phases, they utilized hydrophobe, hydrophilic, and unaltered glass or SiO2 particles ranging from 0.7 to 35 mm in diameter.
Small particles have been utilized to separate oil and water because they promote
emulsion coalescence in a column packing material consisting of glass beads of size
14 mm diameter were used to disperse oil and water. The oil coating on the surface
of the bead was noticed, which increased coalescing efficacy. With the help of microparticle and nanoparticles, techniques for separating oil and water have become
increasingly complex. A vinyl-trimethoxy-silane oligomer was formed by room temperature reaction in the presence of fluoroalkyl-clad nanoparticles consisting of vineyardtrimethoxy/tery. 2-Hydroxy-4-methoxybenzophenone, bisphenol A (3-(hydroxyalkyl),
A. Overview on oil pollution and its effect on environment
5.5 Conclusion
93
and perfluoro-2-methyl-3-oxahexaniccid can be encapsulated and applied to textiles,
glass surfaces, and the SP of the guest molecules. The combination of columncombined PS microbeads (size 92 mm) and silica gel (s diameter 22 mm) created a
surface-stabilized emulsion of oils/waters. It was shown that occur only when both
particles may be partly wetted with both fluids and aggregation facilitated by wetting
the particles with a single fluid where they form a suspension. Therefore weight and
volume fractions are both critical for these systems using this process.
Liu et al. (2015) used polyaniline deposition to build a tougher oil or water separation system. Aniline solution-based oxidation was applied to commercial sponges, stainless steel
meshes, and textiles, after which hydrophobium was added to make them more hydrophobic.
Gao et al. reported that the metal nanostructures on-site have nickel (Ni) substrate was utilized to build an ammonia evaporation method to produce metal nanoparticles with a diameter
between 30 and 100 nm, and nanowire arrays were operationalized using fluoroalkyl siloxane
(Gao et al., 2014). These foams initially separated at 99.6%, but after 10 cycles, the rate had
dropped to 97%.
5.4.4 Nanocellulose based material
For preparing oil-water separation aerogels, cellulose nanotropic fibers were sometimes
used which was termed as “Nanofibrillated aerogels” (NFCs) from commercial softwood
pulp, with principally 520 nm of cellulose nanofibers present (Kong et al., 2016). To carry
out a solvent exchange for ethanol, the nanofibers were immersed in a monochloroacetic
acid solution for 30 min, heated in a NaOH solution made up of methanol/isopropanol,
and then carboxymethylated. The modified cellulose was obtained using CVD after washing, freeze-frying, and vacuum.
NFC aerogels can extract waste oil and up to 45 g/g of oil while floating on water. The
aerogels are prepared by mixing homogenized wood pulp in water and then freeze dried
as described by Korhonen et al. (2013).
For hydrophobic qualities, atomic layers were deposited on the aerogels to a 23 nm
TiO2 layer, which was then repeated to enhance the layer’s thickness. The ice crystals
growth caused cellulose fibers to form sheets which improves the stability and 2040 g/g
paraffin oil may be absorbed by the aerogel, after which the gel may be extracted into an
organic solvent.
5.5 Conclusion
Based on the studies and the practical implication of the materials, it can be determined
that its reduction in the environment is the future goal of the researchers. The advance
materials which are nanobased are more effective in the sepration of oil and water.
Complex formation of nanomaterials will bring more involvement in the implementation.
The absorption materials have shown more improvemnt in the absorption of oil and water
mixture. More fundamental research is required to achieve better large-scale separation,
recyclability, and sustainability of wetting materials. Developing ultrawetting smooth surfaces also takes substantial effort. Scale-up, simple, and cost-effective preparation
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94
5. Technological aspects of different oil and water separation advanced techniques
techniques should be implemented. Only a limited number of surfaces are accessible, making separation of huge volumes of mixed oil/water possible using oil and water-repellent
surfaces.
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A. Overview on oil pollution and its effect on environment
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C H A P T E R
6
Impact analysis of oil pollution on
environment, marine, and soil
communities
Shipra Jha and Praveen Dahiya
Amity Institute of Biotechnology, Amity University Uttar Pradesh, Noida, India
O U T L I N E
6.1 Introduction
99
6.2 Composition of petroleum
hydrocarbon
100
6.3 Sources and fate of oil spill
6.3.1 Weathering
6.3.2 Evaporation
6.3.3 Oxidation
6.3.4 Biodegradation
6.3.5 Emulsification
101
101
102
102
102
103
6.4.1 Impact on aquatic and terrestrial
microbial communities
6.4.2 Impact of oil pollution on fish
6.4.3 Impact on seabird population
6.4.4 Impact on marine mammals and
invertebrates
6.4.5 Impact on vegetation
6.4.6 Impact on environment
6.4 Oil pollution and its impact analysis 103
103
104
105
106
107
108
6.5 Future prospects and conclusion
109
References
110
6.1 Introduction
Globally, with an increase in population there is an increase in industrial development
which requires more energy demand, and oil is most essential fuel to fulfill energy demand.
The oil spill becomes threat to human health, destroy the naturals resources and affect the
economy (Anisuddiin, Al-Hashar, & Tahseen, 2005; Anthony, 1994). With the expanding
technical period, developed countries have become dependent on more oil-based machinery
including industrial, pharmaceuticals automobiles, and oil-based home products to enhance
Advances in Oil-Water Separation
DOI: https://doi.org/10.1016/B978-0-323-89978-9.00017-3
99
© 2022 Elsevier Inc. All rights reserved.
100
6. Impact analysis of oil pollution on environment, marine, and soil communities
high living standards (Annunciado, Sydenstricker, & Amico, 2005). In addition to
petroleum-based products, various other oil products include animal fats, vegetable oil are
also being used worldwide. And these oils also contain harmful components adversely
affect human health similarly as petroleum products harm (Alther, 2001). As we use immeasurable quantities, so the oil-based products are stored and transported through large vehicles or by waterways from one place to other. In the course of transporting or storing,
sometimes oil spilled into water or onto land and becomes reason for environment and
human health at risk (Baker, Crothers, Mulett, & Wilson, 1980). To protect environment and
human from oil spill once it occurs, efforts must be made to clean promptly.
During the oil spill, the major forecast is its location and quantity of oil. When the event
adjacent to community and sea beach have significant economic effect including higher
cost cleaning techniques. The oil spill slowly delivers with the time and harm many ways
to the surrounding by breaking down of oil molecule cause risk to human population, natural resources and aquatic life (Bernard et al., 2011). There are many aspects which affect
the spreading efficiency of oil includes composition, type of oil as animal fat, nonpetroleum oils, petroleum oil, chemical or physical properties, surface tension, viscosity etc.
(Bott, Rogenmuser, & Thorne, 1978; Burden, 1991).
Based on the release volume of oil on various environment, oil spills are categories into
four types includes minor, medium, major and disaster. If crude oil releases in low
amount in nature have rare effects on pollution but large quantity of soluble components
of hydrocarbon includes xylol, toloul, and benzol causes high risk to land and sea water
pollution (Butler, 1989; Carmody, Frost, Xi, & Kokot, 2007; Castro, Iglesias, Carballo, &
Fraguela, 2010).
6.2 Composition of petroleum hydrocarbon
The occurrence of hydrocarbon takes place in nature in varieties of forms and petroleum mainly composed of major and minor hydrocarbon compounds. The crude oil is
formed by breaking down oil or wax into smaller molecules to form petroleum and known
as black gold (Chatterjee & Gupta, 2002; Choi & Cloud, 1992). The crude oil formation
started millions of years ago when in sea water aquatic animal died along with marine
plants and buried, settle down in multiple layers in the form of slit, sand on bottom. With
the time due to effect of pressure and heat processes varieties of hydrocarbon starts evolving (Choi, 1996; Daling & Strom, 1999).
The crude oil slowly moves underground as it is in the form of liquid and to extract out
from earth understanding of oil trap and oil pool is important. The reservoir of oil under
the earth is termed as oil pool and when oil vapors are trap by nonporous sandstone associated with other gases to ovoid spreading of oil on earth surface then termed as oil trap
(Dave & Ghaly, 2011; Descamps, Caruel, Borredon, Bonnin, & Vignoles, 2003; Etkin, 1999).
The hydrocarbon is mainly composed of mixture of carbon and hydrogen containing
compound along with mineral salts, minor elements oxygen, sulfur, nitrogen, trace metals
includes chromium, nickel. These compounds also contain olefins, polar, aromatic and
saturates compounds. The crude oil compounds containing saturates include alkanes in
which each carbon is surrounded by hydrogen atoms. Olefins are unsaturated compounds
A. Overview on oil pollution and its effect on environment
6.3 Sources and fate of oil spill
101
containing carbon—carbon double bond and common in refined products. The petroleum
oil accounts for about 1%20% single ring aromatic compounds known as toluene, benzene,
xylene and about 0.2%7% polynuclear aromatic hydrocarbon (Espedal & Johannessen,
2000; Fingas & Fieldhouse, 1994).
Polycyclic aromatic hydrocarbon (PAHs) includes those compounds in crude oil which
have serious toxicity threat to living organisms. The resins are small polar compound and
large polar known as asphaltenes which is part of petroleum industry and contribute
majorly during road construction. If the crude oil containing large concentration of asphaltenes responsible to changes the oil behavior.
Petroleum can be categorizing into many ways. Initially it produced in long chain kerogen form because below the ground it has not been buried at higher temperature for long
term. The kerogen having long chain shows two properties (1) The crude oil made up of
long straight chain are thick and molecules are tightly packed and occupies large mass per
unit volume. (2) The long chain carbon makes it difficult for molecules to flow fast and
pump out harder (Lemiere et al., 2005; Lessard & Demarco, 2000). If the crude oil contains
sulfur is highly viscous, then it is also known as young shallow crudes because under the
earth crude oil have not buried deeply for long time at higher temperature.
6.3 Sources and fate of oil spill
When the spreading of liquid hydrocarbon starts in the environment due to spill event,
failure of system, machinery, cleaning of oil tankers, ship safety features, etc. The region
closes by hydrocarbon handling resources face the higher risk. Oil spill during various
transportation activities may disperse various types of crude oil include petroleum products which acts adversely in ecosystem (Graham, 2010; Janjua et al., 2006). The reason
behind oil spill toxicity is the presence of toxic compounds includes PAHs, volatile organic
compound etc. Spilled oil does not mix immediately with water instead forms thick layers.
The thick layers need to be removed from aquatic ecosystem as responsible to block the
various pathways include oxygen, breakdown nervous system in marine animal (Masoora
& Sommerville, 2009). The Fig. 6.1 shows direct and indirect impact of oil spill.
There are various natural actions includes emulsification, evaporation, weathering, oxidation and biodegradation which works in aquatic environment to reduce the harmful
effect of oil spill.
6.3.1 Weathering
The action of weathering is the combination of synthetic and physical changes responsible
to break down the oil spilled, form a thin layer of oil slick and making the water heavier.
Further oil slick undergoes various degradation under the effect of simultaneous process
include wave action known as oil weathering process. Once the higher quantity of crude oil
spreads on sea surface, it begins to degrade. The weathering process modifies the behavior of
oil slick and modifies the life cycle of aquatic biology (Ventikos & Sotiropoulos, 2014).
A. Overview on oil pollution and its effect on environment
102
6. Impact analysis of oil pollution on environment, marine, and soil communities
FIGURE 6.1 Figure representing direct and indirect impacts of oil spill.
6.3.2 Evaporation
The process of evaporation is considered as one of the essential steps for oil spills, but
less work has been conducted to understand the chemistry of evaporation. Due to the
problem in understanding oil evaporation process because of combination of hundreds of
chemical compounds varies with time and from the source. The release lighter volatile
substances of oil spill on water surface can vaporize up to 45% of the oil volume. The reason behind evaporating the lighter substance form oil spill includes refined products containing flammable properties in them. The lighter volatile substance may evaporate form
water surface in few hours causing less harm to marine environment leaving behind
heavier substances of oil includes animal fats, vegetable oils which gather on the water
surface. The process requires understanding of mechanism that regulates the evaporation
process (Palinkas, Petterson, Russell, & Downs, 2004).
6.3.3 Oxidation
When oil comes in contact with oxygen and water to form water soluble compounds,
the process is known as oxidation. Oxidation affects thick oil slicks which partially oxidizes, and forms sticky dense tall balls may stay in the environment (Shailaja &
D’Silva, 2003).
6.3.4 Biodegradation
When oil releases in the aquatic environment, soil, groundwater and rivers responsible
for pollution. Biodegradation is the process when microorganisms degrade oil hydrocarbons and uses nitrogen and phosphorous for the growth. A wide range of microorganisms
includes bacteria is present in the soil, water and air which actively participate in degradation process in the environment (Stefansson et al., 2016).
A. Overview on oil pollution and its effect on environment
6.4 Oil pollution and its impact analysis
103
6.3.5 Emulsification
During oil spill, oil starts dispersing and floating on the surface of water as free form
because oil and water does not easily mix. The oil pool toxicity affects marine ecosystem and
wildlife. The emulsifiers include detergents when disperse with oil and water to form small
droplets, the process is known as emulsification. Due to the wave action, water trapped
inside viscous oil and called as chocolate mousse which stick to the environment for years.
6.4 Oil pollution and its impact analysis
6.4.1 Impact on aquatic and terrestrial microbial communities
The impact of petroleum oil in aquatic environment mainly decided by factors including
marine geology, temperature, biological activity of sea. During oil spill, petroleum oil disperses on sea water in three ways—a floating form, evaporative and sinking form. In aquatic
ecosystem hydrocarbon become a part which disperse in water through oil spill (Wong, Lim,
& Nolen, 1997). The microbial population have also adjusted themselves to live in their natural condition even in the presence of contaminant by acquired different response includes
gene modification, composition and diversity of microbial population (Varela et al., 2006).
Marine ecosystem is linked directly and indirectly to animals, plants and physical environment. If physical environment is affected, then other species also get affected which
results in disturbance in the whole ecosystem (Burk, 1977). The result of oil spill containing poisonous substances may minimize with time when the certain poisonous substances
vaporize from initial oil spill region without affecting human, plants and animals. Even
though some life form may get severely affected as soon as exposed to oil spill depending
upon exposure duration include short or long term. All categories of oil include petroleum
or nonpetroleum have same chemical and physical properties and affect surrounding environment during oil spill (Peterson et al., 2003).
For better understanding of fate of petroleum hydrocarbon in aquatic environment is to
know bioavailability and bioaccumulation mechanism. The chemical substance when move
or bind to cell membrane or gut lining through physical, chemical or biological processes.
Deposition of petroleum oil depends on metabolic modification in entity, duration of exposure, biotic availability of oil and mainly biological and climatic availability (Peterson, 2001).
Terrestrial oil spill is a threat for human health including neurological disorder,
tumor, disruption of cellular function due to its lethal effect on soil sediments, underground water, fresh water and affecting whole ecosystem if remains untreated.
According to research finding, responsiveness of vegetation to oil contaminant also
depend on type of root system they contain. As compared to plants containing stock
roots, the plants having shallow roots are affected with oil spill. Depending upon the
soil composition, bioavailability of hydrocarbon compounds differs either maximum
oil compounds absorbed by organic part of soil and reduce bioavailability with low
effect on soil microflora. During oil spill event on soil, microflora affect in numerous
ways includes mobile genetic alteration in soil contaminated microflora. And if genetic modification expressed then play important role in breaking down biological impurities. In order
A. Overview on oil pollution and its effect on environment
104
6. Impact analysis of oil pollution on environment, marine, and soil communities
to understand more about natural oil degradation mechanism of microorganism extended
research needs to be done. To find out distribution of soil microbial population with their
gene activity for breakdown of oil compounds in fertilize rich soil. Table 6.1 represents the
various oil spill incidents in history across the globe.
6.4.2 Impact of oil pollution on fish
The aquatic environment is full of entity starting from microbes to algae and other forms of
life. The primary food producers play role in transferring food to higher organisms and responsible for enriching food with vital nutrients necessary for human health. The aquatic family
maintains balance between water and terrestrial food chain (Bly, Colcomb, & Reynolds, 2007).
TABLE 6.1 Past incidence of oil spill in history across the globe.
S.
no. Country
Incident and year
Quantity
(tones)
Reference
1
Indonesia
In Malacca Straits spilling crude oil Nagasaki
burned out after collision with ocean blessing (1992)
12,000
2
Nigeria
Breakdown of pipeline to one of Mobil’s terminal
(1998)
5456
Nnadi, El-Hassan, Smyth,
and Mooney (2007a)
3
United
States
Argo Merchant oil spill in Nantucket Island (1976)
24,961
Winslow (1978)
4
Trinidad
and
Tobago
Collision off Tabago during tropical rainfall (1979)
287,000
Hooke (1997)
5
Kuwait
Kuwait crisis after final phase of Iraqi attack (1991)
7,557,935
Quamar and Kumaraswamy
(2019)
6
United
Arab
Emirates
Crude oil leaked after explosion between Baynunah
tanker and Supertanker seki (1995)
15,900
Shriadah (1998)
7
Brazil
Oil spilled from refinery (2000)
31,491
Braz (2006)
8
Pakistan
Oil tanker broken up in Pakistan’s Arabian (2003)
10,000
Siddiqi and Munshi (2014)
9
Lebanon
At Jiyeh thermal power station oil spill (2006)
20,000
Khalaf et al. (2006)
10
United
States
Oil spill in New Orleans (2008)
8800
11
Nigeria
Oil Explosion in the Niger (2010)
3246
Kadafa (2012)
12
Canada
Little Buffalo HC spill
3800
Chang, Stone, Kyle, Demes,
and Piscitelli (2014)
13
United
States
Arthur storage tank crude oil spill (2012)
1090
Vanea, Kima, Moss-Hayesa,
Turnera, and Simon (2020)
14
United
States
Crude oil spill in Magnolia (2013)
680
Juan, Saqalli, Laplanche,
Locquet, and Elger (2018)
A. Overview on oil pollution and its effect on environment
6.4 Oil pollution and its impact analysis
105
The crude oil spill also affects water animal including varieties of fish in many ways; growth
and reproduction rate, respiration, gill structure, morphological abnormalities, lethal effect on
fish larva. Even at low concentration of oil can affects circulatory system of fish and may cause
death in early developmental stage (Hicken, Linbo, Baldwin, Willis, & Myers, 2011). According
to the studies it was found that adverse effects of oil spill in case of juvenile growing salmon
showed instability and erratic swimming with low and slow movement due to changes in gene
expression, tissues, or organs. The cyclic hydrocarbon also interferes with normal development,
contractility defect of developing heart (Bellas, Saco-Alvarez, Nieto, Bayona, & Albaiges, 2013).
6.4.3 Impact on seabird population
Seabirds are open water creatures that are highly vulnerable to oil spills. Oil spill will
harm seabirds such as sea ducks, penguins, alcids, cormorants, etc. Oil spills can influence
sea birds during primary oiling, secondary during release of oil and clean-up activities which
ultimately results in decreased population size, lower reproductive rates, reduced habitat
occupancy, reduced food supply, altered foraging behavior, emigration, and direct/indirect
mortality. The primary problem is coating of bird feathers with oil. When swimming in or
diving in the oil polluted water the seabirds’ feathers become oiled. The oiled feathers
become matted and waterlogged which will destroy the buoyancy and insulation leading to
starvation, hypothermia (death due to excessive heat loss) and ultimately drowning of birds.
Oil results in alteration of the feather structure and disrupts the systematic arrangement of
feather barbules and barbicelles resulting in waterlogged feathers. Preening behavior of seabirds also aggravated the impact of oil toxicity in the case of sea birds encountering polluted
waters because the oil will spread to all parts of their plumage. The harmful oil is also
ingested when the seabird cleans its feathers by preening. The feeding behavior of seabirds
such as Calidris alba and Charadrius semipalmatus after oil spill was reported by Burger (1997).
He observed that the bird soaked in oil is spending maximum time preening and is devoting
very less time for foraging in comparison to the unoiled seabirds. Spill events at small doses
may impact sea birds like alcids which mainly rest and also consume its feed from the sea
surfaces. The insulating properties of plumage in arctic seabirds is very crucial as they live in
cold conditions, so these birds are highly vulnerable to oil spill pollutions.
6.4.3.1 Toxic effect of oil
Seabirds exposed to oil contaminated water will ingest oil during preening and by taking food from the polluted water mainly exposing themselves to toxic hydrocarbons in
crude oil. These toxic hydrocarbons include PAHs whose ratio depends on the type of oil
and level of weathering. Once ingested, the oil proves highly toxic in the body and can
lead to various issues including liver damage, lung damage, affects the kidney function,
hemolytic anemia (Troisi, Borjesson, Bexton, & Robinson, 2007), gastrointestinal issues,
immunotoxicity (Troisi, 2013) and endocrine disruption (Fowler, Wingfield, & Boersma,
1995; Fry & Lowenstine, 1985). PAHs will enter the circulation resulting in plasma and tissue contamination (Troisi, Bexton, & Robinson, 2006). Even at low doses, the oil ingestion
may influence the survival rate and reproduction capacity of seabirds (Lance, Irons,
Kendall, & McDonald, 2001). The survival rate of rehabilitated oiled sea birds is observed
A. Overview on oil pollution and its effect on environment
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6. Impact analysis of oil pollution on environment, marine, and soil communities
to be unfortunately low in case of common guillemots. PAHs toxicity and almost no
increase in weight are observed as the main reason of mortality (Grogan et al., 2012). In
birds, thyroid hormone which is in control of HPT axis (hypothalamus-pituitary-thyroid)
is important for weight gain, reproduction potential, metabolic activities, thermoregulation
and development processes. Exposure of birds to oil may disrupt the HPT axis. Various
field experiments performed have shown that slightly oiled adult birds can transfer oil to
the eggs while incubation or by its feathers which will ultimately decline the hatching rate
and sometimes bird embryo is killed by the contaminated parent.
The oil spill will slowly undergo weathering, during which the highly toxic components
are evaporated. The oil composition begins to vary with less volatile components and light
and biodegradable components. Thus weathered oil is considered to be less toxic compared to
fresh oil. Simultaneously, direct exposure (via preening) of seabirds to oil spills also shift
towards indirect exposure via food intake. Mallard duck fed on weathered crude oil showed
no significant impact on the reproduction potential, growth and survival at those concentrations. Whereas, at subsequently high concentrations of oil in diet (20 g of oil/kg), eggshell
thickness and strength was significantly reduced. However, unweathered oil of highly toxic
nature remained preserved in the seabed, under rock armor and in mussel beds over quite
long period of oil spill incident ultimately impacting some fishes and invertebrates. These oil
spills possess long term impact on the seabirds as studied by Lance et al. (2001) who reported
that after 10 years of oil spill, only four bird taxa out of 17 showed recovery signs, no recovery
was observed in case of nine taxa and four bird taxa showed higher impact of oil spill. This is
because of the oil contaminated food available in shallow waters and intertidal zone preferred
by seabirds. Increase in water temperature in the particular area may be another factor which
will influence the rehabilitation of the seabird taxa (Lance et al., 2001).
Some species of seabirds are found more vulnerable compared to others depending on
their lifestyle and population regulation. Some birds spend maximum time on the surface of
sea swimming or diving and are found to be most vulnerable in case of oil spills in comparison to others which are mostly airborne are less affected. Some birds feed at sea throughout
includes diving ducks, various terns, gulls and alcids whereas, other birds feed at sea only for
some part of year including grebes, some ducks, phalaropes etc. Seabird populations seriously
impacted by oil pollution includes the ones with long lifespan and lower reproductive potential (e.g., alcids and fulmars). Few evidences available suggests that seabird Fulmarus glacialis
can deliberately avoid settling on seabed polluted with oil.
6.4.4 Impact on marine mammals and invertebrates
In coastal environment, crude oil further breaks in three different components such as
volatile, floating and sinking component. Within a week, low molecular weight either dissolve, evaporates or are degraded photochemically. Due to advection and turbulence, the
oil gets dispersed on the surface and form emulsion which is commonly named as “chocolate mousse.” This mousse will impact the marine mammals and also suffocate the invertebrates. Gesteira and Dauvin (2000) studied the impact of oil pollution microbenthic
sp. and few important observations were made: (1) the crustaceans and amphipods
showed maximum mortality rate thus were first to disappear, (2) opportunistic sp., like
A. Overview on oil pollution and its effect on environment
6.4 Oil pollution and its impact analysis
107
polychaetes increases in number due to increase in quantity of organic matter after 13
years after stress, (3) positive and negative effects on population dynamics observed.
Physical smothering with oil will impact the respiration rate and movement in the case of
invertebrates of benthic and pelagic zones, the extra weight added and shear forces during
movement may result in the death of animals. Mussels and barnacles may survive short term
impact, but they may suffocate due to a heavy layer of oil. Whereas, crustaceans were
reported to move to deeper waters if possible, in case of oil pollution (Bonsdorff & Nelson,
1981). In case of oil spill initially significantly higher mortality rate was reported in all the
taxa which will subsequently impact the infaunal species such as amphipods, bivalves and
polychaetes. As all the rocky shores are covered by oil it will significantly impact the mobile
fauna like crabs, gastropods, amphipods, and echinoderms. If the oil layer is thick it can also
smother mussels or barnacles. Some jellyfish and anemones (Anthopleura and Actinia sp.)
are found surviving in severe oil pollution. Whereas other Cnidaria like hydroid Tubularia
are found very sensitive toward oil spill pollution even at very low concentrations.
Oil pollution also impact the marine mammals present in the area of oil spill. Various marine
mammals present includes whales, seals, dolphins, fins, sea otters, manatees, cetaceans, pinnipeds
etc. Whales and adult seals are found less effected by oiling when compared to seal pups. As
whales mainly depend on blubber layer and not its fur for insulation but seal pups depend on
their fur for insulation (Geraci, 1990). The oil reaches finally to the pups from their mother seal
during nursing. Amongst seals, hooded seal and harp seals are found more vulnerable to oiling
than ringed seals (St Aubin, 1990a). If the oil pollution is in between ice then it whales (white and
bowhead whales), seals (ringed and bearded seals) and walrus are at higher risk as they live-in
ice-covered waters (Boertmann, Mosbech, & Johansen, 1998). Fur is required for insulation in case
of polar bear thus the polar bears are sensitive to oil pollution. The oil can be ingested from the
fur while grooming (Stirling, 1990). Ingestion of oil is highly toxic which will lead to poisoning.
Oiling will subsequently result in hypothermia, drowning and smothering in these animals.
Pinnipeds are severely affected due to contamination of shores by the oil. Marine mammals inhale volatile hydrocarbons evaporating from oil which contain extremely toxic benzene, xylene, toluene and aliphatic compounds. Theses toxic vapors result in congestion of
lungs, pneumonia and inflammation of mucus membrane. Benzene and toluene once
inhaled will enter the bloodstream which will further transfer to the lungs, brain, and liver
resulting in damage of liver and neurological problems (Neff, 1988).
A few sources of information are available regarding impact of terrestrial oil spills in relation to mammals. Terrestrial mammals can easily smell and see the oil spills therefore it can
be easily avoided by them getting in contact with oil. Faulty pipelines break or blowouts
from oil wells may lead to terrestrial oil spill, but it is mainly confined to limited area. Cases
of huge oil spills are reported from Usinsk, Komi republic in Russia. There are no available
reports of such oil spills and their impact on terrestrial mammals. Similarly, oil spills
reported from Greenland reported minor impact on the population of caribou and muskox.
6.4.5 Impact on vegetation
Phytoplankton’s reported very limited direct impact of oil spill pollution. In the Artic
pelagic zone, the impact is not much visible compared to laboratory studies which shown
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6. Impact analysis of oil pollution on environment, marine, and soil communities
response to the toxic compounds of oil. The coastal communities are found severely
exposed to contamination due to oil stranding. The stranded oil and its associated toxicity
enhance the barren period and reduces the recolonization of that area. Exxon Valdez oil
spill, Alaska showed only few survivors like seaweeds and it took two years for polluted
shores appeared recovered and gained the pre- oil spill vegetation (Dean, Stekoll, & Smith,
1996). Some studies based on freshwater ecosystems reported that perennial vegetation
including emergent, submerged and floating plants are possessing better tolerance capacity and higher recovery potential from oil spills compared to annuals. The impact was
even less in case of flowing water in comparison to stationary water.
Oil spill is reportedly badly impacting the terrestrial vegetation in Arctic wetland plant
communities which shows heavy damage to the plant tissues and similarly mosses were
also totally eliminated but, sedges were observed to be the first one to recover. The oil
spills will show immediate influence on vegetation cover as within few days of the spill
the vegetation turns yellow or brown in color, losing chlorophyll and falling of leaves.
Higher susceptibility was reported in case of forbs whereas graminoids possess resistance
at mesic sites but were killed when at dry sites. Shrub Salix arctica was found to possess
least susceptibility whereas, lichens were found prone to diesel oil. The complete vegetation cover in an area was found drastically reduced in dry/xeric conditions compared to
wet/mesic conditions as in dry conditions oil can penetrate the roots easily.
The adverse effect of heavy fuel oil pollution was studied on Salicornia fragilis, an edible
species in greenhouse studies (Meudec, Poupart, Dussauze, & Deslandes, 2007). In order
to analyze the effect of oil pollution on the growth and development of Salicornia, phytotoxicity assessments and PAH shoots assays were conducted. Chemical toxicity due to oil
pollution was reported in the form of chlorosis, yellowing and reduction in growth. Shoot
tissues showed significant accumulation of PAHs even at lower concentration of contamination which proves toxic impact of fuel oil contamination on the edible species.
Huge amount of crude oil spill was reported from the area of coral reefs, mangroves
and seagrasses, at the Caribbean entrance to the Panama Canal in year 1986. All the vegetation in the area were covered by the oil like mangroves, sea grasses, algae and associated
invertebrates and die within some time. Subsequently at the same site, seedlings of
Rhizophoram angle were planted but it failed to survive. Intertidal seagrass (Thalassiat estudinum) could not survive the oil pollution and was found to be dead and floating ashore
whereas, the subtidal Thalassia was found to survive the oil spill. The subtidal Thalassia
leaves turned brown and are heavily fouled by algae in areas which are heavily oiled.
Tarn, Wong, and Wong (2005) reported smuggled oil spill incident and its impact on mangrove plants in Hong Kong. In year 2000, approximately 500 mangrove saplings were contaminated due to fuel oil spill incident that lead to the death of more than 80% saplings.
After one year of oil spill, the effected mangrove saplings recovered and regrown from the
root-zone sediments with the decreased total petroleum hydrocarbons concentrations.
6.4.6 Impact on environment
Accidental oil spillage taking place at higher concentrations will pose a serious influence on the environment unless the oil is diluted/degraded. In the Arctic regions the effect
A. Overview on oil pollution and its effect on environment
6.5 Future prospects and conclusion
109
will persist for long due to lower temperature and ice when compared to moderate conditions. Similarly, the spread and fate of oil spill in marine conditions is more as it can easily
spread to sizeable areas when compared to terrestrial oil spills that are limited to the
impact area only. In colder environments, the oil pollution is controlled via different biological and physical features including dispersion, hardening, biodegradation, bioaccumulation, dissolution etc. Few chemical processes like photolysis can also impact the oil
pollution but it is insignificant the colder environments. The oil pollution may lead to oiling of all vertebrates, invertebrates and vegetation or ingestion of oil in the gut which will
have higher level of toxicity due to low molecular weight compounds (alkanes, aromatics)
and PAHs.
Oil fate from the oil spill environments are vital to understand and analyze. It largely
depends on the surface area covered by oil verses volume of oil. The effectiveness of fate
process depends on higher ratio values and the ratio depends on the environmental conditions of that area such as average temperature, storm activity, ice and snow. Temperature
is considered to be highly significant factor as it will affect the biological activity, viscosity
and density of oil. The oil trapped in rock crevices where surface to volume ratio is quite
less will not undergo weathering process and is leading to long term pollution but at
lower doses. The fate and transport of oil spill will dictate the environmental impact. It
includes (1) formation of oil slicks that are highly resistant towards degradation, during
which the oil will collect on water body surface. Evaporation of volatile components will
occur when the oil slick comes in direct contact with air, (2) Further with time some more
soluble compounds are dissolved, (3) the above mechanisms results in the reduced effect
of oil but increases the mobility of oil thus allowing the oil to spread to larger areas which
will ultimately complicates the clean-up processes and (4) certain oil components becomes
persistent and accumulates in living organisms available and the environment. It will negatively influence the environment as well as shows harmful effects on marine, freshwater
and terrestrial life forms.
6.5 Future prospects and conclusion
Oil spills can have a significant effect on the environment and various life forms present
in the spill area, and thus it raises various guidelines and policy issues related to transportation of oil, remediation and restoration of spill sites in the case of accidents. There is
huge risk associated with petroleum and its associated products due to their rising
demands across the globe in order to fulfill the ever-growing energy needs. Accidental
release of these products will release highly toxic compounds into the marine environment
posing challenging conditions for the survival of biological ecosystem. To mitigate the
effect of oil pollution, focus should be on effective cleaning up strategies which will limit
the chances of secondary pollution. Policies related to contingency planning, mitigation
measures, response team for onshore spill and efficient counter measures should be in
place to protect the biodiversity and aquatic life before any accidental spill.
Various researchers belonging to different domains are constantly working to develop
cost-efficient, simple, and environment friendly techniques/materials to understand and
resolve the major challenge of oil pollution which includes immobilized lipase enzyme,
A. Overview on oil pollution and its effect on environment
110
6. Impact analysis of oil pollution on environment, marine, and soil communities
magnetic nanomaterials, techniques for chemical analysis of pollutants, biomarkers etc.
Methodologies to analyze the diverse pollutants in the environment are continually evolving and now concentrations of toxic compounds up to parts per trillion can be analyzed.
The oil contaminant responsible for causing pollution can be quantitatively analyzed via
Gas Chromatography linked to Mass Spectrometry analysis. Biomarkers are used to analyze the PAHs present in animals due to crude oil pollution. Ethoxyresorufin O-deethylase
activity can detect the enzyme level in liver tissues which is a highly sensitive technique
for analysis of PAH exposure level. Enzyme lipase can catalyze the breakdown on oils and
fats. Lipase isolated from Pseudomonas sp. was immobilized on charcoal and sawdust by
adsorption which was utilized for the biodegradation of crude oil. Nanotechnology has
also opened new approaches of using magnetic materials and checking its capacity as
adsorbent for oil spill. The magnetic adsorbent materials are also utilized in repair work
related to oil leakage. Various new strategies are coming up, but these must be scientifically proven via laboratory and field experiments. Further research is required in all the
above-mentioned techniques, key variables to be incorporated in integrated models which
can provide us a better insight of oil spill and its impacts in particular zones/areas. These
models will consider oil dispersion as well as its impact on economy, ecology and human
health. Such models can answer all critical questions related to pre and postoil spill incidents. It is of immense attention for planners and policy makers to get an insight from
these models for decreasing the occurrence of oil spill events, supports immediate and
effective response and recovery measures.
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C H A P T E R
7
Impact of oil exploration and spillage
on marine environments
Ankita Thakur and Bhupendra Koul
School of Bioengineering and Biosciences, Department of Biotechnology, Lovely Professional
University, Phagwara, India
O U T L I N E
7.1 Introduction
116
7.2 Types of pollution
116
7.3 Types of oils
118
7.3.1 Group 1: nonpersistent light oils
(gasoline, condensate)
118
7.3.2 Group 2: persistent light oils
(diesel, no. 2 fuel oil, light crudes) 118
7.3.3 Group 3: medium oils
(mostly crude oils, IFO 180)
118
7.3.4 Group 4: heavy oils (heavy
crude oils, No. 6 fuel oil,
bunker C)
118
7.3.5 Group 5: sinking oils
(slurry oils, residual oils)
118
7.4 Causes of oil pollution
7.4.1 Natural cause
7.4.2 Anthropogenic activities
119
119
119
7.5 Harmful effects of oil pollution
120
7.5.1 Effects of oil pollution on aquatic
ecosystem
121
Advances in Oil-Water Separation
DOI: https://doi.org/10.1016/B978-0-323-89978-9.00018-5
7.5.2 Effects on marine flora
7.5.3 Effects on marine fauna
121
121
7.6 Bioaccumulation and biomagnification:
marine chemistry
127
7.6.1 Toxins in the marine food chain 127
7.6.2 Bioaccumulation and
biomagnification of hydrophobic
organic compounds in fish
128
7.6.3 Biomagnification and
bioaccumulation of mercury
in an arctic marine food web
128
7.7 Remedies to cope up with oil
pollution
7.7.1 Physical methods
7.7.2 Chemical treatment
7.7.3 Bioremediation
7.7.4 Natural recovery
128
130
130
131
132
7.8 Conclusion
132
References
132
115
© 2022 Elsevier Inc. All rights reserved.
116
7. Impact of oil exploration and spillage on marine environments
7.1 Introduction
Literally, pollution relates to the entry of harmful substances (pollutants) into the
environment. This term has become so common that almost everyone including kids
are aware of and acknowledge the fact that pollution is rising continuously. When we
talk about “pollution on Earth,” we refer to the contamination that is happening
because of natural or anthropogenic activities. In an ecosystem, there could be multiple forms of contamination; streams loaded with toxic chemicals due to the discharge
of industrial effluents, water-bodies overloaded with nutrients from agricultural
fields, litter blowing away from landfill sites, cities enveloped in smog etc. Moreover,
landscapes that seem to be natural can deteriorate due to the source of pollution
located in the vicinity or even hundreds or thousands of miles away. All this is
mainly caused by human activities that harm the environment in so many ways
(Larramendy and Soloneski, 2015).
Oil is the most indispensable commodity in the world for energy production. Due to
its uneven distribution, it is transported by ships over the oceans and by pipelines across
the lands. While transferring the oil to vessels, it results in several accidents, during
transportation, also breaking of pipelines, as well as while drilling in the earth’s crust.
As a result of an accident or human error, contamination of seawater due to an oil pour
is termed an oil spill (Kaushik, 2019). An extensive amount of oil enters the coastal
region by accidental spill, continuous discharge, and custom activities. It is obvious that
oil is toxic for many marine organisms but the present information does not provide a
clear understanding of environmental destruction that comes from oil pollution
(Howarth, 1989; Gros et al., 2014)
During this extensive phase of oil exploitation in the marine environment, the adverse
effect of the same has been recorded in various aspects (Elmgren et al., 1983; Fukuyama
et al., 2000; Kurylenko and Izosimova et al., 2016). Thus oil spills are of great concern due
to the tremendous economic loss and the long-term, notable harm to marine ecosystems,
regional economy, coastal society, and communities (Clark, 1982; Brussaard et al., 2016;
Zhang et al., 2019). The fishing vessels, ferryboats, or recreational ships are comparatively
smaller in size but are a major cause of pollution, contributing little by little. Oil is an
indispensable commodity and a major revenue-generating resource for many countries
with immense oil reserves. Therefore transporting oil from the sea can never be put to an
end; rather we need to look for safer driveways. Moreover, we must be ready for any
emergency associated with an oil spill and oil clean up from the sea. A novel approach
need to be adapted that may provide a complete solution to combat oil spills (Yuan &
Chung, 2012).
7.2 Types of pollution
Pollution can be categorized into five major types. Table 7.1 shows the source, impact,
and possible remedies for each type of pollution.
A. Overview on oil pollution and its effect on environment
117
7.2 Types of pollution
TABLE 7.1 Types of pollution along with their sources, impact, and solutions.
Types of pollution
Type of
S. no. pollution
Sources/causes
Impacts
Solution
1.
Air
pollution
Burning of fossil fuels, exhaust
from factories and industries,
mining operations, agricultural
activities
Respiratory illnesses and
allergies ranging from coughs
to asthma, cancer or
emphysema, Acidification
Replacing fossil fuels with
alternative energies like solar,
wind and geothermal,
Ecofriendly transportation,
green building
2.
Water
pollution
Sewage, industrial waste,
private waste, mining, oil
leakages, dumping, fossil fuels,
chemical fertilizers, pesticides,
leak of sewer lines, radioactive
garbage
Effects on humans, animals,
plants, water animals and
plants. Disruption of the food
chain, diseases,
eutrophication, destruction of
whole ecosystems
Responsible use of fertilizer
and pesticides, Discourage
firms from disposing of their
trash in rivers, lakes or oceans,
Replace fossil fuels by
renewable energies
3.
Soil
pollution
Phenomena such as erosion,
loss of organic carbon,
increased salt content,
compacting, acidification and
chemical pollution
Damage to health, poorer
harvests, climate change,
desertification, decline in soil
productivity and loss in crop
diversity
Produce home compost,
improve urban planning,
transport planning, and
wastewater treatment, improve
management of mining waste,
implementation and
assessment of sustainable land
and soil management.
4.
Noise
pollution
Industrial sources, transport
vehicles, household, public
address system, agricultural
machines, defense equipment
Noise induced hearing loss,
high blood pressure, heart
disease, sleep disturbances,
and stress, impairments in
memory, attention level, and
reading skill.
Avoid of noisy leisure
activities, installing noise
insulation in new buildings,
creating pedestrian areas,
replacing traditional asphalt
with more efficient options
that can reduce traffic noise by
up to 3 dB, among others.
5.
Thermal
pollution
Water as a cooling agent in
power, manufacturing and
industrial plants, soil erosion,
deforestation, runoff from
paved surfaces, retention
ponds, domestic sewage
Decrease in DO (dissolved
oxygen) levels, increase in
toxins, loss of biodiversity,
ecological impact, affects
reproductive systems,
increases metabolic rate,
migration
Cooling ponds, cooling towers,
artificial lake, water recycling,
the thermal discharge of power
plants can be used in other
purposes like: Industrial and
space heating, soil warming,
Fish culture, livestock shelters
and heating greenhouses.
6.
Radiation
pollution
Nuclear accidents from nuclear
energy generation plants, the
use of nuclear weapons as
weapons of mass destruction,
use of radioisotopes, mining,
spillage of radioactive
chemicals, tests on radiation,
cosmic rays and other natural
sources, nuclear waste
handling and disposal
Genetic mutations, diseases,
soil infertility, cell destruction,
burns, effects on wildlife,
effects on plants, effects on
marine life
Proper method of disposing of
radioactive waste, proper
labeling, banning of nuclear
tests, alternative energy
sources, proper storage,
reusing, precautions at the
personal level
A. Overview on oil pollution and its effect on environment
118
7. Impact of oil exploration and spillage on marine environments
7.3 Types of oils
When spilled, the different types of oil can affect the environment differently. They can also
be grouped as per the extent of labor/trouble required to clean up. Spill responders group oil
into five primary groups. Each group oil along with its characteristics are mentioned below.
7.3.1 Group 1: nonpersistent light oils (gasoline, condensate)
• Highly volatile (evaporate within 12 days).
• Does not leave a residue behind after evaporation.
• High concentration of toxic compounds.
• Restricted, severe impacts on the water column and intertidal resources.
• Cleanup can be hazardous due to high flammability and toxicity.
7.3.2 Group 2: persistent light oils (diesel, no. 2 fuel oil, light crudes)
• Slightly volatile; leave residue (up to one-third of spill amount) after a few days.
• Presence of moderate concentrations of toxic compounds.
• Long-term contamination potential.
• Cleanup can be mapped efficiently.
7.3.3 Group 3: medium oils (mostly crude oils, IFO 180)
• About one-third will evaporate within 24 h.
• Oil contamination of intertidal zones can be severe and long-term.
• Oil impacts on waterfowl and fur-bearing mammals can be severe.
• Cleanup most efficient if managed promptly.
7.3.4 Group 4: heavy oils (heavy crude oils, No. 6 fuel oil, bunker C)
• Little or no evaporation or dissolution.
• Heavy contamination of intertidal areas.
• Severe impacts on waterfowl and fur-bearing mammals.
• Long-term decay of sediments possible.
• Shoreline cleanup is difficult under all circumstances.
7.3.5 Group 5: sinking oils (slurry oils, residual oils)
• Will sink in water.
• If spilled on the shoreline, the oil will behave similarly to that of heavy oils.
• If spilled on water, oil usually sinks swiftly enough that no shoreline contamination
occurs.
• No evaporation or dissolution when immersed.
• Severe impacts on animals living in bottom sediments, such as mussels.
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• Long-term contamination of sediments possible.
• Can be eliminated from the bottom of a water body by dredging.
7.4 Causes of oil pollution
Oil spills may originate from natural or anthropogenic activities.
7.4.1 Natural cause
Oil exists in various environments and may be naturally spilled due to multiple factors.
Such natural oil spills may occur in oceans due to the decaying of sedimentary rocks at
the bottom of the ocean. However, the major natural cause of oil pollution is oil seep also
known as petroleum seep. An oil seep is a natural leak of crude oil and gases from the
depth of the ocean. Seeps occur when crude oil leaks from the crevice and sediments of
the seafloor and migrate up. The seep oil varies in appearance depending upon the place,
weather, condition of the sea, and rate of the flow. The consistency of the seep can be
thick, sticky, tar-like in others it is dark like used motor oil. The seeped oil behaves exactly
like spilled oil which is spread by the water currents and wind, which later on form mats
and tar balls.
7.4.2 Anthropogenic activities
Anthropogenic causes—including accidental oil spills as well as leaks and spills due to
a large variety of human activities associated with oil refining, handling and transport,
storage, and use of crude oil and any of its distilled products. Thus it is evident that a variety of sources for oil spills and a variety of ways the oil could be spilled exist. While
numerous anthropogenic and natural sources of oil spill pollution determine the type and
amount of oil spilled, as well as the location of the oil spill, the type of the oil spill pollution is important for the fate and transport of the spilled oil and its impact on humans and
the environment. Moreover, numerous climate determinants and natural disturbances can
generate oil spills, the main causes of oil spill pollution are usually of anthropogenic origin. The most ordinarily found anthropogenic sources are the following:
7.4.2.1 Accidental spills
Accidental spills may occur in various circumstances, most often during the following
activities:
7.4.2.1.1 Storage
Oil and oil products may be stored in different ways including underground and
aboveground storage tanks; such containers may develop leaks over time.
7.4.2.1.2 Handling
Oil may leak/spill during transfer operations for various uses.
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7.4.2.1.3 Transportation
There could be large oil spills (up to millions and hundreds of million gallons) on water
or land through accidental rupture of big transporting vessels (e.g., tanker ships or tanker
trucks). For example, the Exxon Valdez spill was a massive oil spill off the Alaskan shoreline due to ship failure which happened in 1989. Major oil spillage like these have longterm effect on our environment, while several minor oil spills, through pipelines and other
devices also impact significantly.
7.4.2.1.4 Offshore drilling
Offshore drilling/oil platform/offshore platform is a mechanical process of extracting
petroleum and natural gas that lies in rock formation underneath the seabed. The offshore
drilling equipment is a large structure that facilitates well drilling to extract, process, and
store petroleum and natural gas.
7.4.2.1.5 Routine maintenance activities
The most common cause of oil spills are accidents concerning pipelines, tankers, pieces
of equipment, or storage facility. Fortunately, these accidents are often preventable. Proper
maintenance secures that oil-related equipment is in good working order and can also
serve in cleanup endeavors.
7.4.2.1.6 Road runoff
Road runoff pollution appears when pollutants from oil spills and brake wear of vehicles build up on roads and are then washed into nearby rivers when it rains. Road runoff
is a significant source of oil pollution because it includes a large number of different substances, all potentially dangerous. Trace metals, hydrocarbons and other organic pollutants
carried into the river pose a significant threat to river health.
7.4.2.2 Intentional oil discharges
Intentional oil discharges are not necessarily malevolent. Most of them occur in the following circumstances: (1) Through drains or in the sewer system. This includes any regular activities such as changing car oil if the replaced oil is simply discharged into a drain
or sewer system, and (2) Indirectly through the burning of fuels, including vehicle emissions; they release various individual components of oils and oil products, such as a variety of hydrocarbons (out of which benzene and PAHs could pose serious health risks).
7.5 Harmful effects of oil pollution
In the last few decades, the problem of oil spills and their consequences has brought
significant attention. When an oil spill occurs, it causes a plenitude of problems for the
environment and us. Oil spills have individual effects on the environment and the economy. On a primary level, oil spill impacts degrade waterways, marine life and plants, and
animals on the land. Cleansing an oil spill is quite expensive and the expenses get circulated to government agencies, nonprofits, and the oil transport company itself. Every time
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an oil spill befalls, the public loses faith in the oil company’s capability to manage this critical but needed product.
7.5.1 Effects of oil pollution on aquatic ecosystem
Oil spills can cause a wide range of impacts on the marine environment and are often
portrayed by the media as “environmental disasters”. When the oil is spilled into an
aquatic environment, it can harm organisms that live on, around, and beneath the water
surface by both chemical toxicity and by coating and suffocating wildlife. Petroleum contamination is a thriving environmental solicitude that harms both terrestrial and aquatic
ecosystems.
7.5.2 Effects on marine flora
Plants most affected by the oil spills grow near the shore or in the marshes. Mangrove
trees growing alongshore or in the marshes and coral reefs can suffocate in heavy pollution. Marine algae and seaweed respond variably to oil, and oil spills may result in dieoffs for some species. Algae may die or become more abundant in response to oil spills.
Although oil can prevent the germination and growth of marine plants, most vegetation
appears to recover after cleanup. Any effect on the marine plants weakens the entire food
chain and massive loss of phytoplankton in large oil spills will have a profound effect on
marine plants and ultimately on the food chain.
7.5.3 Effects on marine fauna
7.5.3.1 Impacts of oil spills on vertebrates
7.5.3.1.1 Fishes
Oil spills harm fishes in multiple ways; including increased mortality, kill or induce
sublethal loss to fish eggs and larvae for example, morphological malformations, reduced
feeding and growth rates, increase vulnerability to predators and deprivation, habitat degradation, loss of hatching ability of eggs, defiling of gill structures, impaired reproduction,
growth, development, feeding, respiration (Rice et al., 1984; Incardona et al., 2014;
Langangen et al., 2017).
7.5.3.1.2 Birds
Exposure to oil can have damaging repercussions on bird health and behavior, and
when consumed can prompt harm to the lungs, liver, and kidney. One of the common
results of oil on birds is the entrapping of their feathers which alters the feather
microstructure. Entrapping causes the organisms to lose their floating and flying ability due to compressed plumage and permits water to contact the skin causing hypothermia and ultimately death; especially during cold weather. Birds flashed to oil
experience impaired health such as ulcerations, embryotoxicity, cachexia, hemolytic
anemia, and aspergillosis, etc. (Finch et al., 2011).
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7.5.3.1.3 Mammals
Marine Mammals are most exposed to oil on the sea surface and shoreline causing adenoidal tissue damage, low immunity, lung, and adrenal diseases. Sea otters have their fur soiled
which blocks insulation and water repellence. Dolphins, sea turtles, and whales are known to
breathe at the sea surface and ingest oil after an oil spill ending in respiratory irritation, skininflammation, emphysema/pneumonia, gastrointestinal inflammation, ulcers, bleeding, diarrhea, and may induce damage to different organs (Drabeck et al., 2014; Venn-Watson et al.,
2015; Van Dolah et al., 2015).
7.5.3.2 Impacts of oil spills on invertebrates
7.5.3.2.1 Crustaceans
Marine crustaceans are divided into planktonic (open waters, free-living, ability to move)
and benthic (deep sea, terrestrial, estuaries, mobile, attach to substrates and rocky areas). Crabs
are often susceptible to oil toxicity due to the oil coat formation on their body surface which
cause suffocation. Moreover, feasting on oil-polluted debris causes blockage in their gills.
7.5.3.2.2 Molluscs
Mussels accumulate oil in their gills through filter-feeding, which exposes their tissues
to a high level of PAH (Polycyclic aromatic hydrocarbons). The constant accumulation of
oil exposes mussels to change in the cell structure, decreased overall immunity, weakened
development, gamete alteration, and DNA destruction. Mussels lose their nutritive value
and deteriorate the marine food web as they are the major food source for other organisms
in the marine ecosystem (Bellas et al., 2013).
7.5.3.2.3 Zooplanktons
Zooplankton is an important food resource, especially for whales. It can affect or constrain
the primary productivity by top-down effects in return. Some zooplankton, such as copepods,
euphausiids, and mysids, assimilate hydrocarbons directly from seawater and by ingesting oil
droplets and oil-contaminated food. The ingestion of oil by these organisms frequently induces
mortality, while the organisms that survive often show developmental and reproductive irregularities (Antonio et al., 2011; Jiang et al., 2012; Almeda et al., 2014). Due to the inefficiency of zooplanktons to move against currents, they tend to be stranded in oil-polluted waters and are
prone to reduce physiological functions and mortality. Free-floating embryos and larvae that
encounter oils exhibited miniaturized physiological functions such as growth, egg production,
nutrition which eventually affects the health of the matured communities (Rodrigo et al., 2013).
7.5.3.3 Effects of oil pollution on wildlife
Oil causes harm to wildlife through physical contact, ingestion, inhalation, and absorption. Floating oil can contaminate the plankton, which includes algae, fish eggs, and the larvae of various invertebrates. Fish feeding on these organisms can subsequently become
contaminated through ingestion of contaminated prey or by direct toxic effects of oil. Larger
animals in the food chain, including humans, can consume contaminated organisms as they
feed on these fish. Although oil causes immediate effects throughout the entire spill area, it
is the external effects of oil on larger wildlife species that are often immediately apparent.
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7.5.3.3.1 Birds
• External effects
• External effects of oil are the most prominent and are the most rapidly debilitating.
Oil, by disrupting the interlocking structure of feathers, damages the waterproofing
properties of the external feathers and soaks the downy insulating layer.
• This in turn can lead to:
• Hypothermia by lessening or eliminating the insulation and waterproofing attributes
of feathers.
• Sinking or swamping as oiled feathers weigh more and cannot entrap sufficient air to
keep the birds buoyant
• Risk of predation, as feathers coated with oil decrease a bird’s ability to fly away.
• Internal effects
• The internal effects of oil on birds might not as visually apparent as the external effects are
evenly life-threatening. Birds can ingest or gasp oil as they try to spruce oil from their feathers or dine on a tainted food source. Depending on the type of petroleum product, its
weathering stage, and its toxicity, poisoning through ingestion can vary from sublethal to
acute.
• Ingestion of oil usually results in injury to the gastrointestinal tract, blocking the animal’s digestive system from processing food or water and prompting the animal to
become progressively more vulnerable in a very short period.
• Inflammation of other mucosal exteriors can be seen, such as ulceration of the eyes
and the moist areas inside the mouth.
• Kidney damage is believed to occur as a direct effect of the toxins in the oil and as a secondary effect of critical dehydration. As an oiled bird becomes more debilitated, its
immune system is affected because of which the bird becomes susceptive to bacterial and
fungal infections.
• The oil may also influence the efficacy of those birds that survive the oil spill to reproduce. Breeding and incubating response, number of eggs laid, the fertility of the eggs,
and shell thickness may all be affected.
7.5.3.3.2 Marine mammals
• External effects
• The external effects of oil on marine mammals including sea otters, sea lions, seals,
walruses, sea cows, polar bears, dolphins, porpoises, and whales, vary, depending on
the species but may include:
• Hypothermia in polar bears, sea otters, and fur seals pups, are caused by reduction or
damage to the insulation of their thick fur. Adult fur seals have blubber and are therefore less likely to suffer from severe hypothermia if oiled.
• Skin lesions are a problem for dolphins and whales that swim through oiled areas as
they do not have any fur on their body
• Eye irritation is a problem for all marine mammal species exposed to oil
• Marine mammals, especially seal and sea lion pups, become easy prey while oil sticks
their flippers to their bodies, making it hard for them to evade predators; fur seal
pups can drown in this situation
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• Marine mammals lose bodyweight when they cannot serve due to contamination of
their environment by oil
• The scent that seal and sea lion pups and mothers rely on to recognize each other gets
concealed, leading to denial, abandonment, and starvation of the pups.
• Infection or poisoning in manatees and trouble eating due to oil spiking of the sensory
hairs around their mouths
• Abridged ability to hunt due to fouling of the baleen of surface feeding whale species
• Internal effects
• Internal effects further differ by species but may include:
• Obstruction of lungs and impaired airways from inhaling of oil vapors and droplets
• Emphysema and pneumonitis are common in most marine mammal species but a special concern is for sea otters that spend much of their time on the surface and cetaceans who come to the surface to breathe.
• Kidney, liver, and brain damage, as well as anemia and immune suppression, are
implied side effects of ingestion and inhaling of oil
• Gastrointestinal ulceration, anemia from damaged red blood cells, and injury to
mucous membranes.
7.5.3.3.2.1 Sea turtles
• External effects
• Sea turtles can grow poisoned when they arise to the surface to breathe and discover
themselves amid an oil slick.
• During the breeding season, females may become oiled when they appear in the contaminated area or when they arrive at the seashore to lay eggs.
• Juveniles may display greater risk of inhaling and ingesting the oil as they get captured in oil when they travel to sea after hatching.
• Internal effects
• Poisoning by ingestion of toxic ingredients through the skin, leading to damage to the
digestive tract and other organs
• Damage or irritation to airways, lungs, and eyes
• Infection of eggs, which may inhibit their maturation
• Consequence assessment results from the deep water horizon spill in the United
States, which happened during sea turtle nesting and hatching season.
7.5.3.3.2.2 Seals
• External effects
• Seals (true seals, sea lions, fur seals, and walruses) are flashed to oil pollution because
they employ enough of their time on or nearby the water surface. They need the surface to breathe and frequently wriggle out onto beaches.
• During an oil pollution incident, they are at risk both when surfacing and at hauling out.
• Fur seals are more defenseless due to the possibility of oil adhering to their fur which
will result in the fur losing its insulating ability.
• Due to the heavy oil coating on fur seals they may exhibit diminished swimming
strength and lack of movement when the seals are on land.
• Internal effects
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• Seals may also get infected through the ingestion of oiled food or the inhaling of oil
droplets and mists.
• Light oils and hydrocarbon vapors, will strike revealed sensitive tissues. These involve
mucous sheaths that envelope the eyes and line of the oral cavity, respiratory surfaces.
• This can produce conditions like corneal abrasions, conjunctivitis, and ulcers.
Consumption of oil-contaminated prey could guide to the accumulation of hydrocarbons in tissues and organs.
7.5.3.3.2.3 Polar bear
External effects
The polar bear is an apical predator and a generic image of the Arctic. Petroleum exploration and extraction have been in motion along the coast of northern Alaska for more than 25
years. Contact with oil spills can reduce the insulating effect of the bear’s fur. They must then
use more energy to keep themselves warm and balance it by increasing their caloric intake,
which may be difficult. Polar bears are known to groom themselves regularly to sustain the
insulating properties of their fur and an oiled bear would be expected to ingest significant
quantities of oil during grooming. Oiling of fur and associated thermoregulatory stresses.
Internal effects
While combing an oil-contaminated fur (self-grooming) or feeding on an oiled prey,
they may consume the oil which may culminate in the death of polar bears.
7.5.3.4 Impact of oil pollution on human health
Oil and gas has remained the powerhouse of the world economy for more than 100
years. Notwithstanding this, we understand little regarding the health consequences of
spills and purposefully executed oil waste.
Studies associated with biomarkers have revealed major irretrievable harm to humans
exposed to oil and gas spills. These outcomes can be grouped into respiratory damage, liver
damage, lowered immunity, enhanced cancer risk, reproductive impairment, and higher levels
of unspecified toxins. Webb et al. (2016), conducted a study that revealed that men who had
worked cleaning up the spill had twice as mercury in their urine as did men who had not been
involved in the struggle to restore the inlet in which the oil had deteriorated. Mercury damages
the brain and the liver. Each time a pipeline ruptures or a waste pit drains, we can suspect that
the people in the vicinity may get affected with mercury, through the contaminated water, the
fish they eat, and the air they breathe (Fig. 7.1).
Oil spillage is enduringly harmful to human health and as well as animals. Oladejo and
Onyejiaka (2017), proclaimed that there is a relationship between vulnerability to oil pollution
and the progress of health problems. Drinking water from polluted sources or consuming
marine creatures such as fish, oysters, mussels, etc., automatically brings in high levels of carcinogenic chemicals. Other conditions associated with the carcinogenic chemicals include respiratory difficulties, skin diseases such as rashes or dermatitis, gastrointestinal dysfunctions, eye
problems, water-borne diseases, and neuronal predicaments joined with an unhealthy diet.
7.5.3.5 Effect of oil pollution on economy
Infection of waterfront areas with high convenience value is a constant trait of many oil spills.
In addition to costs incurred by cleanup activities, serious economic losses can be experienced
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7. Impact of oil exploration and spillage on marine environments
FIGURE 7.1 Effect of oil spill on human health.
by industries and individual’s dependent on coastal resources. Ordinarily, the tourism and fisheries divisions are where the greatest repercussions are felt. However, there are also many other
business activities and sectors that can potentially suffer disruptions and loss of earnings.
7.5.3.5.1 Tourism
Separation of recreational ventures such as swimming, sailing, angling, and diving induced
by oil-contaminated shores is ordinarily relatively short-lived. Once shorelines are clear, normal
sales and actions would be expected to continue. Still, more long term and damaging commercial impacts can befall when the communal judgment of extended and wide-scale pollution
remains long after the oil has gone. In these circumstances, it takes an even longer period for
business activities to return to normal, sometimes with far-reaching consequences.
7.5.3.5.2 Fisheries and mariculture
Fishing formations can be influenced by spilled oil, both as a result of contamination of containers and by fishing bans. Oil spills can produce serious harm to fisheries and Mariculture
sources. Physical poisoning can affect stocks and obstruct business ventures by staining gear or
hindering access to fishing sites. The degree to which economic results will be felt by the fisheries division following an oil spill will depend on numerous factors such as the characteristics of
the spilled oil, the details of the episode, and the type of fishing activity or business affected.
The physical characteristics of the marine environment and coast also play a role in determining
the range and extent of economic impacts.
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127
7.5.3.5.3 Other industries/businesses affected by marine oil spills
Heavy production that relies on seawater for common services can be at high risk, particularly
if water consumptions are near to the surface. If such plants are accountable for satisfying needs
on a social scale, disturbances can be far-reaching. Other types of coastal industry such as shipyards, ports, and harbors can also be disrupted both by oil spills and consequent cleanup services.
7.6 Bioaccumulation and biomagnification: marine chemistry
Petroleum or crude oil is one of the most common pollutants released into the marine
environment (Wang et al., 2019). Increasing global power demand has increased in the
quest for and shipping of crude oil in the sea, making marine ecosystems uniquely susceptive (oil pollution cycle) to the increased risk of crude oil spills (Fig. 7.2).
7.6.1 Toxins in the marine food chain
Chlorinated hydrocarbons including polychlorobiphenyls, and DDT derivatives, bioaccumulate, and biomagnify as they move up the marine food chain; from phytoplankton to
copepods to fish to seals to killer whales. These hydrocarbons are fat-soluble and are not
FIGURE 7.2 Oil pollution cycle.
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7. Impact of oil exploration and spillage on marine environments
generally metabolized. Rather, they collect in the blubber of aquatic creatures with the conclusion that killer whales have multiple thousands of events the level of toxins than
plankton.
Researchers have documented that migrating whales and inhabitant whales in the Gulf
of Alaska are genetically distinct populations. While some visitors travel throughout the
Gulf and prey mostly on marine mammals, citizens usually have a more limited range
and prey essentially on fish.
7.6.2 Bioaccumulation and biomagnification of hydrophobic organic compounds
in fish
Biomagnification of hydrophobic organic compounds (HOCs) increases the ecoenvironmental hazards. Dietary uptake models influence bioaccumulation and biomagnifications of HOCs
in fish. Wang et al. (2019) indicated that in addition to the well-known lipidwater partitioning, the bioaccumulation of HOCs in fish is also an irregular kinetic process created by the
inconstancy of HOC concentration in the gastrointestinal tract as a result of the discrete food
ingestion. The discontinuity and randomness of dietary uptake can partly explain the differences among aquatic ecosystems concerning biomagnifications for species at similar trophic
levels and provides new insight for future analysis of bioaccumulation data for fish.
7.6.3 Biomagnification and bioaccumulation of mercury in an arctic marine
food web
Several recent studies have shown that the use of delta 15N analyses to characterize trophic relationships can be useful for tracing contaminants in food webs (Atwell et al.,
1998). Most vertebrates show greater variance in mercury concentration than invertebrates,
and there is a trend in seabirds toward increased variability in mercury concentration with
the trophic position. Within species, no confirmation of bioaccumulation of mercury with
age in the muscle tissue of clams (Mya truncata) or ringed seals are found.
7.7 Remedies to cope up with oil pollution
Oil is one of the most copious pollutants in the oceans. According to marine insight,
about 3 million metric tons of oil pollutes the oceans yearly. Oil spills fluctuate in their
cruelty and the degree of destruction they cause. This can be charged to disparities in the
oil type, the location of the spill, and the weather circumstances present. The spread and
behavior of spilled oil in the seas is governed by a variety of chemical, physical, and biological processes. The first step to tackle the oil spill is to restrict the oil spill from its loading. This typically involves preparing the units and accompanying standard systems while
leading the ships to the port, moving through small channels, and staying on the designated path for the course. In case of any spill, there are diverse clarifications measures
based on the quantum of the spill and the area of the spill (Table 7.2 and Table 7.3).
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7.7 Remedies to cope up with oil pollution
TABLE 7.2 Methods for cleaning up spilled oil.
Methods for cleaning up
Sr. no. oil
Pros and cons
When to use
Inexpensive, effective, but hard to
control and still poses risks on
human health
Bacteria needs to be readily available,
when other methods will cause harm
to natural environments
1.
Bioremediation (use of
biological agents to break
down or remove spilled
oil).
2.
Controlled burning/in situ Reduces oil but can cause wind
burning
pollution
Large oil slick, when human health is
not at risk
3.
Dispersants (cause the oil
Separates the oil slick, but still
slick to break up and disband) pollutes the water
Large oil slick, bacteria needs to be
readily available
4.
Vacuum and centrifuge
(collects and separated the oil
and water)
Effective method, but can disturb
the natural environmental with
heavy clean up machinery
When oil is floating, when oil can
easily be collected, when location
allows access
5.
Natural attenuation
(method of allowing the
natural environment to)
Used in ecological sensitive areas
like wetlands
When other methods will disrupt the
natural environment
6.
Dredging (for oil that is
dispersed with detergents)
Eliminates oil by physical removal,
but can only be used for oils denser
than water and can disrupt the
surrounding environment.
When the environment allows access,
when oil has been removed from the
top layer of sediment but still exists
below.
7.
Skimming (traps spilled oil Effective method, but requires calm When oil is floating, easy to surround
for later separation)
waters at all times during the
the oil, clam winds and ocean current
process of skimming
TABLE 7.3 Equipment used for cleanup operations.
Sr. no. Oil spill clean up equipment
Description
1.
Booms
Floating connected barriers that gather the oil for easy
collection, can relocate oil floating on ocean’s surface, can be
used as a sorbent as well
2.
Oil skimmers
Skims the oil floating on the ocean’s surface for Collection and
separation.
3.
Oil sorbents
Large solid absorbents that absorbs oil, can be chemical and
natural forms
4.
Chemical and biological agents
helps to break down the slick oil, and disperse the oil for later
collection
5.
Vacuums
Removes spilled oil from fouled coastlines and Ocean surface.
6.
Shovels, tractors, bulldozers, conveyor
belts, and other road equipment
Manual labor tools used to clean up/collect oil on beaches
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7.7.1 Physical methods
7.7.1.1 Oil blooms
Oil booms are the most popular and recommended equipment employed in oil cleansup due to their more simplistic design and smoother performance. These are also perceived as containment booms that confine the oil to a more petite area and check it from
spreading further. Tools termed containment booms act like a barrier to prevent the oil
from additional spreading or drifting away. Booms float on the water surface.
7.7.1.2 Skimmers
Once the oil is surrounded by oil booms, it can be extracted or skimmed easily with the
direction of skimmers or oil scoops. Skimmers are devices specifically produced to suck
up the oil from the water surface like a vacuum cleaner. These skimmers are outfitted
onto boats to eliminate the floating oil or oily contaminants. They are used to physically
separate the oil from the water so that it can be collected and provided for reuse.
7.7.1.3 Sorbents
Sorbents are substances that mop up liquids by both absorption or adsorption. Both
these features make the method of cleanup much more manageable. Substances generally
utilized as oil sorbents are hay, peat moss, fodder, or vermiculite. The application of sorbents is a simple method of oil cleanup.
7.7.1.4 Burning
It is relative to lighting rice husk after yielding rice crop. In this way, the volatile oil is
set to fire by lighting it cautiously. In this method, the oil hovering on the surface is
inflamed to burn it off. It is the most skilled method of oil cleanup, as it can efficiently
exclude 98% of the total spilled oil. According to Obi et al., (2008) The smallest concentration of the slick on the sea surface for each moderate effectiveness of in situ burning is
3 mm. This is because it would be very challenging to ignite a layer that is not dense
enough.
7.7.2 Chemical treatment
7.7.2.1 Dispersant
Dispersals are chemicals expanded above the spilled oil to begin the disintegration of
oil. After disintegration, the exterior area of oil particles develops and it becomes more
manageable for them to form a bond with water. This method uses the bonded particles
immersed in water and makes them convenient for microbes, which deteriorate them later
on. Dispersal agents, such as Corexit 9500, are chemicals that are spattered upon the spill
with the help of aircraft and boats, which support the natural breakdown of oil elements.
They release the oil to chemically bond with water by expanding the exterior area of each
molecule. This guarantees that the slick does not move over the surface of the water, and
is simpler to deteriorate by microbes.
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7.7 Remedies to cope up with oil pollution
7.7.2.2 Hot water and high-pressure washing
This process is practiced to remove the captured and exposed oil from areas that are
usually unavailable to machinery. Water heaters are employed to heat up water to about
170 C, which is then sprayed by hand with high-pressure rods or outlets. The oil is thus
flushed to the water surface, which can be accumulated with skimmers or sorbents.
7.7.2.3 Chemical stabilization of oil by elastomizers
Immediately after an oil spill, the immediate solicitude is to restrict the oil from growing and
polluting the adjoining areas. While mechanical systems like handling oil booms efficiently hold
the oil, they have some restrictions to their use. Very lately, specialists have been using compounds like “Elastol,” which is primarily polyisobutylene in a white powdered form, to confine
oil spills. The compound gelatinizes or solidifies the oil on the water surface and thus prevents it
from spreading or escaping. The gelatin is simple to recover, and this makes the method
extremely efficient.
7.7.3 Bioremediation
Bioremediation deals with the use of particular microorganisms to eliminate any toxic
or dangerous substances onsite or off-site. There are several species of bacteria, fungi,
archaea, and algae that deteriorate petroleum products by metabolizing and splitting them
into simpler and nontoxic molecules. Sometimes, reagents and fertilizers may be affixed to
the area. The phosphorus-based and nitrogen-based fertilizers contribute sufficient nutrients to the microorganisms so that they are capable to develop and multiply quickly. This
process is usually not used when the spill has occurred in the deep seas and is increasingly put into operation once the oil starts to surround the shoreline. Table 7.4 shows different microbes used for Bioremediation of oil-contaminated water.
TABLE 7.4 Different microbes used for Bioremediation.
Sr. no. Microbes
Contaminants
Function
Reference
1.
Fungi
Polycyclic Aromatic Hydrocarbon
Biodegradation
Atagana (2009)
2.
Pseudomonas sp., Pycnoporus
sanguineus
PAHs
Biodegradation
Arun et al. (2008)
3.
Acetobacterium paludosum,
Clostridium acetobutylicum
Hexahydro-1,3,5- trinitro-1,3,5triazine (RDX)
Biodegradation
Sherburne et al.
(2005)
4.
Enterobacter strain B-14
Chlorpyrifos
Biodegradation
Singh et al. (2004)
5.
Comamonas testosteroni VP44
-Mono chlorobiphenyls-
Substrate
specificity
Hrywna et al.
(1999)
6.
Rhzobium meliloti
Dibenzothiophene
Biodegradation
Frassinetti et al.
(1998)
7.
Rhodococcus erythropolis TA421
Polychlorinated biphenyl
Biodegradation
Damaj and Ahmad
(1996)
8.
P. pseudalkaligenesKF707-D2
TCE,toluene,benzene
Substrate
specificity
Suyama et al. (1996)
A. Overview on oil pollution and its effect on environment
132
7. Impact of oil exploration and spillage on marine environments
7.7.4 Natural recovery
The most manageable way of dealing with the oil spill cleanup process is to make usage of
the impulses of nature like the sun, the wind, the weather, tides, or naturally occurring microorganisms. It is deployed in several instances when the shoreline is extremely remote or distant,
or the environmental influence of cleaning up a spill could possibly far exceed the advantages.
Because of the reliability of these components the oil regularly evaporates or splits down into
simpler components.
7.8 Conclusion
Oil is exported by nearly 100 oil-trading countries of the world and the economic
growth of some countries directly depends on its export. Oil explorations, transport, storage and distribution activities govern the oil price which affects both the oil-exporters and
the importers. Certainly, the oil is required by every country for transportation, electricity
generation, running machineries, synthesis of oil-based products, etc. But the dark side is
that the oil spills (minor or major) during exploration and transport, influence the environment by damaging and debilitating the marine habitat. These spills can be disastrous
because they disturb the functionality of the marine food chain and the food web as well
and human as well. The oil spill affects a wide range of people, from coastal communities
to a world leader as well either directly or indirectly. Since oil is an important source of
energy, therefore oil exploration activities are a continuous business. However, the lessons
learnt on oil-spill tragedies from the past have made it possible to clean up the oil-spills
without delay, through high-tech instrumentation, materials and quick-response strategies.
There are now several companies which provide quick, oil spill response solutions in case
of accidental or general oil-leakage and spillage (Bashi-Azghadi et al., 2010). These solutions include a complete range of skimmers, oil booms, power- packs and pumps, workboats, landing-crafts, storage, and ancillary equipment. Apart from all this, with the alertness of the work-force during oil exploration and drilling may be instrumental in avoiding
unfortunate tragedies. Moreover, adoption of biotechnologies (Erickson and Mondello,
1993) and forward technologies in oil-exploration regimes like use of uniquely balanced
marine vessels and terminals, use of tankers with double hulls, use of corrosion-resistant
storehouse tanks, etc. However, the responsibility for the prevention of oil spills not only
lies on the engineers/workers of oil-trading companies but also on governments because
the origin of oil-waste in the ocean is usually due to carelessness or purposeful, rather
than accidental. Therefore efficient prevention of oil spills requires combined efforts
towards sustainability and commitment towards the safe-exploration, transport, storage
and distribution and utilization activities.
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A. Overview on oil pollution and its effect on environment
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S E C T I O N
B
Physical processes
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C H A P T E R
8
Superhydrophobic polymeric
adsorbents as an efficient oil separator
Shubhalakshmi Sengupta1,*, Priya Banerjee2,*,
Anil Kumar Nallajarla1, Venkatalakshmi Jakka1,
Aniruddha Mukhopadhyay3 and Papita Das4
1
Department of Sciences and Humanities, Vignan’s Foundation for Science, Technology and
Research (deemed to be University), Guntur, India 2Department of Environmental Studies,
Centre for Distance and Online Education, Rabindra Bharati University, Kolkata, India
3
Department of Environmental Science, University of Calcutta, Kolkata, India 4Department of
Chemical Engineering, Jadavpur University, Kolkata, India
O U T L I N E
8.1 Introduction
8.2 Materials used for oil/water
separation
8.2.1 Meshes and membranes for
oil/water separation
8.2.2 Using inorganic materials
8.2.3 Using organic materials
8.3 Polymer-based adsorbents for
oil/water separation
8.3.1 Plastic-based adsorbents
8.3.2 Polyurethane oil sorbents
8.3.3 Polystyrene oil sorbents
8.3.4 Polyethylene and polypropylene
based oil sorbents
140
8.3.5 Oil sorbents based on the
methacrylate polymers
8.3.6 Oil sorbents based on the
miscellaneous polymers
8.3.7 Aerogels
148
148
8.4 Superhydrophobic polymeric
adsorbents
148
8.5 Conclusion
152
Acknowledgments
152
References
152
142
142
144
145
145
146
146
146
148
146
* Shubhalakshmi Sengupta and Priya Banerjee contributed equally to this chapter.
Advances in Oil-Water Separation
DOI: https://doi.org/10.1016/B978-0-323-89978-9.00010-0
139
© 2022 Elsevier Inc. All rights reserved.
140
8. Superhydrophobic polymeric adsorbents as an efficient oil separator
8.1 Introduction
Polymeric substances revolutionized industrial history of this world ever since their
introduction in the early 20th century (Al-Salem, Lettieri, & Baeyens, 2009). Various technological advancements and research has resulted in wide application of these polymeric
substances in various applications like packaging, electronics, automobile industry, biomedical devices, paints, construction materials, insulators, textile, consumer goods.
However, their extensive use has also led to enormous waste generation which in turn has
cause both direct and indirect detrimental impacts on this planet. Moreover, plastic waste
management is hugely hindered by difficulties in screening and processing processes
(Baroulaki et al., 2006).
Another, environmental hazard which plagues our planet every year is oil spills (AlMajed, Adebayo, & Hossain, 2014). The Erika oil spill of 1999, the Gulf of Mexico oil spill
of 2010, and the South Atlantic oil spill of 2019 (de Oliveira Soares et al., 2020) are examples of such instances. Oil spills over oceans spread very quickly over water and undergo
various physical and chemical processes like emulsification and degradation (Crone &
Tolstoy, 2010). Presence of oils and its degraded products are extremely hazardous to the
marine environment (Rogowska & Namieśnik, 2010). Few impacts of oil spills on marine
ecosystems have been shown in Fig. 8.1.
FIGURE 8.1 Effect of oil spill on marine
organisms. (A) Oil spill on Brazilian beaches
and the resulting damage to different species,
leading to long-term negative consequences:
(B) fish; (C) Marine turtle Chelonya midas covered with oil; (D) zooplankton (crab larvae
(zoea 1) with mouth apparatus (arrows) possibly oiled) pelagic invertebrate; (E) Portuguese
man-of-war Physalia physalis with its tentacles
oiled, as well as macroalgae and marine
plants; (F) seagrass impregnated with oil.
Source: Reproduced with permission from de
Oliveira Soares, M., Teixeira, C.E.P., Bezerra,
L.E.A., Paiva, S.V., Tavares, T.C.L., Garcia, T.
M., . . . Cavalcante, R.M. (2020). Oil spill in
South Atlantic (Brazil): Environmental and
governmental disaster. Marine Policy, 115,
103879 rElsevier.
B. Physical processes
8.1 Introduction
141
Several strategies have been adopted to prevent and remedy oil spills. However, these
are not always environmentally benign. Methods that have been adopted in this regard
include burning of oil layer which does help in removing the oil slicks but results in polluting the environment in return (Mullin & Champ, 2003). Booms are also used to physically contain the oil slicks allowing the skimmers to physically remove the oil layers.
However, this process is very laborious, expensive, and not feasible in rough seas
(Schrader, 1991). Chemical dispersants and biosurfactants produced by microorganisms
result in dispersing and degrading oil spills, but sometimes addition of these chemicals
might prove hazardous to the marine environment due to the toxicity imparted by them
on the marine organisms.
Nowadays, adsorbents of different kinds are used widely to remove oil from the seas.
Natural sorbents like agricultural wastes and minerals (Saleem, Riaz, & Gordon, 2018)
have been used for this purpose. Hydrophobicity is a significant parameter of these materials. Even in the case of hydrophilic materials, surface modifications are done to induce
hydrophobicity (Saleem et al., 2018). With the advent of nanotechnology nanoparticles,
nanowire membranes and other carbonaceous nanomaterials [e.g., carbon nanotubes
(CNTs), graphene] have been used for this purpose (Gupta, Dunderdale, England, &
Hozumi, 2017). Despite the availability of various sorbents, conventional polymers like
polypropylene (PP) and polyethylene are widely used for oil separation owing to their
economic viability (Carmody, Frost, Xi, & Kokot, 2007). Thus newer application areas and
use of more ecofriendly and biodegradable polymers are sought by researchers.
The desired properties which are mostly sought in oil sorbents include a good mutual
solubility of the sorbent and the oil, high surface area, porous structure, and penetration
ability of the oil into network structure of the sorbent (Gupta et al., 2017). Recent studies
have reported superhydrophobic modification of the aforementioned porous nanomaterials for efficient oil/water separation. These engineered materials are a new approach
toward oil recycling and water remediation. Surface modification of porous substances
like sponge, melamine, copper mesh, polyurethrane have rendered them superhydrophobic. Moreover, superhydrophobic aerogels have been prepared using both natural and
synthetic carbon materials. However, these materials, although environmentally friendly,
are often not economically viable (Gupta et al., 2017; Saleem et al., 2018). Nevertheless,
there is tremendous scope and potential for further research in the field of addressing oil
spillage problems in our marine environment (Saleem et al., 2018).
Many industries, such as metal/steel, petrochemical, mining, food, and textile produce
exceptionally large volumes of oily-rich wastewater pose serious global environmental
concerns (Chen & Xu, 2013). For example, a mining operation produces approximately
140,000 L oil contaminated water per day (Guerin, 2002). Frequent oil-leakages/spillages
caused by water vehicles are potential threats to the marine environment and ecology
(Chen & Xu, 2013). Various oil/water separation methods for example, (1) Conventional
cleanup methods like Mechanical methods (Booms, skimmers) and Chemical methods
(Dispersants, emulsion breakers) (Vergetis, 2002), (2) Advanced cleanup methods like bioremediation (Ventikos, Vergetis, Psaraftis, & Triantafyllou, 2004) are reported so far.
However, these methods are energy-intensive. Commonly porous materials are used to
absorb oil from water. However, such materials suffer from low oil separation efficiency,
as they simultaneously absorb water and oil. After that various oil/water separation
B. Physical processes
142
8. Superhydrophobic polymeric adsorbents as an efficient oil separator
methods are reported, most of them have advantages as well as disadvantages. In recent
studies mainly focused on surface superwettabilities (Xue, Cao, Liu, Feng, & Jiang, 2014),
such as superhydrophobicity, superoleophobicity, superhydrophilicity and superoleophilicity (Ragesh, Ganesh, Nair, & Nair, 2014; Wang & Gong, 2017; Wang, Liang, Guo, & Liu,
2015). Surface wettability is an inherent property of solid surface, the surface chemistry
and geometric morphology solid surfaces are influence on the wetting/de wetting behaviors of examine liquids on solid surface (R.N. Wenzel., 1936). Superhydrophobicity/
superoleophilicity exhibiting “oil-removing” properties and superoleophobicity/superhydrophilicity exhibiting “water-removing” properties (Xue et al., 2011). Superhydrophobic/
superoleophilic stainless steel mesh is used for the oil/water separation which is allowing
oil was first demonstrated by Jiang’s group (Feng et al., 2004) and also using hydrophilic
polyacrylamide hydrogel-coated stainless-steel mesh which allows only water to permeate
it (Xue et al., 2011).
8.2 Materials used for oil/water separation
8.2.1 Meshes and membranes for oil/water separation
Over the past few decades, researchers have been using functionalized meshes and
membranes with superwettability to separate oil from water. Due to their simplicity
and low cost, they are ideal candidates for wide scale applications. Functionalization
and mechanism of action of these devices have been explained in the following section.
8.2.1.1 Mechanism of action
Woven metal-wire meshes have been functionalized with various chemicals to create an
oil/water separating mesh having necessary properties. The majority of meshes reported
so far is of hydrophilic in nature. They allow the passage of water and are referred to as
“water selective” meshes and smaller proportion of meshes reported is oleophilic in nature
which allow the passage of oil and are referred to as “oil selective” meshes (Gupta et al.,
2017). Although it is possible to create an oil/water separation mesh which can be programmed to shift between water-selective and oil-selective performance, they are of rare
occurrence (Dunderdale, England, Sato, Urata, & Hozumi, 2016). A mesh having pore size
,1 μm is referred to as a membrane (Gupta et al., 2017). However, these two names are
often used interchangeably. Oil/water separation membranes have been reported with
pore diameters larger than some of the reported oil/water separation meshes. However,
irrespective of pore size, the mechanism of action is same for both. In comparison to other
oil/water separation devices, meshes can separate large volumes of oil water in a given
time, due to its large pore diameters.
Membranes are able to separate emulsions of oil and water due to their smaller pore
sizes. But meshes are limited by the fact that can only separate oil droplets larger than
their mesh size. Nevertheless, meshes are simple and cost effective and low pressure
required to drive liquid through them Moreover, often gravity is sufficient to provide the
low pressure required to drive liquid through them.
B. Physical processes
8.2 Materials used for oil/water separation
143
8.2.1.2 Functionalization of meshes and membranes
Several methods of surface functionalization have been used to alter the surface wetting
properties of woven metal meshes to enable them for oil/water separation. The advantages and disadvantages of using different types of functionalizations have been discussed
herein. Some examples of functionalized meshes and membranes are summarized in
Table 8.1.
TABLE 8.1 Typical filtrationbased oil/water separation materials fabricated by different methods.
Substrates/materials
Surface modification method
Chemicals/materials for surface modification
Metal meshesCu mesh/CuO or Cu
(OH)2
Chemical etching
NaOH and (NH4)SO8Potassium peroxydisulfateAmmonia
vapor
Particles
Electrodeposition
0.1 M CuSO4, 1 M H2SO4
Thermal treatment
_
Deposition
Polyelectrolytes or polymers
Mixed with SiO2 particles
TiO2 particles
Nanotubes
_
Carbon nanotubes
Halloysite nanotubes
Inorganic materials
_
Graphene oxide
Silica zeolite
Silver
Polymers
Atom transfer radical
polymerization
Polymer brushes
Electrostatic deposition
Poly (dimethylamino ethyl methacrylate)
In situ oxidative polymerization
Poly (3-ehylenedioxythiophene)-b-poly (styrene sulfonate)
Grafting polymerization
Polyacrylic acid
Spray drying
PTFE(Poly(tetrafluoroethane))
Poly (dimethyl siloxane) based polyurethane
Gels
SAMs
Dip coating
PTFE
Phase inversion
Polyethersulfone/cellulose acetate
In situ polymerization
Polydopamine
Photoinitiated polymerization
Hydrogel (Polyacrylamide)
Chemical vapor deposition
Sylgard184
Self-assembly from solution
Thiols
Stearic acid
Organosilanes
Biomaterial
Cross linking with glutaraldehyde
Chitosan
Source: Reproduced with permission from Gupta, R. K., Dunderdale, G. J., England, M. W., & Hozumi, A. (2017). Oil/water separation
techniques: A review of recent progresses and future directions. Journal of Materials Chemistry A, 5(31), 1602516058.
B. Physical processes
144
8. Superhydrophobic polymeric adsorbents as an efficient oil separator
8.2.2 Using inorganic materials
The growth of nanostructured copper oxides [CuO or Cu(OH)2] on mesh surface is the most
common type of surface functionalization carried out using inorganic materials (Gupta et al.,
2017). Prior to functionalization, the mesh surface was highly hydrophilic and worked as a water
selective mesh. The structured surface is created by etching Cu meshes with sodium hydroxide
and ammonium persulfate to yield a mesh covered with Cu(OH)2 nanowires. These are used to
purify water from a range of oil/water mixtures (including n-hexane, isooctane, petroleum ether,
diesel, and soybean oil) to have oil content around 25 ppm (Zhang et al., 2013). Another selective
wettability mesh is Cuo-covered Cu surface created through an etching with potassium peroxydisulfate (Liu et al., 2016) functionalized stainless steel meshes with a solution made of CuCl2 and
hydrochloric acid for different periods of time. This treatment resulted in the formation of
Cu crystal like structures on the mesh surfaces (Liu et al., 2016).
Titanium dioxide (TiO2) is also used to functionalize both metal meshes and membranes (Gondal et al., 2014). Schematic representation of fabrication of polyvinylpyrrolidone—TiO2 nanowire coated metal mesh is shown in Fig. 8.2 (Pan, Cao, Li, Du, & Cheng,
2019). Materials like graphene oxide (GO) is also used to create superhydrophilic meshes
that selectively separate water from oil/water mixtures (Dong et al., 2014; Liu, Zhang, Fu,
& Sun, 2015). Incorporation of CNTs into membranes also change the surface morphology
(Gu et al., 2014; Yu et al., 2014; Zhang, Li, Li, & Wang, 2016). In another study, silver
nitrate has been used to coat stainless steel meshes with a layer of silver which in turn
increased surface roughness (Wang, Lei, Xu, & Ou, 2015). This mesh performed as a
water-selective mesh without any further functionalization.
FIGURE 8.2 Schematic illustration of the fabrication of polyvinylpyrrolidone-TiO2 NWs coated stainless steel
membranes with special wettability for oil/water separation. Source: Reproduced with permission from Pan, Z., Cao,
S., Li, J., Du, Z., & Cheng, F. (2019). Anti-fouling TiO2 nanowires membrane for oil/water separation: Synergetic effects of
wettability and pore size. Journal of Membrane Science, 572, 596606 r Elsevier.
B. Physical processes
8.3 Polymer-based adsorbents for oil/water separation
145
8.2.3 Using organic materials
The anionic or cationic polyelectrolytes like poly (2-dimethylamino ethyl methacrylate)
(Cao et al., 2014), block copolymers of poly (methyl methacrylate)-b-(vinyl pyridine) (Li,
Zhou, & Luo, 2015), and poly (ethylene di oxy thiophene)-b-poly (styrene sulfonate) (Teng
et al., 2014) coated meshes are used to create hydrophilic water-selective meshes or membranes. Both polyethylene imine and polydopamine (PDA) are used to convert hydrophobic
PP membranes to hydrophilic ones (Raza et al., 2014). These functionalized meshes or membranes are superhydrophilic in aqueous environments that is they selectively remove water
from oil/water mixtures. Wang, Pan, Li, and Cao (2014) used polyvinylidene fluoride membranes which were rendered hydrophilic through ozone-induced grafting polymerization of
acrylic acid. A recent study has reported the synthesis of hydrophilic poly(vinylidene fluoride) membranes exhibiting underwater superoleophobicity (Zhao et al., 2019). Surface modification of these membranes was carried out using thiolated hyperbranched zwitterionic
poly (sulfobetaine methacrylate). Schematic representation of this membrane surface functionalization has been shown in Fig. 8.3.
8.3 Polymer-based adsorbents for oil/water separation
In the past few decades, polymeric adsorbents have been emerging as highly effective
(Pan et al., 2009) due to their wide variation in porosity and surface chemistry. Generally,
polymeric adsorbents are used to collect the omnipresence organic pollutants such as
Phenols (Abburi., 2003), Organic acids (Yang, Shim, Lee, & Moon, 2003), alkanes, and their
derivatives (Lee, Jung, Kwak, & Chung, 2005). Recently, polymeric adsorbents have also
used for oil sorbents. Here, mentioned the polymeric adsorbents that are used in oil/water
separation processes.
FIGURE 8.3 Schematic representation of
poly(vinylidene fluoride) membrane functionalization using hyperbranched zwitterionic
poly. Source: Reproduced with permission from
Zhao, J., Li, D., Han, H., Lin, J., Yang, J.,
Wang, Q., . . . Chen, L. (2019). Hyperbranched
zwitterionic polymer-functionalized underwater
superoleophobic microfiltration membranes for
oil-in-water emulsion separation. Langmuir:
The ACS Journal of Surfaces and Colloids,
35(7), 26302638 r 2019 American Chemical
Society.
B. Physical processes
146
8. Superhydrophobic polymeric adsorbents as an efficient oil separator
8.3.1 Plastic-based adsorbents
The oil sorbents that are derived from plastics are prepared using single or mixture of plastics (Atta et al., 2013; Guo, Zhou, & Lv, 2013). Generally, plastics are classified as thermo plastic and thermoset plastics. Thermoplastics include PP, low density polyethylene, High density
polyethylene, polyethylene terephthalate (PET), poly methyl methacrylate, polyamide/nylon,
polystyrene (PS), etc., that softens on heating and hardens on cooling. These plastics can be
recycled. Thermoset plastics including polyester resin, epoxy resin, polyurethane, urea formaldehyde, melamine formaldehyde, phenol-formaldehyde/bakelite, etc., harden on heating and
cannot be recycled (Saleem et al., 2018). Different types of plastics reported as potential oil sorbents have been enlisted in Table 8.2.
8.3.2 Polyurethane oil sorbents
Polyurethane foams used as oil adsorbents have been grafted by PS (Tanobe et al.,
2009). Polyurethane sponge material treated with silica sol and gasoline reportedly exhibit
an adsorption capacity of 100 g/g for motor oil (Wu et al., 2014). Oleophilic polyurethane
foams formed by graft copolymerization reportedly demonstrate an oil sorption capacity
of 47 and 41 g/g for diesel and kerosene respectively (Li, Liu, & Yang, 2013). They also
have excellent oil/water selectivity (Wang & Uyama, 2016). Some studies have reported
how absorption capacity of polyurethane foams vary with their pore size (Pinto,
Athanassiou, & Fragouli, 2016). Chemical functionalization of foams also reportedly
increase selectivity and sorption performance of these foams. According to a recent study,
polyurethane sponges coated with graphene sheets exhibit excellent sorption efficiency for
the continuous separation of oil/water mixture (Kong, Wang, Lu, Zhu, & Jiang, 2017).
8.3.3 Polystyrene oil sorbents
Nanoporous PS fibers have been synthesized via an electro spinning process for oil spill
remediation (Lin et al., 2012). A recent study reported magnetic PS foam having high oil
removal efficiency. Electrospun fibers of both PS and polyacrylonitrile exhibited high
buoyancy and adsorption capacity (B195 g/g) for pump oil (Li et al., 2015). In another
study, electrospun PS films showed an adsorption capacity of 131 and 112 g/g for motor
oil and peanut oil respectively (Wu et al., 2012).
8.3.4 Polyethylene and polypropylene based oil sorbents
Oil sorbent films prepared from ultrahigh-molecular-weight polyethylene and other
polyethylene wastes reportedly exhibits high sorption capacity and oil uptake capacity
(B100 g/g) (Saleem & McKay, 2016). Membranes prepared from electrospun PP fibers
have been found to be superhydrophobic with water contact angles greater than 150 (Feng
et al., 2002; Ma, Hill, & Rutledge, 2008). This membrane efficiently separated water from
diesel (Patel & Chase, 2014). Fiber assemblies have also been prepared with PPs, kapok
and milkweed fibers that possess high sorption capacities (Rengasamy, Das, & Karan,
2011). Performance of the PP based oil sorbent materials reportedly on depend on pore
B. Physical processes
TABLE 8.2 Application of different plastics as oil sorbents.
S.
no Oil sorbents type
Product
Origin
Discussion
References
1
Polyurethane foams
Polyurethane
foams used as
mattresses
Polyurethane foam grafted by polystyrene; oil uptake (1958 g/g) Retention values
(5018 g/g)
Tanobe, Sydenstricker,
Amico, Vargas, and
Zawadzki (2009)
Polyurethane sponge material
treated with silica sol and
gasoline successively
Polyurethane
The absorption capacity was 100 g/g sorbent for motor oil. After 15 successive sorptionsqueezing cycles, about 70% sorption capacity was left.
Wu et al. (2014)
2
3
4
5
Polyurethane based
oil sorbents
Polystyrene based
oil sorbents
PP and PE based oil
sorbents
Acrylates based oil
sorbents
Oil sorbents based
on miscellaneous
polymers
Treated polyurethane sponges
Polyurethane
High sorption capacity and excellent oil/water selectivity.
Wang and Uyama (2016)
Oil sorbent fibers
Polystyrene
Submicron fibers from polystyrene waste. Oil uptake measurements not presented.
Wu et al. (2012)
Polystyrene fibers
Polystyrene
Polystyrene fibers fabricated by a facile electrospinning method. The absorption capacity
for PS fibers: about 7 g/g (diesel)82 g/g (silicon oil), 112 g/g (peanut oil) and 131 g/g
(motor oil).
Gong, Qiu, Zhang, and
Wei (2011)
Magnetic polystyrene foam
Polystyrene
The foam possessed high efficiency for the removal of oil from the surface of the water.
Oil absorbent foam
Extruded
polyethylene EPE
used in packing
Oil uptake (30 g/g)
Saleem and McKay (2016)
Oil sorbent film
Waste high density
polyethylene
bottles
Oil uptake capacity, 100 g/g
Patel and Chase (2014)
Polypropylene fibrous membrane
Syndiotactic
polypropylene
Electrospun material was superhydrophobic with water contact angles greater than 150.
The material successfully removed water from diesel (ULSD) samples.
Feng and Xiao (2006)
Butyl methacrylate-lauryl
methacrylate copolymeric
(CPMA) fibers
Butyl methacrylate
and lauryl
methacrylate
Hydroethyl methacrylate was used as a cross-linker. The maximum absorption
capacities of the fibers were about 8 g/g (Kerosene), 15 g/g (toluene), and 35 g/g
(chloroform).
Duan, Bian, and Huang
(2016)
Macroporous ST/BMA copolymer Styrene and butyl
methacrylate
The macroporous resin possessed oil absorbency (about 9 g/g) to crude oil.
Duan et al. (2016)
Stearyl methacrylate-butyl
acrylate copolymer
Stearyl
methacrylate and
butyl acrylate
Porous oil-absorbent microsphere possessed above 95% oil retention for four organic
liquids (toluene, gasoline, diesel and chloroform). The material can be used at least 12
times with little decrease in oil absorbency capacity.
Bukharova, Tatarintseva,
and Ol’Shanskaya (2015)
Oil sorbent powder
PET
Oil uptake capacity, 1.52.5 g/g
Xu, Cao, and Lu (2016)
Nylon 6,6 Nonwoven Fabric
Nylon
The absorption capacity for low area mass density spun bond nylon: 16 times absorbent
mass in low viscosity crude oil.
Electrospun copolymer of styrene
and butyl acrylate
Styrene and butyl
acrylate
The produced fibrous material possessed large specific surface area and fast oil
absorption rate.
148
8. Superhydrophobic polymeric adsorbents as an efficient oil separator
diameter, porosity and oil adsorbing properties of PP (Wei, Mather, Fotheringham, &
Yang, 2003).
8.3.5 Oil sorbents based on the methacrylate polymers
Butyl methacrylate-lauryl methacrylate copolymeric fibers have demonstrated maximum adsorption capacities of 8, 15 and 35 g/g for kerosene, toluene and chloroform
respectively (Feng & Xiao, 2006). The oil adsorption capacity of macroporous styrene and
butyl methacrylate copolymer was found to be 9 g/g for crude oil (Duan et al., 2016).
Porous oil-absorbent microsphere of stearyl methacrylate-butyl acrylate copolymer reportedly exhibited 95% retention of toluene, gasoline, diesel and chloroform (Duan et al.,
2016). This material was successfully reused for 12 consecutive cycles.
8.3.6 Oil sorbents based on the miscellaneous polymers
PET exhibited an oil uptake capacity of 1.52.5 g/g (Bukharova et al., 2015). Though
this value is less in comparison to other oil sorbents, this process involves utilization of
waste plastic. In another study, electrospun copolymer of styrene and butyl acrylate having a large specific surface area exhibited rapid rates of oil adsorption (Xu et al., 2016).
Nylon bags have also been used for separating contaminated gear oil from the oil-in-water
emulsions.
8.3.7 Aerogels
An aerogel is a 3-dimensional porous polymeric gel having high sorption capacity.
Generally, aerogels are foam or sponge like structures having high surface area and pore
structure (Pinto et al., 2016). Various polymeric aerogels like poly dimethyl siloxane
sponge (Choi et al., 2011), polyurethane (Ruan, Ai, Li, & Lu, 2014), PS foams (Yu et al.,
2017), PP sponge (Wang, Elimelech, & Lin, 2016) have been used for the oil adsorption. A
recent study reported fluorinated PDA/chitosan/reduced GO composite aerogel having
high oil/water separation efficiency. Schematic representation of facile synthesis of this
aerogel has been shown in Fig. 8.4 (Cao et al., 2017).
8.4 Superhydrophobic polymeric adsorbents
Superhydrophobic materials are widely used due to their superhydrophobicity, high
sorption capacity, and selectivity for oil recovery (Gao et al., 2016; Mi, Jing, Politowicz,
et al., 2018; Shuai et al., 2015). Superhydrophobic materials having applications like selfcleaning, corrosion resistance, antiicing and drag reduction (Chen, Li, Li, & Sun, 2015; Rao
et al., 2017; Si & Guo, 2015; Wang et al., 2014; Zhu et al., 2018). They can easily absorb oil
from water due to their porous sponge-like structures (Wang et al., 2016). Surface modification of polyurethane sponge have been carried out to make the same superhydrophobic
(Li et al., 2016; Wang, Wang, et al., 2015).
B. Physical processes
8.4 Superhydrophobic polymeric adsorbents
149
FIGURE 8.4 Schematic illustration of facile synthesis of fluorinated polydopamine/chitosan/reduced
graphene oxide composite aerogel. Source: Reproduced with permission from Cao, N., Lyu, Q., Li, J., Wang, Y.,
Yang, B., Szunerits, S., & Boukherroub, R. (2017). Facile synthesis of fluorinated polydopamine/chitosan/reduced
graphene oxide composite aerogel for efficient oil/water separation. Chemical Engineering Journal, 326, 1728.
r 2017 Elsevier.
However, the dissociation of particle is a potential threat to environment when
long term using of modified sponges are considered as degraded polymeric particles
can have other environmental impacts (Cong, Ren, Wang, & Yu, 2012). Ultralight
carbon-based aerogels having high absorption capacity and low density are another
type of superadsorbent material (Wang et al., 2017; Zhang, Gu, et al., 2016). These are
normally fabricated by pyrolysis of natural materials and polymer foams (Das & De,
2015; Feng, Nguyen, Fan, & Duong, 2015; Li, Hu, Sun, Zhang, & Wang, 2017) and cellulose (Mi, Jing, Xie, Huang, & Turng, 2018). Nevertheless, these methods of fabrication have high cost and less durability. Recently, researchers have reported
conventional low-cost processing methods for the preparation of superhydrophobic
porous polymeric materials, the most used method is phase inversion (Yuan, Meng,
Hao, Wang, & Zhang, 2015). However, materials synthesized by these method have
low hydrophobicity and absorption capacity. Another method is supercritical gas
foaming. It is used in the fabrication of superhydrophobic polymer foams. This is
cost-effective and environment-friendly but often produces foams having lower
hydrophobicity and absorption capacity. The composite of poly(tetrafluoroethylene)
(PTFE) with PP prepared using twin-screw extrusion was formed in presence of
supercritical CO 2. The special PP/micro or nanoparticles of PTFE foam having multidimensional hierarchical structure was created by using nanoparticles and microparticles of PTFE. The resultant superhydrophobicity was retained even when the
composite was cut, fractured, or sanded. The PP/mnPTFE composite reportedly has a
high water contact angle (WCA) and low contact angle hysteresis of 156.8 and 1.9
respectively.
Nanoporous polydivinylbenzene (PDVB) is also used for the adsorption of
organic pollutants from air and water (Häder, Kumar, Smith, & Worrest, 1998;
B. Physical processes
150
8. Superhydrophobic polymeric adsorbents as an efficient oil separator
Jones, 1999; Godduhn & Duffy, 2003). PDVB has high surface area with large pore
volume and controllable average pore size (Fuertes, Marban, & Nevskaia, 2003).
They exhibit specific selectivity for organic compounds. The synthesis material is in
the form of PDVB-x, where x is the solvent used in the starting solutions. Solvent
and sufficient time of solvothermal process are significant parameters guiding the formation of porous structure. Acetone, benzene, THF (Tetrahydrofuran), Dimethylformamide,
ethyl acetate, etc., are considered as most suitable solvents for the synthesis of nanoporous PDVB. For example, PDVB synthesized using THF as a solvent (under a temperature
of 60 C100 C for 348 h) was found to have a contact angle of 156, indicative of the
superhydrophobic nature of the same. It also showed the immediate adsorption of oil
droplet in contact with its surface, indicating the superoleophilicity. The sample showed
a hierarchical nanoporous structure and great adsorption property. This superhydrophobic polymer could also be recovered by using low-pressure distillation and reused.
Nanocellulose aerogel is also used for the adsorption of oil and organic pollutants from
water. Nanocellulose based adsorbents have attracted more attention than other adsorbents due to its complicated fabrication processes, environment incompatibility and insufficient buoyance. However, the nanocellulose aerogels are flexible, light in weight, have
high adsorption capacity, are environmentally friendly, biodegradable, and extremely sustainable (Chen et al., 2004; Paakko et al., 2008). Moreover, hydrophobic cellulose aerogels
have higher oil/water selectivity and porous structure in comparison to hydrophilic ones.
In a recent study, Wang and Liu (2019) reported the synthesis of superhydrophobic cellulose aerogels (shown in Fig. 8.5) having high oil retention capability from raw cotton
fibers.
Several methods have been used for synthesis of hydrophobic cellulose aerogels
from hydrophilic ones including chlorosilanes using chemical vapor deposition
(Klemm, Heublein, Fink, & Bohn, 2005), triethoxyl(octyl)silane through vapor deposition, diffusion of the vapor of methyltrimethoxysilane into the aerogel skeleton to get
hydrophobic surface (Wang, Peng, et al., 2015), etc. However, but by using these
methods, a homogeneous grafting distribution is not obtained in the aerogels
(Chaudemanche & Navard, 2011). To solve this problem, freeze-drying of a nanocellulose suspension treated by methyltrimethoxysilane is carried out (Zhang et al.,
2014). This process yields hydrophobic nanocellulose aerogels but the properties and
structure of aerogels are altered.
Surface of nanocellulose easily can be modified by simply immersing the microfibrillated cellulose aerogels (MFCAs) in ethanol/methyltriethoxysilane (MTES) solution, and
vacuum-dried the product to obtain superhydrophobic and oleophilic MFCAs (HMFCAs).
The MTES solubilized in the ethanol had uniformly diffused into the pores of the
HMFCAs. This method is simple and environmentally benign. The HMFCAs have a WCA
of 151.8 degrees. Hence, it may be concluded that formation of the polysiloxane on the surface of the HMFCAs as a result of the silanization reaction is responsible for the superhydrophobicity of the HMFCAs. These HMFCAs exhibited an oil absorption capacity of up
to 159 g/g from oil/water mixtures (Zhou, Li, & Luo, 2016).
B. Physical processes
8.4 Superhydrophobic polymeric adsorbents
151
FIGURE 8.5 (A) Schematic representation of fabricating superhydrophobic cellulose aerogels; (B) photographs
of superhydrophobic cellulose aerogels with different fiber concentration; (C) photographs of superhydrophobic
cellulose aerogels (density: 0.041 g/cm3) obtained under different scale of preparation; (D) flexibility of the cellulose aerogel (8 3 1.2 cm) containing 3.5 wt.% of raw cotton fiber. Source: Reproduced with permission from Wang, J.,
& Liu, S. (2019). Remodeling of raw cotton fiber into flexible, squeezing-resistant macroporous cellulose aerogel with high
oil retention capability for oil/water separation. Separation and Purification Technology, 221, 303310 r 2019
Elsevier].
B. Physical processes
152
8. Superhydrophobic polymeric adsorbents as an efficient oil separator
8.5 Conclusion
Separation of oil from water is an area of research which is progressing very fast. Since
oil pollution, oil spillage in oceans are crucial environmental hazards that are detrimental
to the aquatic ecosystems, newer methods and technologies have been developed for solving these problems (de Oliveira Soares et al., 2020). One such method is using adsorbents
for this purpose. Although there are a variety of materials available, often polymeric materials are used for this purpose (Al-Majed et al., 2014). Among recent materials known to
mankind, superhydrophobic materials are gaining huge importance due to their applicability in self-cleaning, corrosion resistance, antiicing and drag reduction to mention a few
(Gao et al., 2016). This property of higher capacity of repelling water can be used effectively in separating oil from water. Such superhydrophobic materials formed from synthetic polymers like PDVB, PTFE and natural polymer like nanocellulose are now being
used by scientists for oil/water separation purpose (Godduhn & Duffy, 2003; Wang & Liu,
2019). Thus these novel superhydrophobic polymeric materials have a huge potential for
oil/water separation purposes.
Acknowledgments
Shubhalakshmi Sengupta and Venkatalakshmi Jakka would like to acknowledge DST (SEED div) Government of
India for the financial support they are receiving from of their DST (SYST) project (SP/YO/2019/1283) during the
tenure of writing the chapter.
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B. Physical processes
C H A P T E R
9
Oil spill treatment using porous
materials
Prakash Bobde1, Ajaya Kumar Behera2 and
Ravi Kumar Patel3
1
Department of Research and Development, Energy Acres, University of Petroleum and Energy
Studies, Dehradun, India 2Department of Chemistry, Utkal University, Bhubaneswar, India
3
UPES Council for Innovation and Entrepreneurship, Energy Acres, University of Petroleum
and Energy Studies, Dehradun, India
O U T L I N E
9.1 Introduction
157
9.4 Conclusion
170
9.2 Materials and characterization
160
Abbreviations
170
9.3 Discussion
163
References
170
9.1 Introduction
Oil contamination is a significant environmental problem that is increasing in accordance with the development of petroleum production. In the last decade, an estimated
196,000 tons of transportation caused significant oil leakage, despite the fact that the world
utilizes 30 billion barrels of petroleum each year, with up to five million tons of oil
shipped daily via sea routes. Since the 20th century, oil leaks have been a major threat to
the atmosphere and sea life (Nelson, 2000).
Oil pollutants are a complex blend of aliphatic (CnH2n12), naphthenic (i.e. cycloalkanes),
and aromatic hydrocarbons (Muir & Bajda, 2016). In the water there are several sources of
oil. Natural gas seeps from the seabed and ocean floor, drilling in the ocean floor, leakage
from oil extraction and transportation facilities, inland and marine navigation, emergency
floods (e.g., tanker collisions or breakdowns), road and air transport, waste petroleum-
Advances in Oil-Water Separation
DOI: https://doi.org/10.1016/B978-0-323-89978-9.00005-7
157
© 2022 Elsevier Inc. All rights reserved.
158
9. Oil spill treatment using porous materials
based industrial installations, and storm water from urban areas are the most important of
these (Gutteter-Grudziński, 2012; Polkowska & Błaś, 2010).
The devastating effects of oil spills onto water have resulted in the implementation of
many strategies for eliminating such toxins from the marine environment. The first steps
needed to prevent the harmful impacts of oil spills is the observation and monitoring of
the source of pollution, as well as the preservation of human health and security. The
phrase “response actions” refers to procedures, facilities, processes and practises used to
recover pollutants from spills and reduce their possible impact (Fingas, 2016).
Oil pollution treatment usually involves combustion and collection. Of these, burning
due to additional pollution is not desirable. In comparison with the former system, however, the benefits of the collection process are quick oil recovery, no secondarily contaminated contamination and fast purification. Common techniques for preventing oil spills in
seas and coasts (Fig. 9.1A) involve (Adebajo, Frost, Kloprogge, Carmody, & Kokot, 2003;
Fingas, 2016):
Oil stains are frequently removed using a combination of methods. Their decision is
based on the extent of the leak, the quality of the water, and the temperature, although
there are no uniform deoiling systems that can be used in all circumstances. The use of
porous materials, such as sorbents, is a method that deserves special attention because
they are readily available, easy to use, inexpensive, and, most importantly, nontoxic to the
environment.
Sorption is a physical form of oil removal that involves the absorption and adsorption
of the oil (Fig. 9.1B) (Dı́ez, Jover, Bayona, & Albaigés, 2007). The most popular sorbents
FIGURE 9.1 (A) Oil spill controlling strategies (B) Efficiency of sorbents for oil removal.
B. Physical processes
9.1 Introduction
159
being used clean up oil leaks are classified as follows (Adebajo et al., 2003; Bandura,
Franus, Panek, Woszuk, & Franus, 2015):
1. inorganic mineral materials (e.g., diatomites, diatomaceous earth, perlites, clay
minerals, zeolites, fly ash, activated carbons or silica gel);
2. organic mineral materials (e.g., peat, sawdust, wood, waste bark, cellulose from paper
production, cotton, kapok and rice husks);
3. synthetic organic polymers (e.g., polypropylene, polyethylene, polyacrylate, polystyrene
or polyurethanes).
Oil spills are handled by hydrophobic sponges, which absorb oil in water and can be
recycled through squeezing or distillation (Balat & Balat, 2009). Furthermore, the ideal
adsorption material must have a large adsorption space, a high adsorption rate, as well as
a superhydrophobic capacity. Glass wool falls under the category of inorganic mineral
products, birch bark and cork fall under the category of organic mineral materials, and
polyurethane foam (PUF) falls under the category of synthetic organic polymers. Fig. 9.2A
FIGURE 9.2 (A) preparation schematic diagram and (B) oil-water separation mechanism diagram. Source:
Adapted with permission Zhang, Y., Zhang, Y., Cao, Q., Wang, C., Yang, C., Li, Y. & Zhou, J. (2020). Novel porous oilwater separation material with super-hydrophobicity and super-oleophilicity prepared from beeswax, lignin, and
cotton. Science of the Total Environment, 706, 135807.
B. Physical processes
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9. Oil spill treatment using porous materials
depicts the preparation line representation of the biomass-based porous materials with
super-hydrophobicity and super-oleophilicity. Fig. 9.2B depicts the oil-water segregation
process schematic of biomass-based porous materials with super-hydrophobicity and
super-oleophilicity.
Porous materials are becoming increasingly popular in gas sorption, catalysis, water
treatment, separation, electrochemical energy storage, sensing, proton conduction, biomedicine, and optoelectronics (Wu et al., 2019). Porous materials are empty spaces within a
structured framework, resulting in high surface areas for interaction with atoms, ions, or
molecules in the environment. Controlling the porous architecture and functionalizing it
to enhance interactions, on the other hand, represents a problem (Ci et al., 2017). To ensure
that it selectively absorbs oil rather than water, the ideal porous material for oil-water separation must be super-hydrophobic and super-oleophilic (Chen & Zheng, 2014).
9.2 Materials and characterization
Different types of materials were used for the oil water separation. These include aerogel, foam, sponge, graphene. Yuan et. al. synthesized biomass carbon @SiO2@MnO2 aerogel and modified and to increase the hydrophobicity of the material, the surface of aerogel
was altered by grafting the hydrophobic group on the surface of aerogel. The wettability
of the biomass carbon @SiO2@MnO2 aerogel and modified biomass carbon @SiO2@MnO2
aerogel was studied utilizing contact angle measurement. Yuan et. al. was observed that
water molecule could pierce into the pristine biomass carbon @SiO2@MnO2 aerogel within
1 s. and water contact angle (WCA) was 0 degrees which was found due to the hydrophilicity and intrinsic high surface energy of metallic oxides whereas water molecule could
not pierce into the modified biomass carbon @SiO2@MnO2 aerogel within 30 s. and WCA
was 155 degrees which showed that the hydrophobicity of the material (Yuan et al., 2018).
Cellulose based aerogels (CBAs) were synthesized and characterized for the wettability.
MTMS-modified CBAs showed the WCA and oil contact angle were 154 and 0 degrees
which indicated the combined hydrophobicity and oleophilicity. CBAs showed the high
absorptivity (98.6%99.6%) and low thickness (0.00550.021 g/cm3) belong to the light
weight material, indicated the material could float on the surface of water after absorbing
oil (Yin, Zhang, Liu, Li, & Wang, 2016). Cellulose membrane showed the WCA 20 degrees
and by coating the silane onto the surface of cellulose membrane the WCA enhanced from
20 to 140 degrees. The WCA further enhanced to 160 degrees due to the grafting of myrcene (block copolymer) onto the cellulose membrane surface. This indicated that the block
copolymer successfully polymerized onto the cellulose membrane (Kollarigowda,
Abraham, & Montemagno, 2017). Eggshells modified by ethanol, stearic acid and ZnO for
the absorption of oil from the water. The modified eggshell particles were characterized
for the WCA and slide angle for the detecting of hydrophobicity of the material. Modified
eggshell particles showed the WCA more than 150 degrees which indicated the material
hydrophobicity. Modified eggshell particles were exposed under UV light for 12 h for
checking the UV-durability of the hydrophobic material. After 12 h of irradiation, the surface already had a WCA greater than 150 degrees and a SA less than 10 degrees, indicating exceptional UV-strength. The WCA and SA demonstrated no discernible difference
B. Physical processes
9.2 Materials and characterization
161
after continued irradiation, showing that the as-prepared superhydrophobic material has
excellent UV light resistance (He et al., 2018).
CEC/Fe3O4/PFOS material showed the high absorptivity (83.53%) and low thickness
(0.487 g/cm3) belong to the light weight material, indicated the material could float on the
surface of water after absorbing oil. The WCA for CEC and CEC/Fe3O4/PFOS was found to
be 51.3 and 150.1 degrees, respectively. This revealed the hydrophobicity of CEC/Fe3O4/
PFOS than CEC (Sun et al., 2020). Polydimethylsiloxane-functionalized melamine sponge
(Ms) showed the high porosity (99.4%) and low density (0.0080.026 g/cm3). The WCA of
polydimethylsiloxane-functionalized Ms was found to be larger than 150 degrees, indicated
the hydrophobic nature of material (Chen, Weibel, & Garimella, 2016). FOC-TiO2 modified
sponge revealed the WCA 161.1 degrees, indicated the high water repellency (Cho, ChangJian, Hsiao, Lee, & Huang, 2016). Feng et al. synthesized furfuryl alcohol (FA) modified Ms
and studied the surface wettability of the material. When the water and oil were drizzled on
the surface of unmodified Ms and FA modified Ms, both water and oil were absorbed on
the surface of pristine Ms in 1 s. while on the contrary oil got absorbed on the superficial of
FA modified Ms and water maintained a stable spherical shape on the surface of FA modified Ms. Though the FA modified Ms was divided into two sections, newly divide face still
exhibited a high water repellence. The WCA was estimated to be between 138 and 145
degrees. The findings reveal that after FA alteration, both the internally and externally surfaces were chemically modified, and Ms has a hydrophobic property (Feng, Wang, Wang, &
Yao, 2017). Pristine Ms exhibited absorption bands at 818, 1546, and 3394/cm, which are
attributed to triazine ring twisting, C 5 N stretching, and N-H stretching, respectively.
Bands at 1341 and 1471/cm were also representative of -CH- bending. Furthermore, C-H
stretching was due to two small peaks at 28002900/cm. These absorption band groups verified the chemical structure of the Ms. Because of the attribute motions of Si-O-Si stretching,
new absorption bands at 1048 and 1086/cm emerged after SiO2 adsorption and silanization
procedures. Furthermore, the peak attributed to N-H stretching was significantly red-shifted
to 3381 and 3362/cm, as a result of the integrating reaction of amino groups on the sponge
structure in the course of silica nanoparticle adsorption and the silanization process (Gao
et al., 2018). The WCA of the ODS SAM-modified sponge was 91 degrees and after modification by PODS the same was increased to 153 degrees. This indicated the PODS-modified
sponge exhibited the superoleophilicity (Ke, Jin, Jiang, & Yu, 2014). The specific surface area
of the (Al2O3/PUF) foam sponge was found to be 214.79 m2/g and the aperture diameter
ranged from 1540 nm. The high specific surface area and pore diameter of (Al2O3/PUF)
foam sponge was beneficial for the increased absorption efficiency. Fig. 9.3 showed the
WCA measurement of Al2O3 sphere, hydrophobic Al2O3, PUF, and (Al2O3/PUF) foam
sponge. WCA of Al2O3 sphere, hydrophobic Al2O3, PUF, and (Al2O3/PUF) foam sponge
was found to be 0, 136, 127, and 144 degrees. This indicated the hydrophobicity and oleophilicity of (Al2O3/PUF) foam sponge (Kong et al., 2018).
The polyurethane sponge overlayed with KH-570-improved graphene had a high WCA;
which was inflated apart from the polydimethylsiloxane (PDMS)- overlayed PU sponge
(140 degrees) (Wang & Lin, 2013), PU foam (152.2 degrees) (Su, 2009), and conjugated
microporous polymers (150 degrees) (Li et al., 2011). Water molecules were nearly
adsorbed by the primary sponge, but stayed intact on the substrate of the polyurethane
sponge overlayed with KH-570-improved graphene. In 1 s, a drop of diesel oil dyed with
B. Physical processes
162
9. Oil spill treatment using porous materials
FIGURE 9.3
WCA of void Al2O3
spheres (A), Al2O3 (B), PUF (C) and
Al2O3/PUF (D) foam sponge. Source:
Adapted with permission Kong, L., Li, Y., Qiu,
F., Zhang, T., Guo, Q., Zhang, X., . . . Xue, M.
(2018). Fabrication of hydrophobic and oleophilic polyurethane foam sponge modified with
hydrophobic Al2O3 for oil/water separation.
Journal of Industrial and Engineering
Chemistry, 58, 369375.
Sudan I was totally adsorbed into the spaces of the polyurethane sponge treated with KH570-overlayed graphene, and no CA could be detected. An impacting water column
bounced off the polyurethane sponge overlayed with KH-570-improved graphene surface;
this further showed the superhydrophobicity of the polyurethane sponge overlayed with
KH-570-improved graphene. Superhydrophobic surfaces are typically created by combining sufficient surface harshness with hydrophobic substances. As a result, two variables,
roughness and poor surface energy, led to the superhydrophobicity (Preda et al., 2013).
The sponge was covered with graphene, which improved its harshness. The substrate
energy of all the graphene and the sponge decreased after they were altered with KH-570.
The formed polyurethane sponge layered with KH-570-improved graphene turned superhydrophobic as a result. However, it remained more superoleophilic than the initial
sponge (Li et al., 2015). CS-SiO2-PU sponges were synthesized and utilized for the oil/
water separation. Contact angle calculations were used to assess the hydrophilicity of the
initial and CS-SiO2-PU sponges. As demonstrated in the CA of a water (dyed with methylene blue) particle on the unmodified PU sponge is 100 6 2 degrees, whereas the CA of a
kerosene (dyed with oil red O) particle is around 0 degree. Nevertheless, the CS-SiO2-PU
sponge shows superhydrophobicity and superoleophilicity at the same time. When a kerosene molecule was released on the layer of the CS-SiO2-PU sponge, it was automatically
drained, whereas a water molecule remained on the layer of the pristine sponge and
retained its spherical form. The WCA on the CS-SiO2-PU sponge is up to 155 6 2 degrees
and the SA is as low as 7 6 2 degrees. As a result, the water was annihilated by the pristine sponge, while the oil easily pervaded into it (Li, Zhao, et al., 2017).
Surface chemical composition of synthesized PU@Fe3O4@PS sponge was investigated
from XRD and FTIR characterizations. These results indicated that PS and Fe3O4
B. Physical processes
9.3 Discussion
163
nanoparticles were grafted on the surface of sponge successfully by means of dip-coating
and photopolymerization (Zhou et al., 2019). The PDA covering on the CF layer was responsible for the minor difference in hardness of the CF-PDA. The CF-PDA-Ag, or AgNO3-treated CF-PDA, retained its initial 3D void structure and displayed clear micro/nano
framework owing to the Ag NPs and agglomerates formed by the reducing response among
the PDA surface and Ag1 ions. Furthermore, the centralized micro/nano frameworks on
the CF-PDA-Ag substrate did not alter significantly during the corresponding NDM dipcoating operation. This suggested that the PDA surface on the CF serves an important part
in shielding the CF’s 3D framework from degradation induced by the diffusion interaction
among Cu and Ag1, which enabled the production of Ag NPs and their trapping into the
CF-PDA-Ag substrate (Zhou, Li, Wang, Chen, & Lin, 2017). The unmodified CF had WCA
79.6 degrees showing hydrophilicity of the material. CF-PDA and CF-PDA-Ag showed
lower WCA than unmodified CF due to both of the revised CF structures showed varying
rates of wettability transition. The improved CF structures, synthesized by binding with
NDM to get CF-PDA-NDM and CF-PDA-Ag-NDM, revealed high powerful hydrophobicity.
CF-PDA-Ag-NDM revealed WCA 153.1 degrees indicated the material superhydrophobic
nature (Zhou et al., 2017). PDMS sponge showed superhydrophobic nature with WCA 151.5
degrees. Due to the void framework and superhydrophobic nature, PDMS sponge could levitate on the top of water. When a sponge is submerged in water by a physical pressure it is
covered by an air covering and has a silver mirror-like appearance. The pliability and superhydrophobicity of the PDMS sponge were investigated by keeping in liquid nitrogen and in
an oven at 250 C for 24 h, but PDMS sponge showed very high WCA 151.2 and 150.2
degrees, respectively. TGA characterization of PDMS sponge was carried out to identify
mass drop at different temperatures. No mass drop was observed at less than 322 C. 37.83%
mass drop was observed between 322 C800 C which was attributed to the methyl group
decay (Zhao, Li, Li, Zhang, & Wang, 2014).
The WCA of magnetic foam was found to be 110 6 1.1 degrees, stipulated the hydrophobic nature of material. The hydrophobicity of the magnetic foam was increased by incorporating titanium dioxide and increasing the concentration of titanium dioxide. WCA of magnetic
titanium dioxide foam was found to be 152.1 6 1.2 degrees, showed the superhydrophobic
material. In comparison, oil particles scattered and absorbed entirely into magnetic titanium
dioxide foam in less than 1.2 s, demonstrating that magnetic titanium dioxide foam was both
superoleophilic and superhydrophobic (Yu, Zhou, & Jiang, 2016). WCA of carbon hybridized
ZnO on polymeric foam was found to be 137 degrees, showed the superhydrophobic material.
The control finding demonstrated that ALD accumulation of ZnO, which has a reasonable
surface energy, is a standardized method for imparting hydrophobicity to originally hydrophilic porous foams on the one side, and conclude that ALD accumulation of ZnO is a flexible
method for changing the substrate wettability of porous substrates based on its particular surface properties on the other (Xiong, Yang, Zhong, & Wang, 2018).
9.3 Discussion
Yuan et. al. used modified biomass carbon @SiO2@MnO2 aerogel to observe the oil water
separation. The material showed the maximum absorption capacity for the separation of
B. Physical processes
164
9. Oil spill treatment using porous materials
carbon tetrachloride and minimum absorption capacity for the toluene from water.
Reusability and durability of the modified biomass carbon @SiO2@MnO2 aerogel was also
checked and found that the material showed very high absorption capacity after the 9th
cycle of reuse (Yuan et al., 2018). Effect of cellulose content and PAE concentration on the
different oil sorption capacity of CBAs was investigated. The absorption capacities for all
the oils were decreased as the cellulose content increased from 0.35 to 1wt.%. As the PAE
concentration was increased from 10 to 60wt.%, the absorption capacities for crude oil, diesel oil and lubricating oil was reduced WCA of CBAs after 16th cycle were found to be
113.1128.8 degrees indicated that the recycled CBAs had very low absorption capacity for
water (Yin et al., 2016). Crude oil showed the maximum absorption capacity for the block
copolymer cellulose membrane. The WCA was observed for the block copolymer cellulose
membrane after using five times and it was found that 160 degrees which indicated that the
hydrophobicity and oleophilicity of the material after using several times (Kollarigowda
et al., 2017). Bi et al. synthesized carbon microbelt (CMB) aerogel and used for the absorption of oils and organic solvents. Pump oil and chloroform from various oils and organic
solvents showed the higher absorption capacity for CMB aerogel. CMB aerogel shows the
higher absorption capacity than wool-based nonwoven (Radetić, Jocić, Jovančić, Petrović, &
Thomas, 2003), nanowire membrane (Yuan et al., 2008), magnetic exfoliated graphite (Wang,
Sun, Zhang, Fan, & Ma, 2010). Nitrogen doped graphene foam (Zhao et al., 2012), ultraflyweight aerogels (Sun, Xu, & Gao, 2013) and cellulose nanofibers aerogels (Wu, Li, Liang,
Chen, & Yu, 2013) showed the higher absorption capacity than the CMB aerogel, but the
synthesis method of CMB aerogel is simpler and the raw material used for the synthesis for
CMB aerogel is also very cheap than all the other material. From this point of view CMB
aerogel is the cost effective and promising sorbent for the organic pollutants (Bi et al., 2014).
Twisted carbon fibers (TCF) aerogel was synthesized and utilized for the absorption of oil
and organic solvents from water. The TCF aerogel’s 3D porous structure, strong mechanical
properties, and surface hydrophobicity made it an excellent candidate for the elimination of
contaminants like oils and organic solvents. The results revealed that the pump oil and chloroform absorbed higher onto the TCF aerogel. TCF aerogel could uptake oils and solvents at
50192 times its own weight (Bi et al., 2013).
Lignin modified aerogel was investigated for the absorption of organic solvents and
oils. Oils and organic solvents could be absorbed by a lignin-modified aerogel at rates of
2040 times their own weight. These findings showed that the synthesized improved
aerogel had distinct absorption capacities against various oils and solvents based on their
densities, and that the absorption ability of the improved aerogel could be changed by regulating its density by adjusting the feed solution concentration. This distinguishing feature
assured that the modified aerogels could be used in a wider range of applications. In the
case of determining the reusability of the aerogel by physically pressing, chloroform was
used as an oil evocative. To achieve absorption equilibrium, the improved aerogel was
first dipped in chloroform. Following that, the saturated aerogel was pressed and the desorbed oil was extracted. The desorbed improved aerogel was then utilized in some other
loop. The absorption capacity of the second cycle preserved 82.16% of the first cycle, and
the absorption capacity of the third cycle retained approximately 83.1% of the first cycle.
The reduction in absorption potential may be attributed to the residual oil in the biomassderived aerogel. Many functional groups in the biomass-derived aerogel aided in oil
B. Physical processes
9.3 Discussion
165
absorption; in other words, oil was easily combined with the biomass-derived aerogel.
When physically pressing was insufficient, a minimal%age of absorbed oil could remain in
the aerogel, resulting in a reduction in absorption ability for the following run. The fourth
cycle’s absorption capacity decreased further, reaching roughly 68.55% of the first step,
although following cycles’ absorption capacity remained constant. After ten cycles, the
improved aerogel’s absorption potential maintained approximately 73.71% of the first
cycle, indicating strong absorption efficiency and recyclability (Jiang, Zhang, Zhan, &
Chen, 2017). Modified eggshell particles could uptake oils at 1434 times its own weight.
The separation efficiency was decreased from 93% to 83% after 10 cycles of oil separation,
indicated the reusability of the modified eggshell particles (He et al., 2018). Comparison of
adsorption capacities of various materials in the previous studies are given in Table 9.1.
Chloroform, n-hexane, dichloromethane, motor oil, diethyl ether, cyclohexane, soybean oil
and rapeseed oil were investigated for the separation from water by CEC/Fe3O4/PFOS material. The adsorption capacities of CEC/Fe3O4/PFOS material are different for eight oils or
organic reagents (from 49.97 to 140.90 g/g). Out of these, chloroform showed the higher absorption capacity than others. The adsorption potential of the CEC/Fe3O4/PFOS content is greater
than those of other biomass charcoal compounds. However, only the adsorption potential of an
aerogel component exceeds that of the CEC/Fe3O4/PFOS content. Because of the relatively low
intensity of aerogel materials, many cellulose is employed as an adsorbent, however plant natural resources as an oil adsorbent medium have been rarely utilized (Sun et al., 2020). Lee et al.
(Lee, Lee, Koo, & Choi, 2019) created a magnetic adsorption medium (Ms-PDMS) from sponges
and Fe3O4 nanoparticles; the product is capable of oil/water isolation and adsorption
(34.837.9 g/g). The CEC/Fe3O4/PFOS content outperforms Ms-PDMS in the oil/water isolation
method. The oil adsorption potential of the CEC/Fe3O4/PFOS content (49.97140.90 g/g) is far
higher than that of Ms-PDMS samples (34.837.9 g/g), indicating that it is effective for oilwater isolation. The WCA of the CEC/Fe3O4/PFOS material is greater (150.1 degrees) than that
of the PLA/γ- Fe3O4 composite molecules (148 degrees) and Ms-PDMS samples (141 degrees)
(He et al., 2018; Lee et al., 2019; Sun et al., 2020). Hexane, toluene, octadecene, silicone oil and
motor oil was investigated for the separation from water by the polydimethylsiloxanefunctionalized Ms. The material revealed the high absorption capacity for all the pollutants.
Polydimethylsiloxane-functionalized Ms had the absorption capacity 45.4, 71.5, 55.4, 61.4, and
46.3 g/g for the hexane, toluene, octadecene, silicone oil and motor oil, respectively. The absorption capacity of polydimethylsiloxane-functionalized Ms with different oils remained undiminished after 20 cycles. This indicated the usability of the material for the oils (Chen et al., 2016).
Fig. 9.4A depicted images of the separation operation of organic solvent (toluene) from the
water layer through FOC-TiO2 sponge. Fig. 9.4B showed the organic solvent (chloroform) fell in
the base. Methanol, ethanol, hexane, DMSO, DMF, acetone, chloroform, THF, pump oil and
motor oil were investigated for the separation from water by the FOC-TiO2 modified sponge as
seen in Fig. 9.4C. Based on the, thickness, viscosity, and surface tension of the absorbed solvents, FOC-TiO2 improved sponge has an outstanding absorption potential in the vicinity of
37.288.1 g/g to its original weight. Absorption reusability of the FOC-TiO2 improved sponge
for chloroform, pump oil and hexane was also studied and indicated after 20 cycles, there was
no discernible difference, suggesting outstanding reuse efficiency (Cho et al., 2016).
Turpentine, hexane, cyclohexane, paraffin oil, methyl silicon oil, CCl4, toluene, and chloroform have absorption amounts of 102.1, 78.0, 85.2, 95.9, 82.4, 159.6, 91.5, and 160.0 g/g,
B. Physical processes
166
9. Oil spill treatment using porous materials
TABLE 9.1 Comparison of adsorption capacities of various materials in the previous study.
Separation capacity
(g/g)
Reference
Oil/water
separation
60120
Yuan et al. (2018)
Cellulose based aerogel
Oil/water
separation
58.06101.14
Yin et al. (2016)
Ms-PDMS
Oil/water
separation
34.837.9
Lee et al. (2019)
Cellulose hybrid biomembrane
Oil/water
separation
520
Kollarigowda et al.
(2017)
Carbon microbelt aerogel
Oil/water
separation
56188
Bi et al. (2014)
Carbon fiber aerogel
Oil/water
separation
50192
Bi et al. (2013)
Lignin modified aerogel
Oil/water
separation
2040
Jiang et al. (2017)
Modified eggshell particles
Oil/water
separation
1434
He et al. (2018)
CEC/Fe3O4/PFOS material
Oil/water
separation
49.97140.90
Sun et al. (2020)
Polydimethylsiloxane-Functionalized Melamine
Sponge
Oil/water
separation
1875
Chen et al. (2016)
FOC-TiO2 modified sponge
Oil/water
separation
37.288.1
Cho et al. (2016)
Furfuryl alcohol modified melamine sponge
Oil/water
separation
78160
Feng et al. (2017)
Ms@SiO2@VTMS
Oil/water
separation
60109
Gao et al. (2018)
PODS-modified sponge
Oil/water
separation
4268
Ke et al. (2014)
(Al2O3/PUF) foam sponge
Oil/water
separation
1037
Kong et al. (2018)
polyurethane sponge coated with KH-570modified graphene
Oil/water
separation
1038
Li et al. (2015)
CS-SiO2-PU sponges
Oil/water
separation
1865
Li, Zhao, et al.
(2017)
compressible and conductive carbon aerogels
Oil/water
separation
3370
Li, Li, et al. (2017)
Carbon fiber aerogels
Oil/water
separation
100170
Liu et al. (2018)
Material
Type of use
Biomass carbon @SiO2@MnO2 aerogel
(Continued)
B. Physical processes
167
9.3 Discussion
TABLE 9.1 (Continued)
Separation capacity
(g/g)
Reference
Oil/water
separation
60150
Oribayo et al. (2017)
PU@Fe3O4@PS sponge
Oil/water
separation
30105
Zhou et al. (2019)
CF-PDA-Ag-NDM
Oil/water
separation
95.098.3
Zhou et al. (2017)
PDMS sponge
Oil/water
separation
500%2100%
Zhao et al. (2014)
Magnetic titanium dioxide foam
Oil/water
separation
35.2364.31
Yu et al. (2016)
ALD of ZnO
Oil/water
separation
85162
Xiong et al. (2018)
Material
Type of use
Formaldehyde-Melamine-Sodium Bisulfite
Copolymer Foam
respectively. The reusability of improved Ms was investigated using turpentine, n-hexane,
and cyclohexane as instances. The ingested oil and solvents into the Ms framework can be
quickly retrieved using a basic pressing process, and the removal efficiency for turpentine oil,
n-hexane, and cyclohexane reduced by 14.0, 5.1, and 5.2 g/g, respectively, after 10 iterations
of absorption and desorption, and prevailed nearly constant in the last few sessions.
Furthermore, despite 10 cycles of absorption and desorption, the WCA of improved Ms
remained in the 138145 degrees region (Feng et al., 2017). Several organic solvents and oils
commonly employed in laboratories and factories were required to test the absorption potential of the Ms@SiO2@VTMS sponges. In fact, the analyzed oils/solvents were easily absorbed
by the sponge in a matter of seconds, indicating good absorptivity (Liu et al., 2013). In the
field of oil extraction and water/oil isolation processes, the material’s renewability or extensibility is often an important attribute to remember. A continuous absorption-compressingdehydrating procedure with hexane as the immersing solvent was used to measure the recyclability of the improved sponge (Arslan, Aytac, & Uyar, 2016). The sponge retained its
normal structure throughout the method, as predicted, and the disappearance of hexane in
the sponge during soaking operation was verified by mass restoration of the sponge. The
hydrophobic sponge’s hexane absorption ability was tested up to 12 loops. During every loop,
an essentially stable absorption potential of B60 g/g was discovered, illustrating the hydrophobic sponges’ strong recyclability (Gao et al., 2018). The absorption capacities for methyl silicon oil, toluene and light petroleum in the range 4268 g/g. These absorption capacities
maintained after 50 cycles (Ke et al., 2014). Chloroform, hexane, tetrachloromethane, bean oil,
methylbenzene and diesel oil were investigated for the separation from water by (Al2O3/
PUF) foam sponge. The absorption capacities found in the range 1037 g/g. Chloroform, soybean oil and methylbenzene were selected to assess the recyclability of the (Al2O3/PUF) foam
sponge. The absorption capacity for chloroform, soybean oil and methylbenzene are 37.0, 6.8,
and 15.8 g/g, respectively (Kong et al., 2018). Soybean oil, diesel oil and pumping oil were
B. Physical processes
168
9. Oil spill treatment using porous materials
FIGURE 9.4 The oil absorption execution of FOC-TiO2 improved sponge. (A) The image of the reduction
action of organic solvent (toluene) flow on the water surface by utilizing FOC-TiO2 sponge; (B) and the organic
solvent (chloroform) fell in the base; (C) absorption capacity of the FOC-TiO2 improved sponge on different
organic liquids and oils. Source: Adapted with permission Cho, E.-C., Chang-Jian, C.-W., Hsiao, Y.-S., Lee, K.-C. &
Huang, J.-H. (2016). Interfacial engineering of melamine sponges using hydrophobic TiO2 nanoparticles for effective oil/
water separation. Journal of the Taiwan Institute of Chemical Engineers, 67, 476483.
investigated for the separation from water by polyurethane sponge overlayed with KH570-improved graphene. Pumping oil shows the high absorption efficiency than soybean and
diesel oil. The maximum absorption capacity of the polyurethane sponge overlayed with
KH-570-improved graphene for various oils did not reduce when the polyurethane sponge
overlayed with KH-570-improved graphene was reused more than 120 times. The recyclability
of the polyurethane sponge overlayed with KH-570-improved graphene was ample superior
apart from other oil absorbents, together with the GN-based sponge (five cycles) (Nguyen,
Tai, Lee, & Kuo, 2012) and the decreased GO-overlayed PU sponge (50 cycles) (Liu et al.,
2013). As a result, after 120 iterations of recycle, the oil-absorbent capacities of the KHGN
sponge barely reduced. Moreover, the mass of the sponge after 5120 iterations of desorption
revealed no improvement, including a small rise during the first five iterations. The mass of
the KHGN sponges rose by 1.61.9 g after five iterations with the three types of liquid. The
absolute amount of adsorption capability may have decreased somewhat. It had no impact,
though, on the overall adsorption capability for oil. These findings indicate that the KHGN
sponge with superhydrophobicity not only had a strong absorption potential for various oils,
B. Physical processes
9.3 Discussion
169
but it was also rather recyclability (Li et al., 2015). For a number of oils and solvents, comprising toluene, tetrachloroethane, petroleum ether, kerosene, hexane, heptane, gasoline, and chloroform, CS-SiO2-PU sponges demonstrated outstanding absorption capacities of up to 1865
times their self-weight. The discrepancy in absorption potential was most likely caused by the
thickness and gel strength of the oils or organic solvents. During the oil/water isolation cycle
capillary forces push oil into the sponge’s interior while repelling water from the exterior (Li,
Zhao, et al., 2017). The compacted and conductive carbon (3C) aerogels with high voids
(B86%) demonstrated extremely high absorption potential for a variety of commonly experienced oils. Depending on the characteristics of the oils, the absorption capacity is 3370 g/g,
which is better than superhydrophobic polyurethane sponges with absorption capacities of
1345 g/g (Wu, Li, Li, Zhang, & Wang, 2015) and silicone sponges with absorption capacities
of 618 g/g (Hayase, Kanamori, Fukuchi, Kaji, & Nakanishi, 2013; Li, Li, Wu, Zhao, &
Zhang, 2014). Even though absorption potential of the 3C aerogel is marginally smaller than
that of the some of the aerogels developed from bacterial cellulose, CNTs, and graphene (Sun
et al., 2013; Wu et al., 2013) its versatility and cheap price rendered it an attractive substrate
for specific oil/water isolation between all of these 3D porous components. Furthermore, the
absorption of the oils by the 3C aerogel is extremely smooth. For a 1 cm3 piece of 3C aerogel,
the absorption maximum could be achieved in 5 s. Furthermore, the 3C aerogel could be
employed several occasions for oil absorption with no improvement in absorption potential
observed (Li, Li, Sun, & Zhang, 2017).
Zhou et. al. synthesized PU@Fe3O4@PS sponge and utilized for the absorption of various
oils and organic solvents. Among all oil and organic solvents, chloroform and carbon tetrachloride showed high absorption capacity. Absorption capacity for castor oil, toluene, diesel
and chloroform on the PU@Fe3O4@PS sponge was evaluated for 20 cycles. Less than 5% of initial absorption capacity for particular oil or solvent was decreased after 20 cycles which shoed
high reusability of the PU@Fe3O4@PS sponge (Zhou et al., 2019). CF-PDA-Ag-NDM was
investigated for the absorption efficiency on the different types of oil or organic solvent and
water system. All oil or organic solvent and water system showed high absorption efficiency
due to the superhydrophobic nature of CF-PDA-Ag-NDM. Among all the systems, dodecanewater system revealed 98.3% absorption efficiency. In realistic implementations the material’s
reliability, in comparison to isolation capacity and invasion strain, should be investigated.
Despite 30 iterations of application with the dodecane/water combination, CF-PDA-Ag-NDM
retains a large isolation performance (higher than 98%) and superhydrophobicity, demonstrating the reliability of the wettability and isolation performance (Zhou et al., 2017). All oil or
organic solvent and water system showed high absorption efficiency due to the superhydrophobic nature of magnetic titanium dioxide foam. The separation capacity was found in
between 35.2364.31 g/g for all oil and organic solvent. The explanation for this trend was
that titanium dioxide were essential in the oil absorption process, and additional titanium
dioxide resulted in increased absorption to a certain amount (Yu et al., 2016). Nevertheless,
additional increases in mass content had virtually no effect on absorption ability; however, the
excess titanium dioxide softened the structure of the foam, which somewhat reduced absorption capacity (Wenzel, 1936). ALD of ZnO was investigated for the absorption efficiency on
the carbon tetrachloride, vegetable oil, liquid paraffin, lubricate oil, cyclohexane and diesel oil.
Among all the systems, carbon tetrachloride-water system revealed 162 g/g absorption efficiency. Despite 20 runs, almost 90% of the original absorption potential is retained, showing
B. Physical processes
170
9. Oil spill treatment using porous materials
the ZnO-deposited foams’ outstanding reusability. The ultrathin ZnO coating, which barely
absorbs any porous structure of the pure foams, is responsible for the large absorption potential and outstanding recyclability. Furthermore, the ultrathin ZnO layer’s binding to the foam
surfaces was quite powerful. The ZnO-deposited foams withstand a rugged ultrasonication
obstacle and retain their high hydrophobicity and potential to efficiently absorb oil from water
for at most 8 months while kept in ambient conditions (Xiong et al., 2018).
9.4 Conclusion
The standard materials and techniques used in the current production of
superhydrophobic-superoleophilic, superhydrophilic-superoleophobic, superhydrophilicunderwater superoleophobic, adjustable super-wetting polymeric oil/water isolation
porous materials like sponge, foam, and aerogels were briefly examined in this review.
The optimal wettability for working with the specific oil/water mixtures was established
by analyzing the impact of wettability on oil/water isolation. Using related methods, different polymers may be utilized to manufacture super-wettable porous materials. Owing
to their distinct functions in distinguishing particular oil/water mixtures, the conditions
for wettability are not the same. Low surface energy polymers and nanomaterials can be
used to monitor surface wettability. The roughness of the used nanomaterials was greatly
increased, which improved wettability and isolation efficiency. Furthermore, the nanomaterials that have been integrated can be used to enhance the mechanical strength of porous
materials. Organicinorganic nanomaterials alteration coatings have a lot of promise for
producing high-performance porous materials to fulfill today’s and tomorrow’s oily wastewater management needs.
Abbreviations
ALD
CEC
CF
CS
Ms
MTMS
NDM
ODS
PDA
PDMS
PFOS
PU
PUF
WCA
atomic layer deposition
carbonized eichhornia crassipes
copper foam
candle soot
melamine sponge
methyltrimethoxysilane
N-dodecyl mercaptan
octadecylsiloxane
polydopamine
polydimethylsiloxane
1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane
polyurethane
polyurethane foam
water contact angle
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C H A P T E R
10
Nanotechnological advances for oil
spill management: removal, recovery
and remediation
Sougata Ghosh1 and Thomas J. Webster2
1
Department of Microbiology, School of Science, RK University, Rajkot, India 2Department of
Chemical Engineering, Northeastern University, Boston, MA, United States
O U T L I N E
10.1 Introduction
175
10.2 Oil pollution
176
10.3 Nanotechnology driven solutions
10.3.1 Nanosensors
10.3.2 Nanofluids
10.3.3 Nanocomposites
176
177
178
182
10.3.4 Nanocoating
10.3.5 Nanomembranes
10.3.6 Nanocatalysts
185
189
191
10.4 Conclusions and future
perspectives
191
References
192
10.1 Introduction
A multidisciplinary approach of nanotechnology has led to its applications in various
fields like medicine, food, electronics, agriculture, and even cleaning the environment.
Attractive physicochemical properties of nanoparticles with a high surface area and
exotic shape have made them the most preferred agents in catalysis, adsorption, coatings, and carriers. Recently, nanotechnology has found its applications also in the oil
industry and refineries. The most important aspect of nanotechnological advances in oil
recovery and spill management is promising from an environmental remediation perspective (Franco, Zabala, & Cortés, 2017).
Advances in Oil-Water Separation
DOI: https://doi.org/10.1016/B978-0-323-89978-9.00025-2
175
© 2022 Elsevier Inc. All rights reserved.
176
10. Nanotechnological advances for oil spill management: removal, recovery and remediation
More research is being carried out to ensure enhanced oil recovery (EOR) and thus several polymer coated nanoparticles are being developed and investigated for their efficiency
toward the same. A high surface area-to-volume ratio, thermal and chemical stability, and
dispersibility makes the nanostructured materials the most promising agents for oil recovery and removal. Various nanofilms and nanofibers play a significant role in energy storage and conversion (Peng et al., 2018).
In this chapter, hazard of oil pollution is discussed. Further, an elaborate account on
nanotechnological advances in several steps in the oil industry that include drilling, refining, recovery, production and damage control is furnished.
10.2 Oil pollution
One of the major concerns of water pollution is due to discharge of oil refinery effluents
that are mostly loaded with hazardous components that include hydrocarbons, ammonia,
phenol, and sulfides. These pollutants have a grave impact on aquatic lives of algae, fish,
plankton and crustaceans. Oil pollutants can kill the aquatic organisms due to poisoning,
coating and asphyxiation, with sensitive juveniles being the most susceptible. Moreover, oil
can cause stress and can be a sublethal apart from being mutagenic and carcinogenic.
Physiological effects due to oil pollution may also result in alterationa of behavioral patterns.
Other hazards include the reduced productivity of phytoplankton and/or algae that can
have notable adverse effects on higher crustaceans and fish that feed on them. Inhabiting the
oil contaminated niche may result in the development of resistant genotypes replacing the
native population that can lead to alteration in the community structure. Such pollution can
lead to selection of dominant species as it has been observed that the fresh water species are
more tolerant to marine/estuarine species. Reproductive impairment is also observed in
aquatic species like Ceriodaphnia that produces fewer young on growing in refinery wastewater. Likewise, a reduction in egg production and the number of broods in the estuarine crustacean Mysidopsis bahia was also noticed. High mortality in fish due to oil pollution is mainly
associated with respiratory distress, surfacing and secretion of mucus (Wake, 2005).
It is important to note that the severity of oil pollution can be controlled and the area of
impact can recover upon the reduction of toxicity of the effluent. However, the time taken
for the remediation and recovery depends on the effectiveness of the strategy and the
area. Recently various nanoscale materials are being developed and used in the oil industry for ameliorating the deleterious effects of oil pollution which is discussed in the following section.
10.3 Nanotechnology driven solutions
Nanomaterials play a multifunctional role in the exploration of refining and drilling as
well as the completion of production due to their smaller size, attractive surface properties
and high stability. There are several types of nanoscale materials that are used in various
processes in the oil industries.
B. Physical processes
10.3 Nanotechnology driven solutions
177
10.3.1 Nanosensors
Remote sensing is now a preferred strategy for detecting oil spills and designing the
response for remediation. Further, remote sensing can play a vital role to trace illegal discharge from ships that is the chief cause for mortality and morbidity of seabirds, fishes,
turtles and other aquatic fauna. Highly effective nanosensors are comprised of highly miniaturized electromechanic integration as the main component. The nano-size enables these
sensors to evade the micro pores for sensing oil spills (Fingas & Brown, 2014).
Several nanosensors that are manufactured using carbon nanotubes, graphene and also
other associated piezoelectric material are resistant to extreme temperature and pressure.
Nano-developer and nano-signal enhancers are nano-robots that can easily move into the
cracks and crevices of the reservoir along with the flow of the fluid. This enhances the local
electric, magnetic and acoustic behaviors of the reservoirs. This further increases electric logging, nuclear magnetic logging and microseismic logging due to an efficient differentiation
degree of oil layers and water layers. Such a phenomenon helps in generating a more
detailed information on reservoir porosity, permeability and oil saturation. However, it is
important to note that the efficiency of a nanosensor largely depends upon the physicochemical and optoelectronic properties of the nanomaterials (Liu, Jin, & Ding, 2016).
Paramagnetic nanoparticles can be used for monitoring the distribution of immiscible fluids
on the subsurface. This is achieved upon inducing their mobility due to the imposition of a magnetic field. Such nanoparticles can be directed for selective adsorption at the oil-water interface.
Moreover, monitoring of their prolong stability in dispersion with a low retention in the porous
medium can be traced to exploit interfacial movements for external detection. Ryoo et al. (2012)
reported surface modified iron oxide nanoparticles (IONPs) for oil detection which was measured by phase-sensitive optical coherence tomography as illustrated in Fig. 10.1. The individual
FIGURE 10.1 Schematic diagram of phase-sensitive optical coherence tomography experimental setup. The
approximate diameters of the cylindrical well, glass slide holder and solenoid are 4, 38 and 50 mm respectively.
The solenoid iron tip is 0.9 mm wide and is 0.2 mm from the glass slide (Ryoo et al., 2012). Source: Reprinted with
permission from Ryoo, S., Rahmani, A. R., Yoon, K. Y., Prodanović, M., Kotsmar, C., Milner, T. E., . . . Huh, C. (2012).
Theoretical and experimental investigation of the motion of multiphase fluids containing paramagnetic nanoparticles in
porous media. Journal of Petroleum Science and Engineering, 81, 129144. Copyright r 2011 Elsevier B.V.
B. Physical processes
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10. Nanotechnological advances for oil spill management: removal, recovery and remediation
nanoparticles in the ferrofluid were between 3 and 5 nm, while the citrate functionalized magnetic nanoparticles were 13 nm in size at pH 8. This novel material can be used for developing a
magnetic field-based method for an accurate, non-invasive determination of multiphase oil distribution in a reservoir rock.
10.3.2 Nanofluids
Although there are effective methods for oil mining, still abundant crude oil residue
remains which are generally extracted by conventional methods like steam flooding, chemical flooding or gas flooding. Nanofluid flooding has emerged as a promising alternative
due to its low cost and environmentally benign nature (Luo et al., 2016). More recently,
Chen, Jiang, and Zhen (2021) employed temperature sensitive iron oxide (TSIO) nanoparticles for an EOR process. Initially IONPs were synthesized by a hydrothermal method
where iron (III) chloride hexahydrate was reacted with sodium acetate trihydrate (NaAc)
and polyvinylpyrrolidone (PVP) at 200 C for 18 h. The IONPs were recovered and further
reacted with N-isopropylacrylamide (NIPAM), potassium persulfate, and sodium pstyrenesulfonate (SSS) at 80 C for 12 h resulting in the synthesis of TSIO that was dispersed in into brine or water to obtain the nanofluid. The IONPs with a comparatively
thicker coating comprised of PNIPAM with styrene sulfonic acid group were irregular in
shape with particle sizes smaller than 100 nm. The agglomeration of TSIO into bigger particles was attributed to the polymer chain around the IONPs. Interestingly, with a rise in
temperature up to 50 C, the particle size of TSIO decreased from 225.3 to 175.6 nm. The
temperature dependent modulation of particle size was due to the temperature sensitive
polymer, PNIPAM. The nanofluid was further used for EOR using a microscopic oil displacement strategy as illustrated in Fig. 10.2.
The experimental device was comprised of five parts that included a fluid reservoir, injection pump, glass holder, analytic system and receiver. The fluid reservoir could store fluids
like water, nanofluid and crude oil that was used for flooding the glass plate fixed at the glass
holder, which was made by etching the holes. Initially, crude oil was used to saturate the
glass plate followed by injection of water into it simulating secondary water flooding. Next,
the nanofluid was injected into the glass plate to drive the residual crude oil after water flooding that could be effectively recorded by a camera. The TSIO facilitated oil recovery was
attributed to the altered wettability of the rocks as well as a decreased interfacial tension (IFT)
of the oil and water. The oil recovery at room temperature was remarkably enhanced from
65.78% to 74.15% while at 50 C, the recovery rate further increased up to 84.02%.
In another study, Sagala, Hethnawi, and Nassar (2020) reported hydroxyl-functionalized silicate-based nanofluids for EOR where nano-pyroxene was used to influence the wettability, IFT
and asphaltene aggregation. The triethoxy (octyl) silane was anchored on the nanopyroxene
(NPNP) surface to synthesize the fully hydroxylated NPNP nanoparticles. The nanofluid was
dispersed in synthetic brine with a pH adjusted to 10. The hydrodynamic size was approximately 10 nm at a high pH while at a neutral pH, the size was found to be 300 nm indicating
aggregation and reduced stability. Interestingly, the presence of nanoparticles reduced the
aggregate size of the n-C7 asphaltenes and IFT in a concentration dependent manner. Fig. 10.3
illustrates the core flooding set up assembly for oil recovery using the nanofluid. Further, the
B. Physical processes
10.3 Nanotechnology driven solutions
179
FIGURE 10.2 Schematic of the microscopic oil displacement experimental device(Chen et al., 2021). Source:
Reprinted with permission from Chen, Q., Jiang, X., & Zhen, J. (2021). Preparation and characterization of temperature sensitive iron oxide nanoparticle and its application on enhanced oil recovery. Journal of Petroleum Science and
Engineering, 198, 108211. Copyright r 2020 Elsevier B.V.
contact angle and wettability index measurements indicated that nanoparticles from the nanofluid adsorbed on the rock surfaces changing the wettability from intermediate wet to stronger
water-wet in the absence and presence of initial water films. In the presence of irreducible
water saturation during wettability index measurements, depending on the brine composition
and pH, initial alteration with aging resulted in a mixed or intermediate wet that changed to
stronger water-wet with an increase in the NPNP concentration. Although IFT was reduced
with a rise in NPNP concentration, it did not alter the ultra-low range that can remobilize
trapped oil due to higher capillary forces.
In another study, Sharma, Iglauer, and Sangwai (2016) reported a silica (SiO2) based nanofluid for EOR. The polyacrylamide (PAM) was used as a dispersant in which SiO2 nanoparticles
were added followed by sonifaction for 23 h during preparation of the nanofluid. Two types
of nanofluids were prepared, one with nanoparticles (N) dispersed only in the aqueous PAM
solution (NP) and the other with an aqueous surfactant 2 polymer (sodium dodecyl sulfate)
denoted as NSP formulations. The average nanoparticle aggregate size in the NP nanofluid was
larger for 1.5 wt.% SiO2 (4.12 μm) and 2.0 wt.% SiO2 (4.54 μm) than for 1.0 wt.% SiO2 (3.54 μm),
and their size further increased in the presence of SDS (5.54 μm for 1.5 wt.% SiO2 and 6.17 μm
for 2.0 wt.% SiO2) as seen in Fig. 10.4. The IFT of the crude oil-SP system (4.9 mN/m on the 1st
day and 5.13 mN/m on the 27th day) was lower compared to the crude oil-P system
(18.03 mN/m on the 1st day and 17.02 mN/m on the 27th day) which might be attributed to
B. Physical processes
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10. Nanotechnological advances for oil spill management: removal, recovery and remediation
FIGURE 10.3 Displacement test diagram: (1) carbon dioxide cylinder, (2),
manometer gauge, (3), (4), and (5) transfer
cells for oil, brine, and nanofluids respectively, (6) valves, (7) pressure transducer,
(8) core holder, (9) data acquisition computer, (10) back pressure regulator, (11)
collector, (12) ISCO pump, (13) overburden
pressure gauge. (Sagala et al., 2020) Source:
Reprinted with permission from Sagala, F.,
Hethnawi, A., Nassar, N.N. (2020). Hydroxylfunctionalized silicate-based nanofluids for
enhanced oil recovery. Fuel, 269, 117462.
Copyright r 2020 Elsevier Ltd.
the adsorption of the surfactant at the crude oil 2 water interface. Further, the IFT of both the
crude oil-NP/NSP systems showed minimum IFT values at 1.0 wt.% SiO2. At higher temperatures, the application of the SiO2 nanofluids remarkably increased oil recovery owing to IFT
reduction, fluid viscosity increase, and wettability alteration (from intermediate-wet to strongly
water-wet).
Recently, Zhou et al. (2020) developed a strategy for oil recovery using a nano-composite
comprised of polymer nanoparticles (PolyNPs) and a betaine-type zwitterionic surfactant. A
nano-precipitation method was employed to fabricate the PolyNPs where Poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(1,4-benzo-{2,10 ,3}-thiadiazole)] (PFBT) and Poly (styrene-co-maleic
anhydride), cumene terminated were dissolved in tetrahydrofuran (THF) followed by ultrasonication. The PolyNPs were recovered by the evaporative removal of THF. In the next step,
the nanofluids were prepared by adding different amounts of PolyNPs into the betaine surfactant solution in 15% simulated brine as illustrated in Fig. 10.5. Interestingly, in the presence of
the nanofluid the wateroil IFT of the Bakken crude oil decreased by 99.49% and the contact
angle increased by 125.73%. Also, the total oil recovery by the nanofluid was enhanced by
9.32% which was attributed to the dynamic displacing processes.
Ehtesabi, Ahadian, Taghikhani, and Ghazanfari (2014) used anatase and amorphous
TiO2 nanoparticles (TiO2NPs) for heavy oil recovery from sandstone cores. At first, the
titanium tetraisopropoxide, H2O2, and H2O were mixed at the volume ratio of 12:90:200,
respectively. Further, the TiO2NP solution was refluxed for 10 h to promote crystallinity.
After injecting a double pore volume of 0.01% anatase structure into solution, 80% of the
oil was recovered. The rock wettability changed from oil-wet to water-wet conditions after
treatment with nanoparticles as confirmed by contact angle measurements. A homogeneous deposition of nanoparticles into the core plug surface along with some nanorods
B. Physical processes
10.3 Nanotechnology driven solutions
181
FIGURE 10.4 SEM images of (A) NP and (B) NSP nanofluids (1.0 wt.%wt.% SiO2) in the presence of aqueous
PAM and SDS-PAM at 30 C, (C) and (D) are SEM images of sand grains, taken from inlet and outlet ends of sand
packs flooded by the NP nanofluid (Sharma et al., 2016). Source: Reprinted with permission from Sharma, T., Iglauer,
S., Sangwai, J.S. (2016). Silica nanofluids in an oilfield polymer polyacrylamide: Interfacial properties, wettability alteration,
and applications for chemical enhanced oil recovery. Industrial & Engineering Chemistry Research, 55, 12387 2 12397.
Copyright r 2016 American Chemical Society.
with a diameter about 60 nm was seen. An increase in the nanorod concentration with the
same diameter resulted in enhanced plugging, facilitating more oil recovery.
More recently, several biogenic routes were developed for synthesizing novel metal and
alloy nanoparticles for diverse applications (Ghosh, 2018). Green routes using extracts of
medicinal plants like Dioscorea oppositifolia, Barleria prionitis, Gloriosa superba, Gnidia glauca,
Litchi chinensis, Platanus orientalis, and Plumbago zeylanica are considered as environmentally benign rapid and efficient methods (Bhagwat et al., 2018; Ghosh, Chacko, et al., 2016;
Ghosh, Gurav, et al., 2016; Ghosh, Harke, et al., 2016; Ghosh, Patil, et al., 2016; Jamdade
et al., 2019; Rokade et al., 2017; Rokade et al., 2018; Shende et al., 2017; Shende et al., 2018;
Shinde et al., 2018). Biologically synthesized nanoparticles do not involve any hazardous, toxic
or corrosive chemicals during synthesis or stabilization. Hence, the biogenic nanoparticles are
more biocompatible and environmental friendly (Ghosh, Jagtap, et al., 2015; Ghosh, More,
Derle, et al., 2015; Ghosh, More, Nitnavare, et al., 2015; Ghosh, Nitnavare, et al., 2015; Kitture
et al., 2015; Salunke et al., 2014; Sant et al., 2013).
B. Physical processes
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10. Nanotechnological advances for oil spill management: removal, recovery and remediation
FIGURE 10.5
Schematic diagram of the designed nanofluid. (A) Polymer PFBT. (B) Polymer poly (styrene-comaleic anhydride). (C) Self-assembled polymer nanoparticle. (D) Polymer nanoparticle augmented surfactant
nanocomposite. (E) The nanofluid formed by dissolving the nanocomposite in brine. (F) The application of the
nanofluid for oil recovery (Zhou et al., 2020). Source: Reprinted with permission from Zhou, Y., Wu, X., Zhong, X.,
Reagen, S., Zhang, S., Sun, W., . . . Zhao, J.X. (2020). Polymer nanoparticles based nano-fluid for enhanced oil recovery at
harsh formation conditions. Fuel, 267, 117251. Copyright r 2020 Elsevier Ltd.
Zargar et al. (2020) grafted titanium oxide NPs (TiO2NPs) synthesized by Euphoria condylocarpa extract on quartz surface to fabricate a green nanocomposite (NC) for EOR. The plant extract
was reacted with a TiO(OH)2 solution to obtain a dark brown greenish precipitate that was
recovered by filtration and heated up to 600 C which was further washed and dried to get
pure TiO2NPs. After mixing the biogenic TiO2NPs with quartz powder, the resulting mixture
was refluxed for 3 h at 80 C. The TiO2/quartz NC was suspended in sea water and distilled
water to obtain a nanofluid which could effectively minimize the IFT and contact angle between
crude oil and water on the surface of carbonate rocks. Significantly, the TiO2/Quartz-nanofluid
exhibited an additional oil recovering capability of 21% original oil in place (OOIP) that was
attributed to the reduction in IFT from 36.4 to 3.5 mN/m. Moreover, the nanofluid improved
the rheological behavior and altered wettability that facilitated a stronger water-wet system
from 103 to 48 degrees contact angles. Similarly, Table 10.1 presents various other nanoparticles
were used for the preparation of nanofluids to ensure EOR.
10.3.3 Nanocomposites
Various graft polymers used in nanocomposites are used effectively for oil recovery
due to their high thermal and shear stability owing to the attachment of PAM chains onto
the rigid polysaccharide backbone. Singh and Mahto (2017) reported a graft polymer
B. Physical processes
183
10.3 Nanotechnology driven solutions
TABLE 10.1 A summary of previous work on effects of various nanofluid categories on interfacial tension
(IFT), contact angles (CA) and oil recovery.
IFT [mN/m]
Nanomaterial
Dispersion media
NP conc. [wt.%]
Rock type
Clean
With NP
CA [degree]
Clean
With NP
EOR
[%OOIP]
Al2O3
Propanol
0.050.3
Sandstone
5.7
2.3
56.6
76.8
19.4
Al2O3
DIW
0.05
Limestone
18
13.4
55.8
65.7
9.9
CuO
Polyethyl glycol
0.10.2
Glass
47.9
1.5
9
1.8
15
Fe2O3
6.3
2.7
56.6
73.9
17.1
Fe3O4/chitosan
Brine
0.010.03
Sandstone
30
17.3
127
92
10.8
SiO2
Ethylene glycol
0.277
Glass
43
8.8
66
25
17
SiO2
PAM
12
Sandstone
27
10.2
24.7
SiO2
Xanthan gum
0.10.5
Sandstone
17.8
6.4
86
20
7.81
SiO2
Ethanol
0.4
Sandstone
26.3
1.7
55
78
23
SiO2
5
1.5
56.6
79.1
21.6
SiO2
Brine
0.05
Sandstone
19.2
12.8
33
26
17
SiO2
16.7
11
54.8
57.7
2.9
SiO2
Brine
0.1
Sandstone
17.5
7
12
40
28
SiO2
LoSal water
0.1
Sandstone
7
SiO2/prop-2-enamide
0.61.2
Sandstone
28
7
87
28
21
0.1
Sandstone
27
14
85
62.2
9.9
SiO2/Poly2(DMAEA)
0.10.2
Sandstone
47
35
5.2
TiO2
17.5
12.5
55.3
61.9
6.6
ZnO
SDS
0.05
Carbonate
2.8
3.5
22.5
72.2
0
ZnO
SDS
0.050.5
Calcite
27.4
18.6
11.8
11
ZnO/SiO2/xanthan
LoSal water
0.050.2
Carbonate
31.8
2.016
137
34
19.3
SiO2/2-Poly(MPC)
Source: Reprinted with permission from Zargar, G., Arabpour, T., Manshad, A.K., Ali, J.A., Sajadi, S.M., Keshavarz, A., Mohammadi, A.H.,
2020. Experimental investigation of the effect of green TiO2/Quartz nanocomposite on interfacial tension reduction, wettability alteration,
and oil recovery improvement. Fuel, 263, 116599. Copyright r 2019 Elsevier Ltd.
nanocomposite hydrogel system composed of a PAM graft starch/clay nanocomposite
and chromium (III) acetate (crosslinker). At first, a gelatinized starch (St) graft PAM
sodium montmorillonite nanocomposite (PAAm-g-St/MMT) was fabricated employing a
free radical polymerization technique in an inert atmosphere of nitrogen using potassium
persulphate as an initiator. Then, the graft polymer nanocomposite hydrogel was prepared
by reacting the polymer with chromium(III) acetate in brine. As seen in Fig. 10.6, starch
exhibited a granular morphology that was distorted to a fibrillar structure grafted with
PAAm. Further, the incorporation of MMT altered the fibrillar structure of PAAm-g-St to
a coherent and near co-continuous structure in PAAm-g-St/MMT. The clay particles were
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10. Nanotechnological advances for oil spill management: removal, recovery and remediation
FIGURE 10.6 FESEM images of (A) starch; (B) PAAm; (C) PAAm-g-St; and (D) PAAm-g-St/MMT (Singh and
Mahto, 2017). Source: Reprinted with permission from Singh, R., & Mahto, V. (2017). Synthesis, characterization and
evaluation of polyacrylamide graft starch/clay nanocomposite hydrogel system for enhanced oil recovery. Petroleum
Science, 14, 765779. Copyright r The Author(s) 2017. (Open Access).
40100 nm in size that formed layers and were well dispersed within the polymer matrix.
The PAAm-g-St/MMT hydrogel exhibited an undulant surface due to the inclusion of a
nanoclay into the hydrogel. In sand pack flooding experiments, the concentration of the
PAAm-g-St/MMT was set at 0.5 wt.%, while the crosslinker concentration varied at 0.4 wt.
% and 0.2 wt.% and also in the conventional gel system [PAM and Cr(III) acetate gel], the
PAM concentration was 1.0 wt.% and the crosslinker concentration was 0.4 wt.% and
0.2 wt.%, respectively. These parameters enhanced the plugging capacity of the graft polymer nanocomposite indicating its promise for water shutoff treatments required for EOR
from oilfields.
In another similar study, Tongwa, Nygaard, and Bai (2013) prepared a hydrogel where
hydrolyzed PAM was mixed with brine following its addition into completely exfoliated
nanoclay Laponite XLG to obtain a nanocomposite gel. The resulting product was cut into
smaller sizes, and dried in an oven at 40 C overnight. The hydrogels exhibited high
mechanical toughness, tensile moduli, and tensile strength. An increase in clay concentration was directly proportional to gel strength.
B. Physical processes
10.3 Nanotechnology driven solutions
185
Similarly, Tongwa and Bai (2014) reported that the incorporation of nanomaterials
increased hydrogel strength up to 394%. Additionally, swelling performance, postdegraded gel viscosity, and long-term thermal resistance of a nanocomposite gel increased
by several orders of magnitude compared to hydrogels with no nanomaterial. Initially,
acrylamide was dissolved in which 0.2% XLG was supplemented and stirred vigorously
for complete exfoliation of the clay nanomaterial. In this reaction mixture, PEG-200 (crosslinker) was mixed and kept for 10 h at 40 C for complete gelation. After cutting the elastic
gel into small pieces, they were soaked in water for 3 days, dried at 60 C and pulverized
to get the preformed particle gels of 80 and 100 mesh (180250 mm) sizes. Fig. 10.7 shows
that the nanocomposites had 3D networks with a viscosity of 4437cp unlike the individual
hydrogel (170cp). The degradable laponite XLG nanocomposite hydrogels can be further
used for secondary polymer flooding due to their high post-degradation viscosity under
anaerobic conditions. The nanocomposite can sweep out oil from regions with low permeability as it can act as a conformance control agent that can plug water-thief zones and
channels. Moreover, after injection into a reservoir, with time, the nanocomposite would
degrade into a more viscous polymer that would enter deeper regions of the reservoir and
mix with the flood water. This in turn would lead to better water and polymer flooding
processes due to enhanced water sweep efficiency, thereby enhancing oil recovery.
10.3.4 Nanocoating
Although various nanostructures are used in the process of separation of oil from water,
a nanocoating is considered to be an attractive alternative for its high efficiency for EOR.
Recently, Gharibshahi, Omidkhah, Jafari, and Fakhroueian (2020) reported the synthesis of
a novel multiwalled carbon nanotube (MWCNT)-Fe3O4 nanohybrid (weight ratio of 3:1)
employing a coprecipitation method as illustrated in Fig. 10.8. The synthesized Fe3O4
nanoparticles were spherical with 30 nm size which were distributed on the surface of the
tubular MWCNT. Some aggregation was also noticed which might be attributed to the
loading percent of Fe3O4 nanoparticles to MWCNT (3:1 wt.%). The resulting nanohybrids
were surface modified with 3-AminoPropylTriEthoxySilane, citric acid (CA), and polyethylene glycol (PEG 6000) to ensure effective dispersion into the water. The coated nanomaterials were magnetic and a significant rise in temperature was observed with an addition
of even 0.1 wt.% of MWCNT-Fe3O4 nanohybrids modified with citric acid after being subjected to microwave radiation for 180 s. An enhancement of the microfluidic oil recovery
up to 30.3%, and 43.9% was achieved with Fe3O4 @ CA, and Fe3O4-MWCNT @ CA with
the use of 400 W microwave radiation.
In another interesting study, Hosseini, Sadeghi, and Khazaei (2017) fabricated a
stable hydrophilic coating on a superhydrophobic surface of carbonate rock using TiO2/
SiO2 hybrid nanoparticles. Firstly, the TiO2/SiO2 nanoparticles were synthesized by a
modified sol-gel method which increased surface hydrophilicity due to specific functional
groups. TiO2 nanoparticles were synthesized reacting titanium isopropoxide (TTIP) dissolved in ethanol with HNO3 for 2 h at 60 C for hydrolysis. Next, a mixture of tetraethyl
orthosilicate (TEOS), ammonia and EtOH, was added to the hydrolyzed TTIP solution and
reacted for another 2 h at 60 C until an opaque suspension with high viscosity was
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10. Nanotechnological advances for oil spill management: removal, recovery and remediation
FIGURE 10.7 Before-degradation
environmental scanning electron
microscopy (ESEM) micrographs of:
(A) A pure LXLG nanomaterial. (B)
A pure polyacrylamide (PAM) polymer. (C) 3-D micrograph of a bulk
LXLG nanocomposite hydrogel. (D)
A hydrogel with no nanomaterial. A
fine, smooth network structure is
observed. (E) A LXLG nanocomposite hydrogel swelled in 1% brine as
the solvent. The presence of brine
almost caused the porous network to
close up. (F) A LXLG nanocomposite
hydrogel swelled in distilled water as
the solvent. A denser, thicker, and corrugated network structure is observed.
(G) An extremely stretched, thin section of LXLG nanocomposite hydrogel
(Tongwa and Bai, 2014). Source:
Reprinted with permission from Tongwa,
P., Bai B., (2014). Degradable nanocomposite preformed particle gel for chemical
enhanced oil recovery applications.
Journal of Petroleum Science and
Engineering, 124, 3545. Copyright r
2014 Elsevier B.V.
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10.3 Nanotechnology driven solutions
187
FIGURE 10.8 A schematic of the surface modification of a synthesized Fe3O4-MWCNT nanohybrid
(Gharibshahi et al., 2020). Source: Reprinted with permission from Gharibshahi, R., Omidkhah, M., Jafari, A., &
Fakhroueian, Z. (2020). Hybridization of superparamagnetic Fe3O4 nanoparticles with MWCNTs and effect of surface modification on electromagnetic heating process efficiency: A microfluidics enhanced oil recovery study. Fuel, 282, 118603.
Copyright r 2020 Elsevier Ltd.
produced. The resulting viscous suspension was dried at 100 C for 24 h followed by
annealing at 600 C for 4 h to form TiO2/SiO2 nanoparticles. These nanomaterials were
amorphous spheres with some agglomeration that might be attributed to the calcination
process mediated growth in particle size. The size of the TiO2/SiO2 nanoparticles was
20 nm. Adsorption of nanoparticles on the rock surface converted the superhydrophobic
rock surface to superhydrophilic. Hence, the nano-coatings with a high thermal stability
and moderate mechanical stability can be used for altering wettability leading to increased
oil wet carbonate rock for EOR.
Kim et al. (2019) developed a continuous ZIF-8/reduced graphene oxide (RGO) nanocoating by growing ZIF-8 on a RGO-coated polyurethane (PU) foam as depicted in
Fig. 10.9. The PU foam was immersed in a GO solution for surface modification which
was then subjected to thermal treatment at 150 C for 4 h converting the GO layer into
RGO layer. Then, 2-Methylimidazole (99%, 2-MeIM) and zinc nitrate hexahydrate were
mixed in water to form a solution in which the RGO coated PU foam was immersed. The
resulting zeolitic imidazole framework (ZIF-8) growth was conducted at 50 C for 1 h.
Fig. 10.9B shows that the PU foam was covered by a continuous ZIF-8/RGO coating with
well distributed N (yellow) and Zn (green) atoms throughout the surface of the PU foam
(Fig. 10.9C). The synergy between the hydrophobic/oleophilic properties of RGO and ZIF-8
enabled selective oil absorption of the PU foam with an absorption capacity of 1535 g/g
which was viscosity dependent. An ultrafast selective hexane flux up to 800,000 Lm22/h confirmed the selective organic solvent filtering ability of the ZIF-8/RGO coated PU foam.
Another study by Shi, Li, Cheng, Zhao, and Wang (2021) on a similar line reported that
a multifunctional nanocoating comprised of nano-Fe3O4 and RGO with photothermal conversion ability and non-flammable nature, could be effectively deposited on the polymer
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10. Nanotechnological advances for oil spill management: removal, recovery and remediation
FIGURE 10.9
(A) Schematic illustration to coat a ZIF-8/RGO film on PU foam. (B) Photographic image of a
ZIF-8/RGO/PU foam. (C) SEM image and corresponding EDS mapping images of a ZIF-8/RGO/PU foam. (D)
SEM image obtained from a skeleton of a ZIF-8/RGO/PU foam. Inset is an SEM image of the neat PU foam. (E)
Top and cross sectional SEM images of ZIF-8/RGO/PU foam, respectively. (F) Schematic illustration exhibiting
the interaction between ZIF-8 and RGO (Kim et al., 2019). Source: Reprinted with permission from Kim, D.W., Eum,
K., Kim, H., Kim, D., de Mello, M.D., Park, K., Tsapatsis, M., 2019. Continuous ZIF-8/reduced graphene oxide nanocoating
for ultrafast oil/water separation. Chemical Engineering Journal, 372, 509515. Copyright r 2019 Elsevier B.V.
foam skeletons employing a facile coprecipitation and dip-coating processes. The selective
superior absorption of various oils and organic solvents by the composite foam was attributed to its high hydrophobicity, robust morphology and low density. Interestingly, the
temperature of the nanoscale coating material could rapidly rise with at a rate of 103.5 C/min
upon irradiation due to the double photothermal conversion effects of nano-Fe3O4 and rGO.
The foam displayed a high absorption capacity of 75.1 times its weight. Also, a faster absorption rate of 9000 g/m2/min for highly viscous oil was achieved upon irradiation. The novel
material is unique and advantageous owing to its properties like high flame retardancy, elasticity, and magnetism. The material is, thus, reusable and recyclable that can be controlled
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10.3 Nanotechnology driven solutions
189
magnetically for effective clean up thereby addressing oil spill mediated environmental
pollution.
10.3.5 Nanomembranes
Oil mixed with water can exist in complex forms that include floated oil, dispersed oil,
stable emulsions (droplet diameter , 20 μm), and dissolved oil (Bouchemal, Briancon, Perrier,
& Fessi, 2004). Since conventional methods, such as sedimentation, flotation, and centrifugation are unable to separate oil/water emulsions, particularly surfactant-stabilized oil-in-water
emulsions (SSEs), newer techniques using membranes have emerged as promising alternatives. Microfiltration membranes made from poly (tetrafluoroethylene), poly (vinylidene fluoride), and cellulose are being used for the separation of industrial emulsions.
More recently, Li, Gao, Wang, Chen, and Yu (2021) synthesized a flexible silica nanofiber/
nanobead (SNB) membrane by combining electrospinning and electrospraying techniques.
Firstly, a poly(vinyl alcohol) (PVA) solution and silica sol (prepared using TEOS) were mixed
in different proportions for 4 h. The resulting silica networks were entangled with PVA
chains by hydrogen bonds, increasing the viscosity of the precursor solutions. Eventually the
SNB membrane was prepared by electrospinning the precursor at a high voltage of 20 kV at
22 C 2 25 C followed by calcination at 800 C. The dimensions of the nanofibers were dependent upon the proportion of the precursor components used. Smooth surfaces with 185 nm
diameter of the nanofibers were obtained when the precursors were mixed at a ratio of 10:10
(polymer and silica sol). However, the nanofibers were spindle shaped with numerous beadon-string structures when the precursor ratio was altered to 2:10 and 1:10. The bead diameters varied from 50 nm to 2 μm which were connected by ultrathin fibers with a diameter
of about 30 2 60 nm. Properties like superhydrophilicity and underwater superoleophobicity
(oil contact angle of 162 degrees), small sliding angles (2.5 degrees), and a small oil adhesion
force (0.4 mN) were displayed by the membrane that was composed of nanofiber-supported
bead-on-string structure. Further, the superwettability and hierarchical pore structure of the
SNB membranes were advantageous for good separation performance toward SSEs with
high efficiency ( . 98.8%) and permeate flux (2237 L/m2/h) under low pressure (,10 kPa).
Such nanomembranes not only possessed robust mechanical properties but also exhibited
superior antifouling properties, and excellent reusability.
In another study, Tai, Gao, Tan, Sun, and Leckie (2014) reported a novel free-standing
and flexible electrospun carbon 2 silica composite nanofibrous (NF) membrane for oil
water separation. Initially, a spin dope for SiO2 2 carbon composite was produced by mixing polyacryonitrile (PAN), and TEOS, in dimethylformamide (DMF)/acetic acid (volume
ratio of 15/1) at 90 C. The SiO2 2 PAN NF mat was prepared by electrospinning the aforementioned spin dope at 0.6 2 0.8 kV/cm electric field strength which were further oxidized (stabilized) at 280 C in air for 2 h and carbonized at 900 C in nitrogen for 2 h.
Fig. 10.10 shows that the nanofibers with an average diameter of 481 6 57 nm were
entangled with the membrane rendering it a 3D macroporous network that facilitated the
liquid permeation rate across the membrane due to the decreased mass transfer resistance.
Further, Fig. 10.10B shows the wrinkles on the nanofiber surface making it rough in
appearance. Maintaining the SiO2 concentration below 2.7 wt.% could enhance the
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10. Nanotechnological advances for oil spill management: removal, recovery and remediation
FIGURE 10.10
Characterization of electrospun composite nanofibers. (A) Top view of electrospun composite
nanofibrous mat; (B) Surface morphology of a single composite nanofiber; (C) XRD pattern showing amorphous
carbon and silica in pristine CNFs and the composite nanofibers; (D) Flexibility of the composite nanofibrous mat,
which can be easily cut into a desirable shape, as shown in the inset (Tai et al., 2014). Source: Reprinted with permission from Tai, M. H., Gao, P., Tan, B. Y. L., Sun, D. D., & Leckie, J. O., (2014). Highly efficient and flexible electrospun
carbon 2 silica nanofibrous membrane for ultrafast gravity-driven oil 2 water separation. ACS Applied Materials &
Interfaces, 6, 9393 2 9401. Copyright r 2014 American Chemical Society.
mechanical strength, toughness and flexibility of the nanomembrane. The wettability was
intact at an elevated temperature up to 300 C in highly acidic or basic conditions. A
surface-coating with silicone oil for 30 mins made the composite membrane ultrahydrophobic with superoleophilic properties which was indicated by the water and oil
contact angles of 144.2 6 1.2 degrees and 0 degrees, respectively.
Wu et al. (2018) reported a facile and green route for fabricating a hydrophilic NF membrane that could effectively separate oil-in-water emulsions. This process is advantageous
as the nanomembrane could be reused and recycled. The hydrophilic polymer filtration
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10.4 Conclusions and future perspectives
191
membranes was synthesized employing in situ cocrosslinked polymer 2 nanoparticle networks by using hydrophilic poly(N-isopropylacrylamide-co-N-methylolacrylamide)
(PNIPAm-co-NMA) as the polymeric nanofiber matrix, and biobased nanoparticles, that
is, chitin nanowiskers (ChNWs) as the reinforcement and cocrosslinked hub. The resulting
cocrosslinked P(NIPAAm-co-NMA)/ChNWs nanofiber was structurally very stable with
uniform, smooth, continuous and bead-free nanofibers without any adhesion among the
adjacent nanofibers. This was attributed to the ability of the ChNWs to disperse homogeneously among the nanofibers. The random 3D nonwoven porous network obtained
due to dense entanglement of the components with each other was ideal for emulsion separation with a separation flux of 1100 2 1300 L/m2/h resulting in a separation efficiency of
.99.5%. Interestingly, for up to five cycles, the membrane could be reused and recycled
without any notable difference in its activity indicating its promising role in addressing oil
spills, industrial oily wastewater treatments and oil recovery.
10.3.6 Nanocatalysts
Various nanocatalysts have promising applications in the oil industry owing to their
high aspect ratio and unique catalytic properties. Metallic nanoparticles with unique optical, magnetic, electronic, and chemical properties were reported to offer better control of
chemical processes, like the Fischer-Tropsch process. Nanoscale metals like cobalt, iron,
nickel, and ruthenium can catalyze the series of chemical reactions involved in the aforementioned process responsible for converting carbon monoxide and hydrogen into liquid
hydrocarbons. Polyvinylpyrrolidone stabilized rhodium (Rh), ruthenium (Ru), platinum
(Pt), and cobalt (Co) tested for catalytic activity for the Fischer-Tropsch reaction revealed
that PVP-Co was remarkably active enhancing the reaction. Likewise, iron or cobalt nanoparticles dispersed in PEG also effectively catalyzed the Fischer-Tropsch reaction.
Interestingly, the catalyst could be recovered after the reaction due to the ferromagnetic
properties of iron nanoparticles. Similarly, carbon based nanocatalysts could significantly
reduce (4%) the high viscosity of heavy oil under microwave heating. Nanomaterials are
also used for downstream processing in oil industries. Engineered Co-Mo catalyst on
MCM-41 mesoporous materials facilitated the hydrodeoxygenation reaction associated
with pyrolysis that increased the heating value reducing the high oxygen content (Peng
et al., 2018). However, optimization is required for rationally employing nanocatalysts in
various processes in the oil industry.
10.4 Conclusions and future perspectives
Attractive physicochemical and optoelectronic properties have made nanoparticles one
of the most important types of materials for applications in managing oil spills and further
recovery and removal. Nanosensors are used for the detection of oil deposits underneath
the Earth’s crust by creating a detailed and accurate 3D/4D seismic view of the deep
wells. Likewise, nanofluids, which are mostly used during the drilling process, help in the
stabilization of the well bore, improve rheology and reduce filter loss. Nanofluids are
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10. Nanotechnological advances for oil spill management: removal, recovery and remediation
attractive materials that can alter the wettability of the porous surface, enhance thermal
stability and reduce viscosity of heavy oils. Another group of nanomaterials, called nanocomposites, are used for manufacturing the equipment used in oil industries. They reduce
fluid invasion into shales. Similarly, nanocoatings provide durability and long life to the
equipment by making them corrosion resistant. Additionally, they can be used for flooding applications as they improve rock surface properties. Nanoparticle impregnated membranes, popularly termed as nanomembranes, help in the separation of the drilled oil from
the impurities, CO2 capture and also in storage. Last, but not the least, nanocatalysts also
play a vital role in pyrolysis and associated processes that enhance both refining efficiency
and capacity. Also these nanomaterials can play an important role in the up-gradation of
heavy oil.
However, there are several factors that limit applications of nanotechnology in thee oil
and gas industry. Firstly, the nanomaterials are expensive, which is a major drawback in
their large scale application. Moreover, the activity of nanostructures is dependent on their
size and shape. Hence, it is critical to design optimized processes for the fabrication of
tailor-made nanoparticles with desired morphological features. On the other hand, toxicological aspects should be considered carefully before field applications as they may persist
for a long duration in the environment and affect the flora and fauna. The nanomaterials
may percolate through the soil and enter the ground water affecting its quality and potability. Similarly, the property of the nanostructures under salinity, temperature, and pH
should be checked before field applications. Careful investigation of the structural features
under simulated natural conditions will provide an insight to the overall fate of the nanostructures during field applications.
The degradation of the nanostructures after use should be checked to predict the time
required for their complete removing from the environment. Similarly, functionalization of
the nanomaterials should be rationally undertaken in order to ensure the safe and biocompatible nature of the nanoparticles before subjecting them to field applications.
Biologically synthesized nanoparticles can provide biocompatible nanoparticles for successful applications in the oil industry. In view of this background, a thorough investigation of the engineered nanomaterials should be conducted before they enter the oil
industry as a promising alternative for the management of oil spills, oil recovery, removal
and remediation.
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B. Physical processes
C H A P T E R
11
Carbon nanotube-based oil-water
separation
Tamanna Khandelia and Bhisma K. Patel
Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati, India
O U T L I N E
11.1 Introduction
195
11.2 Carbon nanotube-carbon-based
sorbent
196
11.3 Principles of oil-water separation
by carbon nanotube
196
11.4 Structure and synthesis of carbon
nanotube
197
11.4.1 Structure
197
11.4.2 Synthesis
198
11.5 Current applications: carbon
nanotube-based oil-water
separation
198
11.6 Future perspective
205
11.7 Summary
205
References
205
11.1 Introduction
The field of oil-water separation is highly significant as it has direct implications in solving
the problems of oil spilling, which is a serious threat to the ecosystem (Gupta & Tai, 2016).
The tremendous development of industries especially petrochemical and marine industries in
the past decades is the major cause of oil-spilling, thereby disturbing the ecosystem. Leakages
during storage and transportation of oil have caused many accidents all over the world (Xue,
Cao, Liu, Feng, & Jiang, 2014). Above this, the planned disposal of oily wastewater into water
bodies by mankind is very menacing. Oil-spill in water bodies is more dangerous than on
land as oil floats over water blocking large surface area of the water body, leading to the
death of many marine life and disturbing the marine ecosystem. Separation of oil-water emulsion is even more important, as emulsions are very stable and a challenging task for scientists
Advances in Oil-Water Separation
DOI: https://doi.org/10.1016/B978-0-323-89978-9.00019-7
195
© 2022 Elsevier Inc. All rights reserved.
196
11. Carbon nanotube-based oil-water separation
all over the world. Emulsions may be of various types, including oil-in-water (O/W) emulsion, surfactant stabilized or surfactant free and of various sizes (micrometer or nanometer).
Among many enormous oil spill incidents, the dreadful aftermath of the Persian Gulf
War oil spill incident in 1991 urges us to learn important lessons from it. Miserably, it was
not an accident but a filthy deed of mankind. Approximately, 4 million barrels of oil were
released into the northern Persian Gulf. The oil penetrated deep down, and it persists to
date, thereby affecting lives mercilessly. The adverse effects of oil-spill, particularly oilwater emulsion demands extensive research to be done in this field (Gupta & Tai, 2016).
Appreciatively, commendable research has been carried out in this field. Jiang et al. in
2004 first introduced the idea of combining both superhydrophobicity and superoleophilicity of a material for the separation of oil and water (Feng et al., 2004). They developed a
stainless steel mesh coated with an emulsion prepared using polytetrafluoroethylene as a
precursor and successfully separated diesel oil and water.
11.2 Carbon nanotube-carbon-based sorbent
The development of various carbon-based materials including carbon dots, graphene,
carbon aerogels, fullerene, carbon nanotubes (CNTs), carbon nanofibers among many
others have been widely explored in various fields like gas purification, wastewater treatment, oil-water separation, cleaning of drinking water, etc. Gupta, Dunderdale, England,
and Hozumi (2017), considering the economic and environmental aspects, the development of CNTs have shed a bright light on gloomy disasters caused by oil spillage and
industrial oily wastewater drainage. CNT was first discovered by Iijima and Ichihashi and
Bethune et al. independently in 1993 in carbon arc chambers. CNTs are generally chiral
and semiconductors with a moderate band gap, while a few achiral SW-CNT are metallic.
The superhydrophobic and superoleophilic property of CNT makes it an ideal tool for
oil-water separation. Moreover, CNT is laden with many distinguishing physicochemical
properties viz. high surface area, low density, chemical stability, excellent mechanical
properties, large pore volume, environment-friendliness and high sorption capacity. The
absorption capacity of CNT sponge is exceptionally high and ranges between 1550 times
their own mass and can be reused by repeated heating and mechanical squeezing.
11.3 Principles of oil-water separation by carbon nanotube
The theoretical aspect of oil-water separation revolves around the subject matter of contact angle (CA) θ. CA is the angle measured through the liquid, where the liquid-vapor
interface meets the solid surface. It gives a quantitative measurement of the wettability of
a surface via the Young equation:
γ 2 γ SL
cosθ 5 SV
γ LV
Here, γ SV, γ SL, and γ LV denote the interfacial tension between solid-vapor, solid-liquid
and liquid-vapor respectively as shown in Fig. 11.1.
B. Physical processes
11.4 Structure and synthesis of carbon nanotube
FIGURE 11.1
197
Contact angle (θ).
The value of CA categorizes a surface into hydrophilic, hydrophobic, and superhydrophobic. With the water CA (WCA) less than 90 degrees, a surface is defined as hydrophilic, when it is in between 90 and 150 degrees then it is hydrophobic and above 150
degrees it is superhydrophobic. The same description is applicable for all liquids including
oil. The phenomenon of non-wettability has been inspired by nature. Since time immemorial, the superhydrophobic nature of lotus leaves and butterfly wings have inspired
researchers all around the world. It is the topography and chemical composition of the
surface that imparts the superhydrophobic nature to a surface. Artificial superhydrophobic
surfaces have been developed by introducing roughness (chemical modification) to them.
In the scenario of oil-water separation, the idea of combining the property of superhydrophobicity and superoleophilicity is a boon to mankind and the idea has been implemented
very successfully. Since the major problem faced by human beings is the spillage of oil in
water or oil-water emulsion; materials with both the properties combined, have the potential to absorb oil besides repelling water.
11.4 Structure and synthesis of carbon nanotube
11.4.1 Structure
As the name suggests, CNT has cylindrical structure (infinitely long) with a diameter in
the range of 0.440 nm. It has a hollow one-dimensional structure with rolled up graphene layers; graphene has a two-dimensional layered structure with carbon atoms
arranged in a hexagonal manner. The diameter of CNT is constrained to a narrow range
as the carbon-carbon bond length is fixed. CNT may be both single walled CNT (SWCNT)
or multiwalled (MWCNT). In MWCNT the SWCNTs are nested together bonded by weak
Van der Waals interaction in a tree-ring like fashion. There are two main configurations of
CNT: (1) Zigzag: In the zigzag configuration, a zigzag path can be defined along a direction perpendicular to the length of the CNT. The path turns 60 degrees alternatively left
and right, after stepping through each bond (Fig. 11.2A). (2) Armchair: In an armchair configuration an armchair type of path can be encircled along the diameter of the CNT. The
path takes two left turns of 60 degrees followed by two right turns every four steps
(Fig. 11.2B).
The large surface area of CNT, combined with its oleophilic properties makes it a perfect fit for oil-water separation. The typical nanostructure of CNT and the carbon-carbon
B. Physical processes
198
11. Carbon nanotube-based oil-water separation
(A)
FIGURE 11.2
(B)
(A) Zigzag configuration (B) Armchair configuration.
bond strength imparts it exceptional properties including electrical conductivity and semiconductivity, tensile strength, thermal conductivity. It is because of these properties, CNT
has gained remarkable position in optics, electronics, nanotechnology and many other
applications in materials chemistry. In addition, the structure of CNT can be chemically
modified for superior results. Functionalization of CNT improves the solubility of CNT in
various solvents.
11.4.2 Synthesis
CNTs can be synthesized by various techniques including arc discharge, laser ablation,
chemical vapor deposition (CVD) and high pressure carbon monoxide disproportionation
(Prasek et al., 2011). Among these technique, the CVD is much popular as this method has
control over the length, diameter and morphology of the CNT together with producing
high yields. CVD may be assisted by various sources including oxygen assisted CVD,
radiofrequency assisted, hot filament assisted CVD, water-assisted CVD, microwave
plasma enhanced CVD, thermal and plasma-enhanced CVD (PECVD). Transition metal
catalysts like Ni, Fe, or Co are commonly used in the technique. The role of these catalysts
in CVD is to decompose the carbon source through the energy of plasma irradiation in
PECVD, heat in thermal CVD, etc. The carbon sources which have been most commonly
used here are hydrocarbons- ethane, methane, ethylene, acetylene, xylene, isobutane, and
ethanol.
11.5 Current applications: carbon nanotube-based oil-water separation
In order to increase the efficiency of CNTs, proper functionalization of the CNT wall is
required. This lowers the surface energy and imparts proper roughness to CNTs.
Superhydrophobic CNT films may be produced by the following two main approaches:
(1) Adsorption of low surface energy chemicals onto the CNT surface (bounded by Van
der Waals or π-π interactions) (2) Covalent attachment of hydrophobic groups. CNTs are
used to fabricate many membranes, as the CNTs impart tensile strength, electrical and
thermal conductivities, etc. to the membrane. To date, many applications of CNTs have
been made for the successful separation of oil-water mixtures and emulsions (Bu et al.,
2017; Hu, Li, & Dong, 2018; Peng & Guo, 2016; Zhang et al., 2016).
B. Physical processes
11.5 Current applications: carbon nanotube-based oil-water separation
199
In 2013, Wang et al. coated polyurethane (PU) sponge with the superhydrophobic and
superoleophilic CNT and polydimethylsiloxane (PDMS) (Wang & Lin, 2013). PU sponge
has been widely used in the field of oil-water separation as it is easily available commercially and has the ability to absorb both oil and water. Fabrication of the sponge with various materials can tune its absorption property according to requirements. Upon
fabrication of CNT/PDMS layer onto PU sponge, the wettability of PU sponge changed
from hydrophilic to superhydrophobic nature; thereby repelling water and absorbing oil
and organic solvents. Owing to the robust nature of the prepared CNT/PDMS-PU sponge,
it can be used in conjugation with a vacuum pump for simultaneous removal of oil from
water. The CNT/PDMS-PU sponge could separate micrometer sized surfactant-free waterin-oil (W/O) emulsions with very high efficiency (99.97 wt.%). The method of preparation
of the CNT/PDMS-PU sponge is as follows: A dip-coating method was used to deposit
CNT/PDMS suspension on the PU sponge, which was then heated at 120 C in an oven.
The prepared CNT/PDMS-PU sponge had a WCA of 162 6 2 degrees (superhydrophobic)
and CA of n-hexane, n-hexadecane, and gasoline were all close to 0 degrees (superoleophilic). The fabricated sponge could separate oil up to 35,000 times of its own weight.
In 2013 Jin et al. reported a method of separating both micrometer and nanometer sized
surfactant stabilized and surfactant free W/O emulsions via a free standing ultrathin
SWCNT network film (Shi et al., 2013). The film could separate W/O emulsion with a flux
of about 100,000 L/m2/h/bar and separation efficiency of 99.95 wt.%. The procedure of
synthesis is as follows: The ultrathin SWCNT film was prepared via vacuum filtering of
the SWCNT suspension through a cellulose ester (MCE) filter, followed by releasing it
from the filter. The thickness of the film could be controlled by the volume of the SWCNT
suspension which was to be filtered. The prepared freestanding SWCNT was used as a filtering tool for the separation of the W/O emulsion. It was placed on a ceramic membrane
and the W/O emulsion was filtered via suction. The film possessed high mechanical
strength and good flexibility. When the W/O emulsion was allowed to pass through the
SWCNT film oil droplets permeated through the film, leaving behind the water content,
thereby de-emulsifying the emulsion.
In 2015, Jin et al. focused on separating O/W nanoemulsions. Nanoemulsions or nanosized oil provides a new challenge to scientists as they cause serious damage to the environment and public health (Gao, Zhu, Zhang, & Jin, 2015). They fabricated SWCNTs with
polydopamine (PD) and polyethyleneimine (PEI) to prepare a SWCNT/PD/PEI composite
membrane of nanometer sized pores. The thickness of the composite film is 158 nm and
has a pore size of B10 nm. The film can separate O/W nanoemulsions in an ultrafast manner with a permeation flux of # 6000 L/m2/h/bar. The film is stable in adverse pH conditions, which makes it suitable for treating O/W nanoemulsions in all pH ranges. The
procedure of synthesis of SWCNT/PD/PEI composite film is as follows: Initially, a PD
layer was coated on SWCNT to prepare the SWCNT/PD dispersion. The thickness of the
PD layer upon SWCNT is controlled by the reaction time. The pore size of the SWCNT/
PD composite film is 10 6 5 nm and a thickness of 154 nm. The SWCNT/PD film was further immersed in a solution containing PEI to graft a layer of PEI onto the SWCNT/PD
composite film to produce the final SWCNT/PD/PEI composite film. The final thickness
of the SWCNT/PD/PEI film is 158 nm. The WCA of the raw SWCNT membrane is 120
degrees whereas the prepared composite film displays superhydrophilic and underwater
B. Physical processes
200
11. Carbon nanotube-based oil-water separation
superoleophobic property. The film has a WCA of nearly zero and an oil CA of 162
degrees.
The same group in 2015, reported a photothermal responsive, SWCNT membranebased oil-in water separation technique (Hu, Gao, Ding, et al., 2015). The pore sizes of the
membrane were controlled by light. They prepared an Au nano-rod (ANR)/poly(N-isopropylacrylamide-co-acrylamide) (pNIPAm-co-AAm) cohybrid SWCNT membrane. The
pNIPAm-co-AAm layer imparts a hydrophilic property to the SWCNT network film. The
pNIPAm based copolymer also acts as a chemical valve for the membrane which is triggered by heat, thereby tuning the pore radius of the membrane. On the other hand, Au
nanoparticles add a photothermal response to the membrane. The procedure for synthesis
is as follows: The photothermal-responsive nanoporous membrane was prepared via three
main steps: (1) Coating of the SWCNT with PD. (2) Functionalization of the PD modified
SWCNT with pNIPAm-co-AAm. (3) Decoration of prefunctionalized SWCNT with ANR.
The mechanism of O/W separation is based on the size-sieving effect and the wettability
of the membrane. It is the underwater oleophilicity, hydrophobicity and the nanometer
sized pores that brought about the separation. The membrane displayed a separation efficiency of . 99.99%.
In 2014, Wang et al. also fabricated a superhydrophobic and superoleophilic PU with
CNTs for discriminatory removal of oil from water (Wang et al., 2015). Apart from superhydrophobicity and superoleophilicity, the prepared sponge had marvelous properties
including excellent mechanical strength and elasticity, stability in a temperature range of
50 C to 100 C and selective absorption of oil with a sorption capacity up to 34.9 times of
its own weight. A simple squeeze removes all the absorbed oil and the material may be
reused for up to 150 times with intact efficiency. The procedure for synthesis is as follows:
Being inspired by the adhesive property of dopamine, they coated CNTs with dopamine
film; the dopamine modified CNTs (CNT-PDA) were then anchored on PU sponge
through the self-polymerization of dopamine (PDA). Further, a chemical reaction was carried out where the PDA film was conjugated to octadecylamine to give the resultant
sponge.
In 2014, Chen et al. developed a CNT based material for separation of oil/water emulsions (Gu et al., 2014). It is well known that the separation of oil droplets with small diameters (in the range of μm and nm) as in surfactant stabilized oil-water micro emulsion is
a challenging task and materials with better efficiency are highly desired. The salient features of CNTs attracted them to modify CNTs by covalently linking superhydrophobic
polystyrene (PS) to it thereby preparing PS/CNT hybrid membrane. The prepared PSCNTs membrane could be reused and had a sorption capacity of up to 270 times its own
weight. The hybrid membrane could separate oil-water emulsion with very high flux
(5000 Lm22h21bar21). The synthesis procedure is as follows: A uniform layer of CNTs ethanol dispersed solution was spread over Al2O3 membrane. The superhydrophobic PS
were allowed to covalently attach on the -OH or -COOH functional groups on CNTs via
self-initiated photo grafting and photo-polymerization. The prepared hybrid membrane
drastically changed the WCA of CNT from 62 to 152 degrees.
In 2015, Jin et al. also developed an ultrathin superwetting bilayer membrane based on
SWCNT for a pressure responsive separation of oil-water emulsions (Hu, Gao, Zhu, et al.,
2015). The membrane exhibits asymmetric wettability toward the continuous phase and
B. Physical processes
11.5 Current applications: carbon nanotube-based oil-water separation
201
the dispersed phase throughout the membrane thickness. Simple modulation of the
applied pressure brings about the separation of surfactant stabilized W/O and O/W emulsions. The pressure driven separation was carried out in such a manner that the applied
pressure allows the permeation of the continuous phase selectively; the pressure is such
that Pcontinuous phase (intrusion pressure of continuous phase) , Papplied , Pdispersed phase
(intrusion pressure of dispersed phase). The bilayer membrane has emerged as a very efficient tool for practical use as they exhibit ultrahigh permeation flux and separation efficiency. The procedure for synthesis is as follows: An ultrathin layer of the PD was coated
over SWCNTs which was further fabricated onto a mixed cellulose ester filter substrate
via a vacuum filtration technique. In order to avoid any fouling issues, the underlying
MCE substrate was dissolved in anhydrous acetone. The free standing SWCNT/PD
bilayer was then transferred to a chemically inert porous ceramic membrane.
In 2015, the group of Chen et al. also proposed a controlled functionalization of CNTs
for efficient separation of oil-water mixtures (Gu, Xiao, Huang, Zhang, & Chen, 2015).
They were inspired by the natural water repellent properties of the lotus leaf. Thorough
research in this area led them to modify the -OH functionalized CNTs with fluorine
bearing organosilanes. The strong Si-O bond motivated them to attach 1H, 1H, 2H,
2H-perfluorodecyltriethoxysilane (PFDTS) onto the -OH functionalized CNTs. They successfully separated W/O emulsion using this PFDTS/CNT hybrid. A brief discussion of
the synthesis of the PFDTS/CNT hybrid: On simply mixing CNT and PFDTS in the proper
ratio, PFDTS spontaneously forms layers onto CNTs. It is the ratio of PFDTS: CNT which
determine the characteristics of the hybrid material. They successfully separated W/O
emulsion which were surfactant stabilized with high efficiency even under adverse conditions including all temperature and pH ranges. Also, the PFDTS layer imparts a flame
retardant nature to the PFDTS/CNT hybrid.
In 2016, Chen et al. focused on the simultaneous separation of O/W emulsions and
removal of harmful bacteria from water (Gu et al., 2016). They utilized the bactericidal
effect of Ag nanoparticles (Ag NPs) which has been known since ages. They combined the
antibacterial property of Ag NPs and the superhydrophilic-superoleophobic property of
polyacrylic acid (PAA) grafted CNTs to reach their desired goal. The Ag/PAA-CNTs
exhibited superhydrophilicity and underwater superoleophobicity in a three phasic (oil/
water/solid) system and has a very high flux. The procedure for synthesis is as follows:
The preparation involves a two-step procedure: (1) Firstly, polyacrylic acid (PAA) was
grafted upon CNTs via a free radical polymerization using benzoyl peroxide as the radical
initiator. (2) Next, Tollens reagent was added to the PAA/CNTs suspension under gentle
stirring to reduce the Ag NPs on the surface of PAA-CNT. (3) The final Ag/PAA-CNT
membrane was obtained by filtrating it on the hydrophilic PVDF membrane. The prepared
membrane could separate surfactant stabilized W/O emulsion with a flux of 3000 L/m2/
h/bar. The reported method is a new technique and a potential tool for oil-spill cleanup.
In order to check the bactericidal effects of the Ag/PAA-CNT membrane, they performed
a disk diffusion experiment. Ag NPs were expected to inactivate the microorganism’s cells
by rupturing their cell membrane and inhibiting DNA replication. It was clearly visible
that the bacterial growth was inhibited. Also, morphological studies of the bacteria were
carried out before and after incubation with the Ag/PAA-CNT membrane, which clearly
reflects the bactericidal activity of the Ag/PAA-CNT membrane.
B. Physical processes
202
11. Carbon nanotube-based oil-water separation
In 2016, Sue et al. developed a simple method of fabricating MWCNTs with long chain
alkyl-pyrenes for highly efficient oil-water separation (Huang et al., 2016). With the goal of
synthesizing a superhydrophobic and superoleophilic film in a very simple and commercial way, they ended up in noncovalent functionalization of MWCNT sidewalls. They synthesized alkyl-pyrene by the classic aldehyde-amine coupling reaction which was further
purified by recrystallization from ethanol. The electron rich π-stacked pyrene rings were
covalently absorbed on the sidewalls of MWCNT in organic solvents. The long alkyl chain
attached to the pyrene rings added roughness to the surface, thereby reducing the surface
energy of the MWCNT. The WCA of the resulting MWCNT film increased to 158 6 2
degrees, leading to a superhydrophobic and superoleophilic film. The film allows oil to
pass through it while repels water. In the process, they tried to avoid complex synthetic
procedure including acid oxidation of the CNTs (which damages the CNTs) and multiple
step functionalization.
In 2017, Montemagno et al. developed a gas-switchable CNT/PDEAEMA hybrid membrane which could reversibly switch from hydrophobic to hydrophilic upon absorption of
carbon dioxide and nitrogen gases respectively, for the separation of oil and water
(Abraham, Kumaranab, & Montemagno, 2017). The inspiration behind their discovery was
the voltage dependent potassium channel of the biological cell membranes. Both carbon
dioxide and nitrogen gases being “greenhouse” gases need to be utilized effectively, in
order to cut down their detrimental effects on the environment (global warming). In this
regard, CO2 needs special attention as its emission is increasing at an alarming rate. They
coated CNT walls with an ultrathin film of poly(N,N-diethylaminoethylmethacrylate)
(PDEAEMA). The PDEAEMA layer acts as a chemical valve, triggered by CO2 or N2
which changes its conformation to adjust the pore sizes of the membrane and selectively
manages the permeability and selectivity. Synthesis of the hybrid membrane: Initially,
they functionalized CNTs with carboxylic acid groups. The carboxylic acid derived CNTs
were further functionalized with 2-hydroxyethyl-2-bromoisobutyrate to develop a CNT
grafted atom transfer radical polymerization initiator. This was followed by the development of PDEAEMA brushes by mixing N,N0 -diethylaminoethyl methacrylate (DEAMA) in
a methanol solution (4:1) and CuBr, PMDETA and a CNT macroinitiator (0.05%
DEAEMA) at 80 C for 16 h to yield the CNT/PDEAEMA hybrid membrane. The WCA of
the hybrid membrane drastically changed from 113 6 5.0 degrees to 10 6 8.0 degrees upon
exposure of the membrane to CO2 gas; whereas on passing N2 gas the original WCA was
obtained. This clearly indicates that CO2 turns the membrane to hydrophilic.
In 2018, Qiu et al. developed an underwater superoleophobic membrane to separate
O/W emulsion (Yue, Zhang, Yang, Qiu, & Li, 2018). They were inspired by the underwater hydrophilic and superoleophobic property of the fish scales, which helps the fish to
remain clean in water. Various hydrophilic materials such as hydrogel, cellulose or metal
oxides like ZnO, TiO2 have been studied in this respect, but there were some shortcomings. Polymers like cellulose or hydrogel were water soluble whereas metal oxides were
easily corroded, which made them unfit for oil-water separation. The exceptional thermal,
mechanical, and electrical properties of CNTs have attracted them to use it for oil-water
separation. CNTs have been bestowed with excellent properties including low density and
high porosity, which makes them a perfect fit for oil-water separation. Moreover, CNT can
be easily fabricated on a surface to form a film. They chose MW-CNT over SW-CNT
B. Physical processes
11.5 Current applications: carbon nanotube-based oil-water separation
203
because of the high price of SW-CNT, which would encumber their large scale applications. They fabricated the dispersed MW-CNT on a MnO2 nanowire suspension through a
sand-core filtration system to develop the MW-CNT/UL-MnO2-NWs hybrid membrane.
The method of preparing the hybrid membrane is as follows: Initially the dispersed
MW-CNT suspension was prepared by treating the MW-CNTs with HNO3 at 140 C for
4.5 h, which was followed by sonication. The UL-MnO2-NWs were obtained by a hydrothermal route. The dispersed MW-CNTs and UL-MnO2-NWs were then mixed together
and vacuum filtered to obtain the final (MW-CNT/UL-MnO2-NWs) membrane. The membrane could separate both surfactant-stabilized and surfactant free O/W emulsions with
permeation up to 4900 L/m2/h/bar and a separation efficiency greater than 99.7%. The
MW-CNT/UL-MnO2-NWs membrane had a WCA of 0 degree and displayed underwater
superoleophobicity with an oil CA of 152 degrees.
In 2018, Xu et al. also focused on the separation of surfactant stabilized O/W emulsions
(An, Yang, Yang, Wu, & Xu, 2018). They have reported that it becomes difficult for a general
hydrophilic or hydrophobic membrane for effective separation of O/W or W/O emulsion.
They took help of the Janus membrane, which is a special type of 2-dimensional membrane
having two or more distinct physical properties. The two different property allows the Janus
membrane to act differently on each side in different conditions. It could separate both W/O
and O/L emulsions, on the basis of its sieving effect. For separating O/W emulsion, the
hydrophilic side of the Janus membrane is set upwards and the lower hydrophobic layer easily allows water to pass through it; whereas for separating the W/O emulsions, the membrane
can simply be flipped to make the hydrophobic side face upwards. But there is a chance of
accumulation of the rejected oil which decreases the efficiency of the membrane. In order to
overcome this problem, the pore size of the membrane can be made sufficiently large to allow
the permeation of oil through it. Also, the thickness of the hydrophilic layer needs to be precisely managed. However, complicated preparation steps lead to uncontrolled thickness of the
layer. Further, to get rid of this problem, they fabricated the hydrophilic layer of the Janus
membrane with positively/negatively charged CNTs, which could tune the surface wettability
and the de-emulsifying feature of the Janus membrane. Fabrication of the membrane with
CNTs allows frictionless movement of oil or water through the membrane. The prime reason
of the positive charge of CNT is to demulsify the emulsions which are stabilized by negatively
charged surfactants before the penetration of oil and vice versa. Also, the thickness of the
hydrophilic layer can be tuned easily by regulating the concentration of CNTs in aqueous dispersion. The separation efficiency of the membrane reaches its maximum as the WCA and the
underwater oil CA (UOCA) are around 90 degrees on the CNT-coated surface. The prepared
membrane could separate both light oil and heavy oil from O/W emulsion.
In 2018, Freger et al. took advantage of the electrical conductivity of CNTs for oil-water
separations (Tankus, Issman, Stolov, & Freger, 2018). They converted the CNT mats from
hydrophobic to hydrophilic via electrooxidation (EO). The wetting behavior of the CNT
mats was irreversibly changed to allow the permeation of water and rejection of oil. The
electro oxidation of the CNTs under anodic potential generates oxygen containing polar
groups in a similar way as graphene is converted to graphene oxide (GO) upon oxidation.
Here, MWCNT is preferred over SWCNT as MWCNT is less vulnerable to electrotreatment preserving its mechanical and electrical characteristics. The membrane allows complete separation of oil-water mixtures (including surfactant stabilized oil-water emulsions).
B. Physical processes
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11. Carbon nanotube-based oil-water separation
The EO preserves the morphology and porosity of the membrane. The procedure for synthesis is as follows: The electro oxidation of CNT mat was performed in situ within an airpressurized Amicon filtration cell fitted with a platinum counter. In order to overcome the
competition with water-splitting, high-voltages were required to be applied.
In 2019, Lu et al. designed an extremely durable and self-healing superhydrobhobic
MWCNT film for efficient separation of oil-water emulsion (Ye et al., 2019). They chose
MWCNT over SWCNT as MWCNT has greater stability and diameter compared to
SWCNT. Also, it is cheaper as compared to SWCNT. They modified the MWCNT layer by
fabricating it with a polydivinylbenzene (PDVB) layer followed by a 1-H,1-H,2-H,2-H-perfluorooctyltriethoxysilane (POTS) layer. PDVB was chosen as it is easy to prepare,
stable under a range of conditions and possesses nanoporous superhydrophobic properties. The POTS layer was chosen for its self-healing property, which enables the film to
recover from damages and increases its durability. The self-healing mechanism involves
migration of an alkyl chain in the presence of water. The procedure for synthesis is as follows: Initially, a free standing MWCNT film was prepared by attaching the MWCNT film
to a copper mesh. This was followed by: (1) PDVB modification of the film: The PDVB
layer was introduced via a solvothermal route. The solvothermal reaction cross links and
polymerizes DVB monomer to form a polymer network under the action of AIBN (initiator). (2) POTS modification of the layer: The self-healing, low energy layer of POTS was
introduced upon the PDVB layer. The POTS modification was carried out via CVD. The
prepared MWCNT film showed a WCA of 151.4 6 0.7 degrees, whereas oil was absorbed
within 100 Ms. This confirms the surface to be superhydrophobic and superoleophilic.
In 2020, Feng et al. developed a CNT/poly(N-isopropylacrylamide) modified membrane for
the separation of double emulsions (Qu et al., 2020). Double emulsions (oil-in-W/O emulsion
or W/O-in-water emulsion) are much more difficult to separate as compared to simple emulsions (oil in water or water in oil emulsions). They combined the photo-thermal conversion of
CNTs and the thermal isomerization properties of poly(N-isopropylacrylamide) (PNIPAAm)
and fabricated them to a poly(vinyldenefluoride) membrane to create an IR responsive superwetting switchable material. Both PNIPAAm and CNTs being cheap reagents, proved to be an
economical selection. The prepared sandwich structured PNIPAAm/CNT@PVDF material
could separate different types of emulsions simultaneously, thereby saving energy and simplifies the separation process. Theoretical evaluation of wettability reveals that the phenomenon
is guided by intermolecular and intramolecular hydrogen bonds. Initially, the surface temperature of the PNIPAAm/CNT@PVDF layer was lower than that of the lower critical solution
temperature (LCST), and the N-H and C 5 O groups of PNIPAAm molecular chain formed
intermolecular hydrogen bonds with water molecules, making the membrane superhydrophilic. Upon exposure of the material to IR (800 nm), the CNTs generated a large amount of heat
(ST . LCST) and the molecular chain of PNIPAAm formed intramolecular hydrogen bond,
making the material hydrophobic. After removing the IR source, the material returned to its
original hydrophilic state. The procedure of synthesis is as follows: The PNIPAAm/
CNT@PVDF was prepared via a twostep procedure. Initially, a CNT layer was dispersed over
a pre-treated PVDF substrate via a hydrothermal reaction. Further, the CNT layer was fully
covered by PNIPAAm to form the required sandwich structured membrane. The prepared
PNIPAAm/CNT@PVDF material exhibited WCA of 10.3 degrees whereas upon exposure to
IR source, the WCA changed to 142.4 degrees (superhydrophobic).
B. Physical processes
References
205
11.6 Future perspective
CNT based oil-water separation holds immense potential for practical use. With the
ongoing usage, many challenges of the future can be successfully dealt with proper application of CNTs. CNTs have high flux rates compared to the conventional membranes,
which makes it a perfect weapon for any accidental oil spillage in future.
11.7 Summary
Carbon-based carbon nanotube has flourished as a remarkable tool for oil-water separation in today’s revolutionary world. Being environmentally friendly and biodegradable, it
has been widely accepted. SWCNTs and MWCNTs can either be coated on polymer
sponge or functionalized for efficient oil-water separation. The superhydrophobic and
superoleophilic property of CNTs along with its reusability makes it a superior entity. The
CNT mesh or CNT grafted material can absorb oil up to 37,000 times of its own weight.
This field demands more research to be done, for smarter and convenient separation of
oil-water mixtures and emulsions. In this book chapter, recent applications and developments of CNT as a tool for oil-water separation have been briefly summarized.
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B. Physical processes
C H A P T E R
12
Nanocoated membranes for oil/water
separation
Karun Kumar Jana1, Avijit Bhowal1,2 and Papita Das1,2
1
School of Advanced Studies on Industrial Pollution Control Engineering, Jadavpur University,
Kolkata, India 2Department of Chemical Engineering, Jadavpur University, Kolkata, India
O U T L I N E
12.1 Introduction
208
12.5.1 Surface morphology
12.5.2 X-ray photoelectron
spectroscopy
12.5.3 FTIR
12.2 Nanocoated membrane
technology
209
12.2.1 Organic-based membranes
209
12.2.2 Inorganic-based membranes 210
12.3 Fundamental principles behind oil/
water separation behavior
210
12.3.1 Superhydrophobic-superoleophilic
membrane
211
12.3.2 Superhydrophilic-superoleophobic
membrane
212
12.3.3 Underwater superoleophobicity
membrane
213
12.4 Current application of membranes in
oily wastewater treatment
213
12.4.1 Zwitterionic membranes
213
12.4.2 Biomimetic thin membranes 215
12.5 Morphology and structure
Advances in Oil-Water Separation
DOI: https://doi.org/10.1016/B978-0-323-89978-9.00008-2
216
216
217
218
12.6 Wetting properties
218
12.7 Mechanical strength
219
12.8 Antifouling method
220
12.9 Separation performance of
membranes for the oil-in-water
mixture
220
12.10 Summary
223
12.11 Future perspective
223
Acknowledgement
224
Conflict of interest
224
References
224
207
© 2022 Elsevier Inc. All rights reserved.
208
12. Nanocoated membranes for oil/water separation
12.1 Introduction
During industrial or other oil-related activities processing, (e.g., paper, textile, metalworking, food processing, and pharmaceutical), a mixture of oil-water is produced in our
daily life (Abadi, Sebzari, Hemati, Rekabdar, & Mohammadi, 2011; Cheryan &
Rajagopalan, 1998; Ezzati, Gorouhi, & Mohammadi, 2005; Kong & Li, 1999; Shannon et al.,
2008). Therefore, several studies have also been recently introduced on the improvement
of effectively distinct the oil from water-oil mixtures for worldwide oil spillage recovery
and pollution control. To remove emulsified oil, dispersed oil, and free oil (Bengani-Lutz,
Zaf, Culfaz-Emecen, & Asatekin, 2017; Huang, Ras, & Tian, 2018; Painmanakul, Sastaravet,
Lersjintanakarn, & Khaodhiar, 2010) from water, many methods tested so far. Various conventional water treatment processes, such as absorption, chemical coagulation, air flotation, biological oxidation, and gravity separation (Cheryan & Rajagopalan, 1998; Kusworo
& Utomo, 2017; Peng, Guo, Wen, Yang, & Guo, 2017; Xue, Li, Li, Zhu, & Guo, 2017) are
utilized to remove much smaller droplet size emulsified oil. On the other hand, dispersed
and free oil can be cleaned up mechanically (Ivshina et al., 2015). Moreover, the efficiency
of using freshwater could be improved by recycling oily wastewater (Chakrabarty,
Ghoshal, & Purkait, 2008).
Membrane-based materials bearing superior wettability have received more attention in
oily wastewater treatment fields from both private industry and academia. The operation of
the membrane is very simple, a low defect rate, fouling resistance, high separation efficiency,
can be prepared without additional agents and chemicals (Padaki et al., 2015). Ceramic membranes (Ashaghi, Ebrahimi, & Czermak, 2007), polymeric membranes (Salahi, Gheshlaghi,
Mohammadi, & Madaeni, 2010), mixed-matrix membranes (Wan Ikhsan et al., 2018), and biomimetic thin membranes (Wang, Liang, Guo, & Liu, 2015) are the famous forms of membrane
technology for separating oil from oily water because of their capability to well eliminate the
droplets of oil from water vis-à-vis recent conventional technologies (Ong, Lau, Goh, Ng, &
Ismail, 2014). Membrane separation techniques are one of the most promising methods for an
extensive range of oil/water mixtures. Nevertheless, one of the key problems which arise in
the separation industries is membrane fouling. When organic, inorganic, and colloid particles
are physically adsorbed into the membrane pores or deposited membrane surface with cake
formation, this reduces permeation flux permanently and shortens the life of the membrane
(Obaid, Tolba, et al., 2015; Wei, Qi, Gong, & Zhao, 2018). To avoid the fouling problems,
researchers have developed some alternative new nanohybrids membrane (Karimnezhad,
Rajabi, Salehi, Derakhshan, & Azimi, 2014) and bio-inspired superwetting membrane (Yang
et al., 2017) that will lend the material looked-for antifouling qualities, such as hydrophilicity,
self-cleaning, photodegrading, and photocatalytic properties. Back-washing, chemical cleaning,
or hydraulic cleaning drops reversible fouling, whereas irreversible fouling arises when the
foulant is chemisorbed by the pores of the membrane surface causes the flux to be enduringly
reduced (Bhattacharya & Misra, 2004; Vasanth, Pugazhenthi, & Uppaluri, 2013).
Conventional nanohybrid membranes, nanometer dimension fillers having high surface
areas fall into one of the four significant classifications: (1) organic material; (2) inorganic
material; (3) hybrid material, and (4) biomaterial with two or additional material types. To
date, a variety of advanced nanomaterials could be resolved the issues involving water
B. Physical processes
12.2 Nanocoated membrane technology
209
quality, particularly in cleaning up oil spills because of their oleophilic and hydrophobic
characteristics (Campos, Oliveira Filho, Nobreg, & Sant’Anna, 2002; Feng & Jiang, 2006;
Nasrollahi, Aber, Vatanpour, & Mahmoodi, 2019; Zhang & Seeger, 2011). Advances in
engineering and nanoscale science propose that zinc oxide nanostructure coated membrane is one of the key points for separation technologies because they facilitate the important enhancement of the superhydrophilicity, underwater superoleophobicity, and
excellent separation ability for oil/water separation application concerning commercial
glass fiber membrane (Chen & Xu, 2013; Zhu, Tu, Wee, & Bai, 2014).
Porous or meshes superhydrophobic-superoleophilic membranes has an oil contact angle
(OCA) near 0 degrees and water contact angle (WCA) has beyond 150 degrees can effectively discrete the oil from water-in-oil emulsions by repelling water whereas let oil passes
through a membrane (Xue et al., 2011). On the other hand, a superhydrophilic-underwater/
superoleophobic membrane is appropriate to treat a variety of oily wastewater, here to let
water permeate from the membrane surface and prevent the oil (Darmanin & Guittard,
2014). Typically, superhydrophilic/superoleophobic (i.e., water removing) or superhydrophobic/superoleophilic (i.e., oil removing) are special kinds of wettability materials, can
selectively be dispersed and separate oil or water (Pernites, Ponnapati, & Advincula, 2011).
While some smart responsive oil-water separation materials having switchable special wettability facilitate both “water-removing” and “oil-removing” methods.
12.2 Nanocoated membrane technology
Nano-coated membranes with nanoscale pores are used with the resolution mainly the
removal of contaminants for example biological, physical, and chemical from drinking
water (Humplik et al., 2011; Sorribas, Zornoza, Téllez, & Coronas, 2014; Yin & Deng,
2015). Many different types of nanometer-size filler having high surface area and their
oleophilicity have become a chief point, which led to the production of membranes with
high permeation flux and “oil-removing” property. Engineered nanoporous membranes
having pore size lies between 1 and 100 nm are being explored to enhance the thermal stability, mechanical strength, higher water flux compared with other conventional membranes (Zhang et al., 2012; Zhao et al., 2011). The membranes can be classified into two
types depending on their materials and operating temperature.
12.2.1 Organic-based membranes
Organic membrane fabrication technology and polymer choice depend on a variety of
factors, including stereoisomerism, chain interactions, chain rigidity, and functional group
polarity (Abraham, Kumaran, & Montemagno, 2017; Prince et al., 2016; Saadati & Pakizeh,
2017). It is significant to determine what kind of polymer or membrane is most appropriate for their practical application in oily wastewater treatment. Generally, the polymeric/
organic membranes consist of two kinds of materials synthetic and natural polymers.
Samples of synthetic polymers, for example, poly(vinylidene)fluoride (PVDF), poly(ethylene terephthalate), polycarbonate, and polyacrylonitrile (PAN) whereas cellulose, wool,
and rubber are made of natural polymers (Jana et al., 2015; Jana, Lue, Huang, Soesanto, &
B. Physical processes
210
12. Nanocoated membranes for oil/water separation
Tung, 2018; Saxena et al., 2020; Tiwari, Jana, Singh, Avasthi, & Maiti, 2011). At present,
polymeric membranes (both hydrophilic and hydrophobic) alter the successful separation
performance in the treatment of oil-water mixture. Hydrophilic membranes display superior antifouling properties vis-à-vis hydrophobic membranes presumably due to the permit
water droplets toward transfer from side to side the membrane and prevent oil droplets
(Rahimpour & Madaeni, 2007). In contrast, hydrophobic material surfaces resist water and
permit droplets of oil easily, and it mainly shows fouling problems (Feng, Zhang, et al.,
2004). On the way to progress separation performance of the organic membranes including
separation efficiency, electrochemical and antifouling properties, engineered nanoparticles
are of the range of nanometer-scale such as metal oxides Al2O3, TiO2, SiO2, ZnO (Chena
et al., 2018; Vatanpour, Madaeni, Moradian, Zinadini, & Astinchap, 2012; Yi et al., 2011;
Yu, Xu, Shen, & Yang, 2009), carbon-based materials carbon nanofibers, carbon nanotube,
and graphene (Ao et al., 2017; Jana, Patel, Rana, & Maiti, 2014; Moslehyani, Ismail,
Othman, & Matsuura, 2015) are usually incorporated into the membrane matrix.
Numerous techniques have been used to prepared hybrid systems regarding interfacial
polymerization (Zhao et al., 2012), phase inversion (Akin, Zor, Bingol, & Ersoz, 2014),
cross-linking (Deng et al., 2019), electrospinning (Asmatulu, Ceylan, & Nuraje, 2011), melt
route (Jana et al., 2016), solution casting (Tiwari et al., 2013), and chemical grafting (Jana,
Ray, Avasthi, & Maiti, 2012).
12.2.2 Inorganic-based membranes
Researcher attempts have focused on developing inorganic membranes made of materials such as various oxides (alumina, titania, zirconia), ceramic, silica, carbon, zeolite, and
metals for example silver, palladium and their alloys for aimed at increasing fouling resistance, sustainable water purification, and captivating permeation flux for the period separation of oil-in-water mixture (Lin, 2006; Sun et al., 2018). Among different commercial
inorganic membranes, porous membranes have driven significant attention in recent years.
Microporous inorganic membranes having pore dimensions lesser than 2 nm are always
equipped as thin films reinforced on good quality porous inorganic supports with oil content, strong cleaning agents, and higher resistance to high temperature (Zhang et al., 2018;
Zhang, Zhang, et al., 2013). There are some advantages about inorganic membranes for
example high thermal and chemical stability, withstanding harsh chemical cleaning, frequent backwashing, inertness to microbiological degradation as compared to polymeric
membranes (Kokotov & Hodes, 2010; Wang, Han, et al., 2017). Nowadays, significant R&D
efforts are prepared porous inorganic membranes include crystalline and amorphous
membranes, but one key disadvantage for inorganic membranes is more expensive vis-àvis organic membranes (Wang, Yiming, Saththasivam, & Liu, 2017).
12.3 Fundamental principles behind oil/water separation behavior
Surface engineering developed the design of super wetting materials, which have harvested efficient processes for industrial emulsion wastes treatment and environmental
B. Physical processes
12.3 Fundamental principles behind oil/water separation behavior
211
cleanup. So far, superoleophobic or superhydrophobic membranes for oil 2 water emulsion separation are adopted as oil and water have different surface tension, which directly
intermingles with super wetting behavior (Ge et al., 2017; Gu et al., 2014; Huang, Chen,
et al., 2018). The surface wettability of membranes was depending on their surface geometrical structure and free energy (Adebajo, Frost, Kloprogge, Carmody, & Kokot, 2003).
Although in the presence of surfactant the super wetting materials are always difficult to
distinct immiscible oily wastewater and turn into ineffective intended for oil-water emulsions (Ichikawa, 2007). Especially, three types of separation materials have been classified
into (1) superhydrophobic-superoleophilic, (2) superhydrophilic-superoleophobic, and, (3)
underwater superoleophobicity membrane.
12.3.1 Superhydrophobic-superoleophilic membrane
The superhydrophobic/superoleophilic separation materials are typically oil removal
membranes, it is easily separate oil from dispersed oil-in-water emulsions (Ke, Jin, Jiang,
& Yu, 2014; Zhou & He, 2018). Nevertheless, this process shows lowered surface-tension
liquid towards barrier both phases (water and oil), decreasing both separation efficiency
and flux when oils willingly foul these oleophilic surfaces (Shang et al., 2012). The superhydrophobic/superoleophilic membranes having a low contact angle for oil while exhibiting a larger contact angle for water and can fascinate oil from mixing of water and oil
(Zhang, Shi, et al., 2013). There are two categories of superhydrophobic/superoleophilic
materials: (1) two-dimensional (2D) materials built on a metal mesh membrane, which are
basically “filter type” oil separation materials, and (2) three-dimensional (3D) materials
with the porous structure for example foam, and aerogels, which are primarily “adsorption type” separation materials (Zhu, Pan, & Liu, 2011). The porous structure of the superhydrophobic/superoleophilic poly(vinylidene fluoride) membranes prepared by the
phase-inversion method has been presented in Scheme 12.1 (Zhang, Shi, et al., 2013). In
this method, the addition of inert solvent additive like ammonia water into the poly
SCHEME 12.1 Schematic representation of phase-inversion method for the development of a poly(vinylidene)
fluoride membrane (Zhang, Shi, et al., 2013).
B. Physical processes
212
12. Nanocoated membranes for oil/water separation
(vinylidene fluoride) solution forming the polymer clusters in the solution. It is noteworthy to see the effectiveness of membranes for separating various Oil-in-Water Emulsions
with surfactant-free dispersed.
12.3.2 Superhydrophilic-superoleophobic membrane
It was found that superhydrophilic-superoleophobic membrane in oil spill wastewater
is an extraordinary membrane for filtering or absorbing water and oil retention in the separation process (Brown, Atkinson, & Badyal, 2014). It is essential to build a hydrophilic
oleophobic surface, construct a low-surface-energy than oil (Cheng et al., 2011). The
superhydrophilic-superoleophobic membranes are a benefit of antifouling by oil when
dealing with oil spill wastewater (Wang & Gong, 2017). During the separation process,
this kind of membrane is easily contaminated by oil because of its oleophilic properties,
which might be a decrease in secondary pollution and separation efficiency (Wang, He,
et al., 2015). The water removal processes of separation membranes have been made by
using a variety of materials including graphene oxide, hydrogels, and zwitterionic polymers, which have the design of superhydrophilic surfaces that display superoleophobicity
(Yang et al., 2012). As shown in Scheme 12.2, perfluorinated thiol-acidic acrylate UV
photopolymerization was employed to fabricate the rapid superhydrophilic/superoleophobic membrane with a hydrophilic silica nanoparticle via spray deposition method,
which showed the treatment of spilled oil and industrial daily waste (Xiong et al., 2018).
SCHEME 12.2 Hydrophilic silica nanoparticles loaded with hybrid organic-inorganic thiol-acrylate resins via
photopolymerization and spray-deposition process (Xiong et al., 2018).
B. Physical processes
12.4 Current application of membranes in oily wastewater treatment
213
12.3.3 Underwater superoleophobicity membrane
The underwater superoleophobicity membrane is used extensively in the treatment of
oil-in-water emulsions and achieved the real oily wastewater samples from water (Teng,
Xie, Wang, Zhu, & Jiang, 2016). The membrane surface has displays good separation efficiency and low fouling, to avoid fouling problems of the membrane it should be prewetted with water (Yong et al., 2018). It is notable to see a superhydrophilic/underwater
superoleophobic membrane appropriate for cleaning up water from water-in-oil emulsions
when the water tends to produce a barricade among the membrane surface and oil. Sawai,
Nishimoto, Kameshima, Fujii, and Miyake (2013). Fig. 12.1A shown a PAN membrane by
a hydroxylamine-induced phase-inversion method for diesel oil/water emulsion separation (Zarghamia, Mohammadia, Sadrzadeha, & Bruggend, 2019). The hydroxylamine
hydrochloride accumulated into a clotting bath leads to the hydroxyl and amine groups
into polyacrylonitrile chains through amidoximation of PAN membranes. As exposed in
Fig. 12.1B, the WCA and Underwater OCA (UOCA) of the modified membrane are about
1 and 156 , correspondingly.
12.4 Current application of membranes in oily wastewater treatment
Numerous applications can affect the efficiency of water-in-oil emulsions by membranes and can be approximately classified into Zwitterionic and Biomimetic thin
membranes.
12.4.1 Zwitterionic membranes
The development of zwitterionic materials is of current attention globally and the
zwitterion-coated membrane has excellent antifouling ability and greater flux recovery
rate. But different from poly (ethylene glycol) byproducts as they produced ionic interactions with water molecules, making it tight and stable (Venault et al., 2016). It has come
mostly from amino acids, which contain ammonium and a carboxylate group through a
FIGURE 12.1 (A) Development of a polyacrylonitrile membrane via hydroxylamine-induced phase-inversion
method, (B) Photo of the modified membrane showing a water contact angle of ,1 degrees (left) and a UOCA of
156 degrees (right) (Zarghamia et al., 2019).
B. Physical processes
214
12. Nanocoated membranes for oil/water separation
kind of intramolecular acid/base reaction (Davenport, Lee, & Elimelech, 2017). Selfcleaning zwitterionic nanofibrous membranes are one of the major industrial applications
in oil/water separation performance and display great chemical stability in acid, alkaline
and salty environments owing to their can resist not only crude oil fouling but also bacteria adhesion and reduce biofilm formation (Yu, Cao, et al., 2009). Membrane surfaces
grafted or coated with zwitterionic polymers for example polycarboxybetaine, polysulfonbetaine, and polyphosphobetiane are proven to be more resistant against the adsorption of
biological and organic components (Dizon & Venault, 2018). In recent times, several zwitterionic polymers have been explored as surface modifiers of some substrates, and the
third generation of low fouling materials for oil/water separation, these modifications
have enhanced the membrane antifouling properties (Sin et al., 2017). The zwitterionic and
pseudozwitterionic materials are the tendency to bind a strong bond with the water molecules through hydrogen bonding and electrostatic interactions, and well inhibit the oil
adhesion on membrane surface (Li et al., 2008). A schematic has been presented where the
zwitterionic polymer blended PVDF membrane is prepared via an in situ crosslinking
through nonsolvent phase separation followed by sulfonation reaction (Scheme 12.3) (Zhu,
Xie, Zhang, Xing, & Jin, 2017). The reaction was performed between the PVDF matrix and
zwitterionic polymer, which resolves the matter of poor compatibility and is altered into a
zwitterionic polyelectrolyte by functionalization/sulfonation. The prepared membrane
demonstrated outstanding performance to discrete oil from the oil-in-water mixture, in
addition to a possible upgraded of the oil-fouling and high water flux recovery (98%) of
the membrane.
SCHEME 12.3 Schematic illustration of Zwitterionic poly(vinylidene)fluoride-PSH-blend membrane through a
mutual method of in situ cross-linking of random copolymer PDH as an additive, for the duration of phase separation and subsequently membrane was sulfonated (Zhu et al., 2017).
B. Physical processes
12.4 Current application of membranes in oily wastewater treatment
215
12.4.2 Biomimetic thin membranes
The biomimetic thin membranes having superwetting property making from the superwetting microorganisms used for water-in-oil emulsions, particularly several oily wastewaters,
have attracted much attention because of their high separation efficiency and fouling resistance (Pengab & Guo, 2016). Biomimetic and bioinspired membranes have high porosity and
stability/resistance can be applying for separation purpose, and healthcare (Chen, Chen, Yin,
Ma, & Jiang, 2009). Biomimetic membrane material improved by the engineered/modified or
natural proteins, with the desired separation and sensing properties of bioderived additives
(Li, Wang, Wu, Wang, & Jiang, 2012). Biomimetic membranes with superwetting property,
primarily connecting superhydrophilic/underwater superoleophobic, superhydrophobic/
superoleophilic, superhydrophilic/superoleophilic (superamphiphilicity), and superhydrophilic/superoleophobic membranes show a principal role in separating an oil/water mixture
(Zhang et al., 2014). Fig. 12.2 illustrates the schematic diagram of an innovative strong biomimetic and ultra-robust porous ceramic membrane (Liu et al., 2020). The lightweight and hierarchically membrane were fabricated through hydrophobic coating linking and self-assembly
of the Al2O3 powder and used for oily wastewater separation with high efficiency (99.98%).
Initially, propionic acid was used for modifying the Al2O3 ceramic powder (I), and afterward,
oil and PVA were quickly added to form the ceramic wet emulsion (II). A biomimetic hierarchically macroporous ceramic was gotten after the drying and sintering process (III), and
lastly, the PDMS coating period (IV) goes to superoleophilic and superhydrophobic.
FIGURE 12.2 Schematic design displaying the creation method of the hierarchically macroporous ceramic
membrane by a mixture of (A) emulsion-assisted self-assembly of the altered Al2O3 powder and, (B) the ceramic
membrane after hydrophobic PDMS coating (Liu et al., 2020).
B. Physical processes
216
12. Nanocoated membranes for oil/water separation
12.5 Morphology and structure
12.5.1 Surface morphology
The surface microstructure has been demonstrated through AFM surface topography of
both isotropic and anisotropic polyethersulfone (PES) membranes as exposed in Fig. 12.3
(Abdel-Aty et al., 2020). The root means square roughness values (Sq) of both the membranes provided a detailed comparison from the 2D and 3D AFM morphology. During the
phase inversion process surface roughness is influenced by several issues, for example, the
altercation rate amongst solvent and nonsolvent (Sadeghi, Aroujalian, Raisi, Dabir, &
Fathizadeh, 2013). The Sq of the anisotropic PES membrane is 16 nm, while the Sq of isotropic PES improves to 71 nm. The smaller roughness in anisotropic PES membrane vis-àvis isotropic membrane is presumably owing to the creation of a compact skin layer that
shows average pore diameter and lower surface porosity. It is notable to mention that, the
increased roughness in anisotropic PES membrane is sturdily connected to the creation of
skinless porous structure and the increase in average pore diameter and membrane surface porosity.
FIGURE 12.3 Two-dimensional and three-dimensional AFM topograph of PES membranes: (A) Anisotropic
and (B) Isotropic (Abdel-Aty et al., 2020).
B. Physical processes
12.5 Morphology and structure
217
12.5.2 X-ray photoelectron spectroscopy
X-ray photoelectron spectroscopy (XPS) can detect the elemental composition that exists
within a material. XPS analysis spectra of the pure cotton fabric (CF), VPOSS@CF, and CPOSS@CF are shown in Fig. 12.4A indicating two distinguished peaks C1s and O1s, corresponding to a surface of neat CF, whereas more or less different peaks at 227.8 eV (S2s),
163.9 eV (S2p), 154.4 eV (Si2s), 103.0 eV (Si2p) respectively, have appeared after functionalization in the VPOSS@CF and C-POSS@CF membranes, are accredited to the sign of S and
Si element (Zhou et al., 2021). The high-resolution C1s spectrum of virgin CF is clear from
the deconvoluted peaks, which are allocated to the CaC (284.7 eV), CaO (286.3 eV), and
CQO (288.1 eV) bond, correspondingly as exposed in Fig. 12.4B. The intense bond at
CQC (288.6 eV) and CaSi (284.1 eV) of the VPOSS@CF sample are detected, indicating
grafting of VPOSS-MPTMS (Fig. 12.4C) with the surface of cotton fiber. Fig. 12.4D has
shown the high-resolution C1s spectrum, which can be split CaS (287.6 eV) bond in CPOSS@CF. In the meantime, CaO and CQO bond their peak intensities are reinforcing as
compared to the VPOSS@CF.
Nevertheless, the comparative content of C, O, Si, and S elements have been quantified
using deconvolution of XPS peaks and found to be 35.2, 23.9, 36.5, and 4.4 wt%, correspondingly in VPOSS@CF. The content of C, O, and S elements increases after the grafted
2-mercaptoacetic acid followed by thiolene functionalization amongst surface vinyl groups
FIGURE 12.4 (A) XPS spectra of the pure cotton fabric (CF), VPOSS@CF, and C-POSS@CF. C1s spectra of the
pure CF (B), VPOSS@CF (C), and C-POSS@CF (D) (Zhou et al., 2021).
B. Physical processes
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12. Nanocoated membranes for oil/water separation
of the cotton fiber and 2-mercaptoacetic acid and found to be 45.6, 29.1, 16.5, and 8.8 wt%
for C-POSS@CF.
12.5.3 FTIR
Infrared spectra testing is particularly useful to a determination of the chemical composition existing in polymeric, organic, and in some cases, inorganic materials. Fig. 12.5 displays ATR-IR patterns of neat PVDF membrane and TA-Fe@PVDF nanohybrid
membranes and confirms the existence of dissimilar functional groups because of surface
coating technology. The peaks at 3300 cm21 are accredited to OaH stretching vibration for
the PVDF membrane (Yanga et al., 2020). A characteristic peak at around 1612 cm21,
which could be ascribed to the stretching vibration of the CQC bond, and the peaks at
1202 cm21 are attributed to the C-F stretching vibration. Moreover, after coating of TAphenolic complexes, the TA-Fe@PVDF nanohybrid membranes shown a band at
1714 cm21, which assigned to the stretching vibration of the CQO bond in the TA molecules (Xie et al., 2016).
12.6 Wetting properties
Fig. 12.6A shows the WCA of the APM-260 membrane in the air (Li et al., 2015). The
CA is 0 degrees due to the intrinsic hydrophilicity of as-calcined TiO2 nanotubes (Balaur,
Macak, Taveira, & Schmuki, 2005) and the porous architecture. The membrane demonstrating superhydrophilicity, because within several seconds the droplet of water can permeate through the porous membrane rapidly. On the other hand, the APM-260 membrane
displays the UOCA, which was resolute to be B156.7 degrees using 2 μL of dichloromethane as an oil probe (Fig. 12.6B) (Li et al., 2015). The porous APM-260 membrane was
FIGURE 12.5 FTIR spectra of the neat
PVDF and TA-Fe@PVDF nanohybrid
membranes (Yanga et al., 2020).
B. Physical processes
12.7 Mechanical strength
219
FIGURE 12.6 (A) The CA of APM-260 membrane, (B)
The OCA of APM-260 membrane. The membrane was
shown a maximum pore size of 260 mm. Li et al. (2015).
FIGURE 12.7 (A) Tensile stress-strain curves for different membrane, (B) membranes showing similar
Young’s modulus (Mousaa et al., 2020).
immersed in the aqueous environment, water takes place in the pores in place of air and it
prevents the infiltration of oil to be the pores.
12.7 Mechanical strength
A perfect separation of oil spill wastewater membrane should be a free-standing
film with adequate durability, and processability (Pandey, Jana, Aswal, Rana, & Maiti,
2017). The Young’s modulus of the polysulfone (PSF)-based nanofiber membrane has
been corroborated using a tensile tester machine. The tensile curves of the fabricated
membranes are existing in Fig. 12.7A displaying decreased strain for iron acetate and
three times increased the tensile stress as compared to pure PSF membrane (Mousaa,
Alfadhel, Ateiac, Abdel-Jabera, & Gomaa, 2020). Besides, the comparable magnitude of
Young’s modulus is shown in Fig. 12.7B indicating considerably without alterations in
the elastic performance of the PSF composite. These results can be accredited to the
membrane porosity and the nanofiber diameters (Obaid, Barakat, et al., 2015). In contrast, the polyamide (PA) layer illustration a distinctive higher Young’s modulus and
tensile stress in mutually cases are primarily owing to the polymer matrix and its nanohybrids interfacial interaction through a novel hydroxide group of PA layer (Huang
et al., 2017). On the other hand, membranes make brittle behavior and higher mechanical strength when the strain rate was decreased.
B. Physical processes
220
12. Nanocoated membranes for oil/water separation
12.8 Antifouling method
The fouling affects the membrane lifetime and efficiency, which forms the surface of the
membrane throughout the operation and afterward leads to flux worsening. The antifouling
capacity of the modified membranes was evaluated using the emulsion flux decay ratio (Dr)
and flux recovery ratio (FRR) of oil-in-water emulsion (Ahmad, Majid, & Ooi, 2011). To
remove the size factor of the channel, merely Dr and FRR values of PSF-1 and PSF-3 which
have actual near channel dimensions were calculated. The matrix PSF is functionalized by
blending in presence of SiO2 nanoparticles and promotes the membranes’ antifouling properties. The Dr and FRR were resolute from the following equations (Ahmad et al., 2011).
(12.1)
DR 5 Jw1 2 Jp =Jw1 3 100%
FRR 5 Jw2 =Jw1 3 100%
(12.2)
where, Jw1 is the flux of water which was calculated through assessing the permeated
water and the pressure was compact near 0.1 MPa, Jp is the flux which was calculated in
the same way as Jw1, Jw2. The cleaned membranes were washed with distilled water for
30 min underwater flux, which was also calculated in the similar mode of Jw1. The ultrafiltration experiment was measured at room temperature and a stirring high speed of
400 rpm. The lower Dr value in membrane suggests a superior antifouling property shows
in modified membranes. It should also be mentioned that a better antifouling property has
been displayed in the membrane for the higher FRR value.
The antifouling properties of blended membranes are reported in Table 12.1 (Ahmad
et al., 2011). The Dr value reduced from 98.28% down to 86.55% for the SiO2 content of
blended composition with PSf improved from 1.0 to 3.0 g. Hence, oil droplet’s adsorption
and deposition have reduced on the advanced membrane surfaces vis-à-vis pure membrane presumably owing to the incorporation of SiO2 nanoparticles along with enhancement of hydrophilicity. Interestingly, the FRR value has increased from 10.34% to 34.01%
showing better oil droplets cleaned from the SiO2 surrounded membrane with respect to
virgin PSF membrane. These results demonstrated that blending of PSf/SiO2 was performed in template system via 2D nanoparticle and its larger antifouling properties.
12.9 Separation performance of membranes for the oil-in-water mixture
At present, porous membranes with superwetting behavior, which interact with borders
of the solid phase, water phase, and oil phase was developed for manageable separation
of oily wastewater (Feng, Feng, et al., 2004). The water-in-oil emulsions sources are
TABLE 12.1 The PSF/SiO2 membranes showing antifouling properties (Ahmad et al., 2011).
SiO2 content (g)
Dr (%)
FRR (%)
1.00
98.28
10.34
3.00
86.55
34.01
B. Physical processes
12.9 Separation performance of membranes for the oil-in-water mixture
221
universal for example tannery, and petroleum industries (Feng et al., 2002). The oil/water
mixture can be classified into dissolved oil (,0.1 μm), emulsified oil (0.12 μm), dispersed oil
(10100 μm), and oil slick ( . 100 μm), as said by the form of oil in water (Deng et al., 2020).
Throughout the separation process of oil and water, the common corrosive constituents for
example acids, alkaline, or salts are frequently contaminated on the surface of the membrane
to make the defeat its superhydrophobicity (Fang et al., 2020). Dispersing a few percentages
of nanoparticles into materials, it is usually anticipated to effectively isolated water and oil
because of the economic and environmental demands (Feng, Sun, & Ye, 2017). There are various functional materials with extraordinary wettability to separating oil/water mixtures. In
the latest decades, many researchers have developed membranes for the oil/water separation
field, using numerous techniques, amongst them membrane filtrations were the greatest
prime. It has been observed that application of conventional filtration membrane in oily
wastewater treatment have a propensity size-sieving outcome motivated by pressure as the
droplets of oil have to not permitted to pass through the channels of the membrane.
Usually, for the treatment of oil-in-water mixture, we should deliberate the systematic
design of porous materials by two critical physical characteristics, (1) the breakthrough
pressure (i.e., pore size) and, (2) surface structure (i.e., porosity). The maximum pressure
is called the breakthrough pressure (ΔPC), which is practical on the surface before the
assumed fluid infuses into the channels (Mosadegh-Sedghi, Rodrigue, Brisson, & Iliuta,
2014). For the cylindrical geometry of the pores, ΔPC can be resolute using the YoungLaplace equation (Kim & Harriott, 1987)
ΔPC 5 2
2γL cosθ
rp
(12.3)
Anywhere, the surface tension of the fluid is denoted by γ L, θ represents the intrinsic
contact angle, and rp signifies the radius of the pore. This is to mention that the breakthrough pressure can considerably be affected by the wettability of a material.
Separation of membrane for oil/water separation has great impact because of its lower price,
high efficiency, and simplicity of procedure (Chen, Weng, Mahmood, Chen, & Wang, 2019).
Fig. 12.8 illustrates the water permeation flux and separation performances of the membranes
FIGURE 12.8 The experimental setup and separation method of oil and water of the membranes after 8 h sintering: (A) photographs of the oil (dyed red) and water (dyed blue) mixture, (B) photographs of oil and water on the
surface of membrane displaying different wettability, (C) photographs viewing the mixture was transferred into
the upper tube, (D) photographs presenting oil and water were separated (Qing et al., 2017).
B. Physical processes
222
12. Nanocoated membranes for oil/water separation
for a mixture of oil and water into a custom-made separation module apparatus (Qing et al.,
2017). When the membrane surface was absorbed by an oil droplet, however a droplet of
water trying to retain its circular shape on the surface (Fig. 12.8B). The membrane fluid
(water) entrance pressure were approximately 193.5 6 2.1 kPa, which outcomes in the
superhydrophobic-superoleophilic membrane. Fig. 12.8B illustrates the separation cell toward
the upper tube, where the mixture of oil-water has been poured. This is to mention that the
membrane is fully wet by oil for quite some time after oil permeate was performed throughout
the membrane toward the foot tube. The separation has been completed after only 3.5 min
exhibit two stages of water separation were retained into the upper tube whereas oil was separated to the bottom tube (Fig. 12.8D). Underneath the gravity/driven condition in the separation
process the membrane’s average permeate flux was about 1143 6 69 L/m2/h1 without external
driven force. Furthermore, the membrane has the characteristics of good separation efficiency
of oil-in-water mixture presumably due to the blue colored that is water was not found in the
bottom tube.
For oil/water separation, some mixtures of oil and organic solvents were poured into
distilled water in addition to oil/water emulsions added onto the zwitterionic nanogels
modified polyacrylonitrile nanofibrous (ZPAN) membranes for evaluating the separation
performance. A milky emulsion which was obtained by mixture stirred vigorously, is
stable for the period of emulsion separation without demulsification as shown in
Fig. 12.9C (Zang, Zheng, Wang, Ma, & Sun, 2020). It is seen through optical microscopy,
the state of oil droplets from equipped oil/water emulsion (inserted photograph in
Fig. 12.9A). Simultaneously, the dynamic light scattering in the emulsion was also measured and this data illustrates the size of oil droplets, which fluctuates from nanometers to
micrometers (near to hundred) range (Fig. 12.9A). The ZPAN membrane has been stationary at a dead-end into the filtration module (before the separation test) and the pre-wetted
membrane surface is covered by milky emulsion has been shown in Fig. 12.9B. For the
ZPAN membrane, the liquid height of about 10 cm is obtained at a constant gravitational
FIGURE 12.9 (A) Image of the optical microscopy (interleaved photo) and oil size distribution of oil/water
emulsion, pictures of (B) the filtration instrument, and (C) the oil/water emulsion containing oil and organic solvents were added to deionized water, and (D) the equivalent filtrate, (E) Image from optical microscopy of the filtrate from experiment (Zang et al., 2020).
B. Physical processes
12.11 Future perspective
223
pressure of 1 kPa. This is worth mentioning that such microfiltration membrane having
low driving pressure shown less fouling primarily due to the membrane channel-filling by
oil droplets and saving energy, as compared to the conventional ultrafiltration and nanofiltration methods. This outcome shows that the electrospun ZPAN membrane with superhydrophilic outward has to capture water molecules. In the meantime, our membrane
surface formed the hydration layer which can resist surfactant-free oil droplets. Oil droplets tend to move on the surface probably because of the short adhesive surface and it is
coalescing into bigger droplets leading to additional demulsification. Moreover, the prominent microporous structure in the ZPAN membrane indicates greater interconnected water
channels. Therefore, below capillary and gravity force the apprehended water effortlessly
passed through the membrane (Ge et al., 2017) is shown in Fig. 12.9D. No oil drops were
observed in the filtrate as exposed by the optical microscopy image (Fig. 12.9F).
12.10 Summary
The separation process with a nanocoated membrane for oil-in-water emulsions has
been presented in this chapter. The present revision for producing organic-based and
inorganic-based membranes was discussed. The nature of three kinds of superwetting
materials has been progressing oil-in-water emulsions separation and their proper modifications required to analyze the current research status. In the meantime, membrane applications comprising zwitterionic and biomimetic thin membranes also play significant
factors in the separation performance among oil and water. As well as the superwetting
property, there is an improvement in other properties like surface morphology, structure
by the use of nano-coated membrane systems. Consequently, a summary of the important
characterization in the next-generation membranes (wetting behavior, antifouling properties, mechanical strength, etc.) and an explanation of the steps for oil/water separation
technologies is explained well. Finally, a comprehensive survey of all varieties of the oilin-water mixture in different membranes and their separation performance was studied.
12.11 Future perspective
So far, a molecular level phenomenon containing structural and morphology have
exposed that the lead to the production of organic and inorganic multifunctional membranes with high surface areas. Spilled oil samples and different types of nano-coated raw
material are the motivation for future achievements. All of these outcomes resourcefully
regulate the surface hydrophilicity and structural alteration of membranes for controllable
oil-water separation. Therefore, the altered (nano-coated) membranes show better wetting
behavior, higher mechanical strength, superior antifouling properties, and higher separation performance vis-à-vis pristine membranes. More studies are still needed to improve
polymeric, ceramic, and mixed matrix membranes for water treatment application.
Moreover, the recent literature has been focused on the low-cost membrane with outstanding separation performance in the removal of oily wastewater treatment.
B. Physical processes
224
12. Nanocoated membranes for oil/water separation
Many challenges still remain for achievements regarding the new membrane materials
with lower production cost and water purification application. Accordingly, there are
some challenges to be talked about in this area may include the subsequent parts: Initial,
nano-coated membrane should be less fouling resistance and easy to backwash for the
purification process. Second, ceramic membranes with lower cost are very crucial and
more effective for study the oil/water separation processes. Third, various multifunctional
membranes with high prospective and innovation have been used for the oily wastewater
treatment research field. Lastly, a control surface modification method is necessary to
increase the efficiency of the membrane.
Acknowledgement
The authors are thankful for the award of the Post-Doctoral Fellowship of JU-RUSA 2.0, India.
Conflict of interest
The authors confirm that there is no conflict of interest for this publication.
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S E C T I O N
C
Thermo-chemical processes
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C H A P T E R
13
Chemical stabilization of oil by
elastomizers
Sankha Chakrabortty1, Jayato Nayak2 and
Prasenjit Chakraborty3
1
School of Bio-Technology and Chemical Technology, Kalinga Institute of Industrial
Technology, India 2Department of Chemical Engineering, School of Bio and Chemical
Engineering, Kalasalingam Academy of Research and Education, India 3Agni College of
Technology, Thalambur, Chennai, India
O U T L I N E
13.1 Introduction
233
13.2 Characteristics of oil spills
13.2.1 Physical characteristics
13.2.2 Chemical characteristics
235
236
236
13.3 Oil spill stabilization/remediation
techniques
13.3.1 Physical stabilization process
13.3.2 Adsorbent materials
13.3.3 Thermal remediation process
236
237
238
240
13.3.4 Bioremediation method
240
13.3.5 Oil stabilzation by chemical based
elastomizers
241
13.4 Future perspective for oil stabilization
through chemical process
245
13.5 Conclusions
245
References
245
13.1 Introduction
From the initiation of the global industrial uprising, high turnover aimed market outlook in fully competitive production strategies, enabled extreme exploitation of fossil fuels.
Year-by-year, the amplified human population density accustomed with the modern
sophistication, forced to uprise the demand for electrical power on the power production
houses. Along with the booming of manufacturing sectors, the tuning of urbane
Advances in Oil-Water Separation
DOI: https://doi.org/10.1016/B978-0-323-89978-9.00022-7
233
© 2022 Elsevier Inc. All rights reserved.
234
13. Chemical stabilization of oil by elastomizers
commodities from luxury items to basic needs, and the upsurging of transportation sectors
triggered the increased production of earth oils for continuous fuel supply. Due to
increased demand and global financial analyses, fuel oil production, selling import-export,
and earning of revenue by any country is identified as one of the greatest pivotal factors
of a country’s economic standpoint (Wang et al., 2020). Eventually, the extraction of crude
oil got amplified along with the petroleum and petrochemical production sectors to cater
to such demand and to maintain global financial dignity for a country. In the current
times, the largest extractors of crude oil extraction companies are ExxonMobil, BP, Sinopec
Group, Royal Dutch Shell, Valero, Gazprom, Phillips 66, Kuwait Petroleum Corp., Pemex.,
Chevron Corporation, National Iranian Oil Co, Total, etc. With the exponential growth in
oil extraction, about 5.6 billion/m3 of impure oil mixture (crude oil, shale oil, and liquid
content of natural gas) was extracted in 2019, from where, about 4.8 billion m3 of usable
oil in different forms were produced (Garside, 2020). World-widely, the crude fuel oil is
extracted from the sea-shore or gulf regions of a country employing huge investments for
oil extraction. In fact, specially design machinery and skilled manpower are involved to
control and maintain the safety and security of a floating crude oil extraction unit. But,
unwanted spilling of crude oil is now a major concern of the marine environment that cannot be avoided. In fact, the spill could be arrested only to a partial fraction even if highly
skilled professionals are involved. Spilled oil is basically waste from an offshore crude oil
extraction unit because it could be hardly recovered. Because of its low density than seawater, leaked or spilled oil volume keeps floating on the water surface. Along with that, it
is proved to be crucially harmful to marine aquatic eco-systems because it breaks the oxygen transfer from the atmosphere to water. Thus, the biotic communities of the marine
ecosystem or the ecosystems dependent on it are facing critical issues of survival regarding the oil spillage problem. But, during the current decades, the emergence of ecologically
sensible legislative actions are getting stricter with prompt actions on extraction sectors
(Elliott, 1999; Osuji & Chukunedum, 2006). The most adopted conventional and emerging
technologies for oil spill control are the use of oil booms, skimmers, absorbent or adsorbent or dispersant materials, burning in situ, hot water and high-pressure washing, manual cleaning, bioremediation, and stabilization by Elastomizers. Along with that, priorities
are being given to the use of alternative materials for spilled oil capture and separation
which would be low-cost and environment-friendly. This has started to give more encouragement to the industrialists and global research communities while fostering novel
research towards the exhaustive reviews, material development, analyses, and testing.
Indeed, such advanced materials are the need of the hour that can capture/immobilize
and stabilize the spilled oil effectively at a low cost (Czarnecki, 2009). Moreover, the
concern should be towards the use of a low content of mas which is efficient in arresting spilled volume to mix further with the marine aquatic system. Therefore newer
routes are getting opened focusing on the growth of clean technologies for a wide
plethora of stabilizing chemicals which leads the crude oil extraction process towards
the least environmental degradation by waste oil-spilling (MI News Network, 2020;
Younis, AliMaitlo, Lee, & Kim, 2020). Immediate to the spilling of oil, as it becomes
essential to prevent the spreading and contamination of it in the adjacent regions of the
origination spot. In fact, mechanical technologies e.g., oil booms come up with certain
demerits. Oil booms are like fences preventing the spread of oils, and found to be
C. Thermo-chemical processes
13.2 Characteristics of oil spills
235
effective for single-spot spillage which could be accessed within a short time of occurrence. This technology is not successful for large spillage areas or regions with heavy
marine waves, air-flow speeds, or unstable tides. Skimming machines work as same as
vacuum cleaning apparatus, suck up the spilled into the in-built collection chamber but
the process suffers due to quick clogging. In the case of adsorption, it is a must to
repossess the spent adsorbents which is an extremely tough task. Ineffective collection
imposes a high risk to aquatic life because of leachate formation. In situ burning produces hazardous smoke and temperature difference in the marine aquatic layer. By
using dispersing agents, tiny tarballs are formed which get mixed with seawater and
sands, which may travel towards the seashores. During the use of hot water and highpressure cleaning, hot water at about 170 C, is flushed through high-pressure nozzles.
This high temperature is extremely dangerous for the living species present in the
flushing zone. Manual cleaning process of spilled oil debris could be applied on small
scale in the shorelines because it is labor-intensive and time-inefficient. Though lots of
researches are going on green bioremediation of spilled oil, the process is highly timeconsuming with a high possibility of formation of undesirable algal or fungal species,
that in-turn decreases sunlight and oxygen availability in deep seawater. Thus, the use
of such technologies also could be proved as counter-productive to marine life (Eie,
1995; MI News Network, 2020). But, currently, with the use of “Elastol,” which are the
compounds of amorphous poly iso-butylene is being analyzed to capture and stabilize
spilled crude oil. Gelatinous formations of solidified oil on the water surface arresting
it from spreading or escaping, the technology used to be extremely effective with a typically fast reaction process with ideal reactivity within an hour. Such proposed compound is nonhazardous but, it should be removed immediately after application to
restrict the suffocation of marine animals. In the regions where the oil contamination is
very high with a thick layer formation, the other methods typically fail inefficient
removal/capturing/stabilization of oil. Elastomizers increase the speed of recovery
rate and efficacy of oil removal by capturing oil into the polymer matrix, lessening the
contacts with air and water (Eie, 1995; USEPA, 2011c). But, a lot of researches are
extremely required to gain confidence in such a stabilization process with such novel
polymers, which will foster the implementation of an economic and environmentfriendly process.
13.2 Characteristics of oil spills
The spill of oil in the marine ecosystem has been a major threat to the environment in
current days. The release of various petroleum products, crude oil, waste oil, and bunker
fuel into the marine environment is a key concern for the pollution of the ocean ecosystem.
The oil spill effect asperity mainly confides in the oil amount and its physicochemical
properties which affect different transformation processes such as emulsification, evaporation, dissolution, spreading, and sedimentation (Holakoo, 2001). The chocolate mousse,
several oxygenated products, and tarball formation occur in the various transformation
processes which results in tough recovery of the oil (Daling & Strøm, 1999).
C. Thermo-chemical processes
236
13. Chemical stabilization of oil by elastomizers
13.2.1 Physical characteristics
There are different oil physical properties like surface tension, color, viscosity and specific gravity. The change of oil spill characteristics reliant on the oil category released in
the marine atmosphere. Usually, depending on the oil’s physical properties, the oil color
may transform to yellow, red or green color from the black or dark brown oil color
(Holakoo, 2001). The various characteristics specific gravity, surface tension, and viscosity
are the key factors for spreading capability of oil spill. Oil with high viscosity has fewer
propensity to outspread (USEPA, 1999a). It has been reported by Payne and Philips (1985)
that chocolate moss has been formed due to high viscous oil spill as degradation of chocolate moss is very tough (Payne & Philips, 1985). The density of fuel oil is reduced 0.88 kg/
dm3 to 0.855 kg/dm3 with increased temperature of 10 C50 C and also viscosity
decreased from 5000 to 200 cSt (Nordvik, Simmons, Bitting, Lewis, & Strom-Kristiansen,
1996). The resistance of oil flow is reduced which increases the spreading capability of oil.
The effect of temperature on surface tension of oil can be accredited to the fact that in hot
water, dispersion tendency of oil spill increases than in less warm waters. The rapid
spreading capability has been observed for low surface tension oil even without any wind
or flows. The oil floats on the ocean water surface and horizontally disperses as the density of the marine water is higher than the density of the oil. The oil’s lighter element evaporates which raises the oil specific gravity permitting weightier oils to sink. Oil tar balls
are generated that might be attached with bottom water sea rocks or sediments.
13.2.2 Chemical characteristics
Boiling point, melting point, molecular weight, flash point, partition coefficient, solubility, explosivity limits, and flammability limits are the oil’s chemical properties. The oil
type is related to chemical properties (ASTDR, 1995). The oil contains hydrocarbon with
some composite chemical compositions and also comprises a few metals oxygen, nitrogen,
and sulfur. Alkanes containing mainly saturated carbon and hydrogen atoms which are
hydrocarbon’s mildest form. Whereas, unsaturated carbon and hydrogen molecules with
double or triple bonds named Alkenes and Alkynes. There are four major groups of oil
are aromatic, saturated, unsaturated, and polar groups. Crude oil includes 50% naphthene,
30% alkanes or paraffin, 15% aromatics, 5% nitrogen, oxygen comprising compounds and
sulfur. The key hydrocarbons groups observed in gasoline are aromatics, paraffin,
naphthenes, and olefins.
13.3 Oil spill stabilization/remediation techniques
Control and removal of the oil spill from marine water are very critical which is one of
the most contentious matters for the researcher as total removal of the oil spill from ocean
environment is not possible. Remediation methods have been recognized as an imperative
approach for oil spill cleaning from marine water. Various remediation methods are physical technique, chemical technique, thermal and biological technique (Larson, 2010).
C. Thermo-chemical processes
13.3 Oil spill stabilization/remediation techniques
237
13.3.1 Physical stabilization process
Physical remediation techniques are usually employed for controlling oil spills in
marine water. These methods are mostly used to resist the oil spill dispersion in water as
a barrier without varying chemical and physical properties of oil spill. Different barriers
are employed for oil spill spreading consisting adsorbent materials, booms and skimmers
(Fingas & Fieldhouse, 2011; Vergetis, 2002).
13.3.1.1 Booms
Booms are typical kind of equipment used for oil spill remediation. It prohibits oil spill
spreading through creating a barrier to flow of oil that can enhance oil recovery by different response methods or skimmers. Three types of booms, such as (1) fence boom (2) fireresistant boom and (3) curtain boom are there for oil spill separation from contaminated
water (Potter & Morrison, 2008).
13.3.1.2 Fence booms
Fence booms are floating type fence making of solid and lightweight materials with vertical screen as 60% of the boom stays under the water and 40% stays above the water level.
The height of the boom parts is normally 300, 600 or 800 mm and length is 15 m. Different
boom parts with specific connectors may be attached together. Fence booms are prepared
with PVC or PU fabric which is light weight. The booms having limited storage area, easy
to operate, prevent deformation, fresh and stock are extremely consistent in steady waters.
Less constancy in heavy winds and tides, minor proficiency in high waves and less towing
flexibility are some drawbacks of fence booms (Potter & Morrison, 2008; Ventikos,
Vergetis, Psaraftis, & Triantafyllou, 2004).
13.3.1.3 Curtain booms
Curtain booms are impermeable, and floating type system having a huge foam-filled
circular chamber that stays above water and a malleable skirt that endures underwater.
These booms are built with polystyrene, polyurethane, and bubble cork material. The
width of the chamber ranges from 100500 mm and the length of the skirt varies from
150800 mm. Curtain booms are dependable in seawater in the offshore condition having
great towing flexibility. The performance of curtain booms is higher than fence boom
through cleaning and storage are very tough in these booms (OSS, 2010; Ventikos et al.,
2004).
13.3.1.4 Fire-resistant boom
Fire-resistant metal has been used to make fire-resistant booms that focus on adequate
oil quantity to competently burn at a temperature of 1093 C. These booms are employed
in accordance with techniques for in situ burning (Ventikos et al., 2004). Stainless-steel
booms, Water-cooled booms, ceramic booms, and heat-resistant booms are different forms
of booms that are accessible as fire-resistant booms. Approximately, 1500 m2 of burn area
may produce by 200 m of fire boom length. In marine water, they are effective and have
tremendous ability to save the coastline against the effects of a sea oil fire. However, these
booms are costly and hard to tow as their huge in size and weight.
C. Thermo-chemical processes
238
13. Chemical stabilization of oil by elastomizers
13.3.1.5 Skimmers
Skimmers are a general type of equipment used for oil recovery from the surface of the
marine water combined with booms. Skimmers can be reused and recovered as it operates
without varying its properties. It comprises drums, disks, brushes, and belts (Hammoud,
2001; Larson, 2010). These devices may be vessel-operated or shore-used and selfpropelled. Three types of skimmers are (1) suction, (2) weir and (3) oleophilic (Nomack &
Cleveland, 2010). The skimming achievement depends on the oil spill width and type, climate situations and the place, the contaminant volume in the seawater. Skimmers are productive in marine waters and congestion may occur due to floating contaminants.
13.3.1.6 Wier skimmers
Weir skimmers capture the floating oil from the surface of marine water through gravity action and perform as a dam. The captured oil is transported from the central weir
sink to storage tanks using a pump or through gravity. High efficacy in fast oil recovery
and large static constancy in tides are significant features of skimmers (Hammoud, 2001).
They provide good performance in low density, nonemulsion oil, and less viscous oil.
Skimmers have suggestively less productivity with oil emulsion and are often congested
and blocked through floating debris (Jensen, McClimans, & Johannessen, 1995).
13.3.1.7 Oleophilic skimmers
Oleophilic skimmers contain disks, ropes, drums, belt and brushes type skimmers.
Oleophilic properties materials are used to make all categories of oleophilic skimmers. The
oil complies with material surface that may rubbed from the surface and stored in a tank.
Oleophilic nature of the skimmers can be restored 90% of the oil in marine water.
Oleophilic skimmers are flexible and operative on any thickness spills, fewer affected by
waves and well perform with uneven ice or debris (Nomack & Cleveland, 2010). These
skimmers are not capable of dealing with dispersants mixed oil and separation of waste is
carried out by hand (OSS, 2010).
13.3.1.8 Suction skimmers
The role of suction skimmers is connected to the vacuum pump’s air venture scheme
that extracts oil via large floating heads and moves it to storage tanks. These skimmers are
very active while conducting an oil viscosity of extensive variety. They can also be
obstructed by debris and necessitate trained operators. Suction skimmers are very competent to collect oil residues and are most frequently used to extract oil from beaches,
restricted areas, or oil exclusion from the surface of the soil. They run successfully in offshore areas in combination with the boom in ocean water. However, for use of inflammable oil goods, these skimmers are not worthwhile due to an explosion may occur
(Ventikos et al., 2004).
13.3.2 Adsorbent materials
Oil spills reduction can be accomplished by hydrophobic type adsorbent material which
acts as an ultimate cleaning stage of residual oil after the skimming process. For the
C. Thermo-chemical processes
13.3 Oil spill stabilization/remediation techniques
239
complete oil removal, they promote the transfer of liquid to the semisolid stage (Adebajo,
Frost, Kloprogge, Carmody, & Kokot, 2003). The numerous sorbent materials for oil spill
removal are synthetic materials, natural inorganics, and natural organics.
13.3.2.1 Natural organic adsorbents
Sawdust, kapok, peat moss, vegetable fibers, straw, and milkweed are the common natural organic sorbent. Banerjee, Joshi, and Jayaram (2006) examined the maximum sorption
capability of sawdust and oleic acid affixed sawdust which was 3.6 g/g and 6 g/g respectively in 5 min (Banerjee et al., 2006). It has been reported by Choi and Cloud (1992) that
74%85% of crude oil has been absorbed by cotton fibers and milkweed from crude oil
comprising fabricated marine water bath surface (Choi & Cloud, 1992). Peat moss’s maximum sorption capacity was found to be 6.7 g/g by Ghaly, Pyke, Ghaly, and Ugursal
(1999). Various advantages of natural organic adsorbents are easy availability, well sorption capacity of 315 times of their weight, and cost effectiveness (Ghaly et al., 1999).
There are key drawbacks of these sorbents which are sinking occur due to their sorption
of oil along with water, difficulty on an assortment of sorbents after dispersion on the oil
spill water which is essential to discard for their use and they are labor-intensive (Nomack
& Cleveland, 2010; USEPA, 1999b).
13.3.2.2 Natural inorganic adsorbents
Natural inorganic adsorbents are glass, clay, wool, volcanic ash, and sand (Holakoo,
2001). Teas, Kalligeros, Zanikos, Stournas, and Lois (2001) exposed that for recovery of oil
spill hydrophobic perlite have presented similar sorption capacity with conventional
organic materials (Teas et al., 2001). Clay minerals like pillared and smectites interlayer
clays are employed as sorbents for organic materials in a liquid state in the composed
agrochemicals discharge (Ding, Kloprogge, Frost, Lu, & Zhu, 2001). Alther (2002) stated
that sorption of 50 categories of oil by quats with modified clays performs better than activated carbon. Absorption capacities of these sorbents are 420 times their weight, they are
less expensive and easily available (Alther, 2002). The main limitations of these sorbents
are that they are not recommended for the surface of the water, application in windy
environments is very tough, inhalation of this adsorbent may responsible for possible
health risk, and vermiculite and clay type natural inorganic sorbents are weak material
(USEPA, 2011a).
13.3.2.3 Synthetic adsorbents
The most frequently used trade sorbents are synthetic sorbents. Polypropylene, polystyrene, and polyester foam are employed in synthetic adsorbents. These adsorbents
are accessible in rolls, bars, booms and also applied as a powder to the surface of the
water (Teas et al., 2001). Teas et al. (2001) explored that polypropylene has maximum
oil (light gasoline oil, light cycle oil) sorption capacity of 4.5 g/g. The hydrophobic and
oleophilic nature of synthetic sorbent provides sorption capability of 70100 times of
sorbents weights in oil. Some natural sorbents may be reused many times (Teas et al.,
2001). Jarre et al. inspected that open-cell polyurethane foams and ultralight have
been efficiently adsorbed oil from oil-water mixtures of 100 times their weight.
C. Thermo-chemical processes
240
13. Chemical stabilization of oil by elastomizers
Nonbiodegradability and storage problems are the main drawbacks of these adsorbents
(Choi & Cloud, 1992; USEPA, 2011a).
13.3.3 Thermal remediation process
The thermal method of remediation of oil spills is in situ burning process which is fast
and easy that can ensue with nominal specialized instruments like igniters and fireresistant boom with higher oil exclusion efficacy rates. In situ burning is extensively used
for removing oil spills, snow of pipeline and storage container, jet fuel in ice-enclosed
waters since 1960. This method has been also used to decrease ship accidents in European
countries and also in the Canada and United States (Buist, McCourt, Potter, Ross, &
Trudel, 1999). In situ burning process of oil spill remediation is competent in quiet wind
conditions and fresh oil spills which rapidly burn without producing marine life at any
risk. An underground water source can be sunk and covered by the remaining of this process. Residue reduction can be accomplished by the mechanical way (Davies, Lewis,
Lunel, & Crosbie, 1998). An effective burning process depends on oil thickness and adequate oxygen supply (Buist et al., 1999). Oil combustion sustaining and sufficient oxygen
supply to fire can be conducted through two agents which are burning agents and wicking
agents. Burning agents comprise light crude oils, gasoline, and several commercially existing products and wicking agents consist of wood, straw, silica, and glass beads (Fingas,
Duval, Stevenson, & Galenzoski, 1979). However, in situ burning is a competitive process
for the removal of oil spills. The key limitations of this method are (1) catching risk in the
environment and human health due to the burning by-product (2) worried of secondary
fires (Buist et al., 1999). Burning may affect flora and marine life subsequent to site and
also affects the long-term modification of flora and fauna. The most effective remediation
technique is in situ burning if implemented directly after the spill of oil has appeared.
13.3.4 Bioremediation method
In bioremediation method, degradation of microorganisms and metabolize of chemical
material have been occurred which improve the quality of the environment. The purpose
of this technique is to enhance the natural attenuation method where organic molecules
are incorporated to cell biomass by microorganisms and production of water, carbon
dioxide, and heat as by-products has been appeared (Atlas & Cerniglia, 1995).
Microorganisms have the capability to degrade hydrocarbons which is widespread in
natural oil spill site for marine oil spill. Various type of microorganisms with several
rate of degradation can degrade aromatic and paraffinic hydrocarbons. Over all petroleum products the utmost simply degraded hydrocarbons are aromatics of lowmolecular-weight and alkanes with 1026 carbon train. In marine environments, bacteria
are the leading degraders of hydrocarbon. Several bacterial species that degrade hydrocarbons such as Achromobacter, Pseudomonas, Alcaligenes, Acinobactor, Bacillus
Brevibacterium, Arthrobacter, Flavobacterium, cornybacterium, Nocardia, Vibrio, and
Pseudomonas have been reported (Atlas & Cerniglia, 1995). Numerous microorganisms
leading at various bioremediation stages in which shifting of microbial populations to
C. Thermo-chemical processes
13.3 Oil spill stabilization/remediation techniques
241
aromatic hydrocarbons from alkanes are ensued and easily degraded hydrocarbons are
removed (Sugai, Lindstrom, & Braddock, 1997). The oil spill biodegradation in the
aquatic climate is mostly influenced through the oil concentration, nutrients bioavailability, degree of time in which the environmental biodegradation has been conducted
(Atlas & Cerniglia, 1995; Zahed, Aziz, Isa, & Mohajeri, 2010a). In aquatic ecosystem,
nutrients like phosphorus and nitrogen are consistently in low concentrations has been
essential for the hydrocarbon-degraders development. The natural attenuation process of
oil spills is not performed at a feasible rate due to the insufficient nutrients (Atlas &
Bartha, 1973; Atlas & Cerniglia, 1995). In addition, the high initial oil spilled content has
a detrimental impact on the method of biodegradation producing a substantial 24
weeks lag phase (Zahed et al., 2010a). Microorganisms require minimum of one week to
accustom in the environment after biostimulation, and it can take months and even years
for the whole bioremediation method to accomplish (Zahed et al., 2010a). Oxygen and
temperature are the significant environmental factor where microorganism’s metabolic
rate affected by dissolve oxygen and crude oil viscosity affected by temperature (Yang,
Jin, Wei, He, & Ji, 2009). In order to increase the natural degradation method rate, immunization of polluted ocean water with microorganisms of degradation of hydrocarbon
and fertilizers incorporation or biostimulation are required for successful bioremediation
of oil spill. One of the alternatives for marine oil spill bioremediation is screening of the
microorganisms responsible for petroleum hydrocarbon degradation from earlier polluted area and immunizing them to the polluted marine water. The extensive variety of
bacteria and fungi that degrade hydrocarbons develops a serious competition among
native species and those in the culture media. Several studies reported that bioaugmentation has not a been a feasible substitute for bioremediation of oil spill (Atlas & Cerniglia,
1995). The application of fertilizers as substitutes of nutrients (nitrogen and phosphorous)
has been observed a successful performance for marine oil spills, while the widely efficacy
of bioremediation of degraded oil is restricted. The dispersant or surfactants application has
been stated to be efficacious since they improve the oil bioavailability to degraders of hydrocarbon (Zahed et al., 2010a). The phosphorus and nitrogen inclusion to the aquatic body
resulted eutrophication has been inspected. The algal blooms would not be induced by
using oleophilic fertilizers has been reported by Atlas and Bartha (1973).
13.3.5 Oil stabilzation by chemical based elastomizers
In accordance with physical approaches for ocean oil spill recovery, chemical methods
are used as they minimize the propagation of oil spills and assist to defend shorelines and
fragile marine ecosystems. Several chemical compounds are employed for oil spills treating as they have abilities to modify of oil chemical and physical properties (Vergetis,
2002). Solidifiers and dispersants are used as chemicals for oil spills controlling.
13.3.5.1 Dispersants
In accordance with physical approaches for ocean oil spill recovery, chemical methods
are used as they minimize the propagation of oil spills and assist to defend shorelines and
fragile marine ecosystems. Several chemical compounds are employed for oil spills
C. Thermo-chemical processes
242
13. Chemical stabilization of oil by elastomizers
treating as they have abilities to modify soil chemical and physical properties (Vergetis,
2002). Solidifiers and dispersants are used as chemicals for oil spills controlling.
Dispersants comprise surfactants immersed in one or more solvents. The oil slick has been
imparted effectively into small droplets by dispersants and quick dilution and easy degradation occur in the marine water column (Lessard & Demarco, 2000). Dispersants are typically employed through spraying of the chemical and water mixer and by proper mixing
has been confirmed by wind or the boat propeller (Sitting, 1974). Chemical compounds
which were formerly used are more toxic and less effective than recent existing dispersants (Lessard & Demarco, 2000). Corexit 9500, Corexit 9600, Corexit 8667, Slickgone NS,
SPC 1000, Neos AB3000, Nokomis 3-F4, Nokomis 3-AA, Finasol OSR 52, Saf-Ron Gold, ZI400 are the concentrated dispersants used for oil spill control in water (USEPA, 2011b).
Siang (1998) stated that dispersant Corexit 9500 removed oil spill in 3 weeks which was a
record and created history in Singapore (Siang, 1998). In another study, Corexit 9500 used
as a dispersant where 50%75% of No. 5 bunker slick of oil was dispersed (Davies et al.,
1998). Holakoo (2001) reported that 90% of the oil spill has been treated proficiently by dispersants which were cost-effective compared to physical methods (Holakoo, 2001).
Dispersants could be able to use on uneven seas where mechanical recovery is impossible
and heavy winds are present. In these methods fast treatment is allowed, delay the development of oil-water emulsions which provide less possibility to stick the oil to the surfaces
and speed up the normal biodegradation rate by enhancing oil droplet surface area.
Dispersants’ suitability depends on the temperature, oil categories, sea environments, and
speed of the wind (Nomack & Cleveland, 2010). Though, most of the dispersants have
inflammable nature which causes possible marine life damage and health risks of humans
during operations. Dispersants are also accountable for drinking water source pollution
and shorelines fouling.
13.3.5.2 Solidifiers
Solidifiers are also used for oil spill remediation which are hydrophobic polymers and
dry granular type materials. The reaction between oil and solidifiers transforms to a solid
rubber state from a liquid state which could simply eliminate oil through a physical process. Several forms of solidifiers like semisolid materials which comprise cakes, pucks,
balls, sponge designs, and dry particulate can be used. Pillows, booms, socks, and pads
are different forms of solidifiers (Dahl, Lessard, & Cardello, 1996; Delaune, Lindau, &
Jugsujinda, 1999). In relatively rough marine water, solidifiers can also be employed as the
sea waves produce the mixed energy that consequences in higher solidification (Nomack
& Cleveland, 2010). The solidifier efficacy depends on oil type composition. Previously,
they have not been employed widely due to the recovery of the huge amount of oil mass
16%200% by weight is required after solidification and comparatively their lower competence than dispersants (Fingas, Stoodley, & Laroche, 1990).
13.3.5.3 Stabilization by low cost chemical stabilizers/surfactants
Polyglycerol polyricinoleate and lecithin were the two basic surfactants having a low
molecular weight and mostly used in oil stabilization. Fig. 13.1A and B show the mechanism of oil stabilization by surfactants and behavior of particle attachment to the oil surface respectively.
C. Thermo-chemical processes
13.3 Oil spill stabilization/remediation techniques
243
FIGURE 13.1 (A) Schematic diagram of a W/O emulsion droplet showing different interfacial stabilization by
surfactant, biopolymers or particles. (B) The three-phase contact angle is related to the balance of surface free
energies at the particle-water, particle-oil and water-oil interfaces (Zembyla, Murray, and Sarkar, 2020). Source:
Copyright is taken from Zembyla, M., Murray, B. S., & Sarkar, A. (2020) Water-in-oil emulsions stabilized by surfactants,
biopolymers and/or particles: A review. Trends in Food Science & Technology, 104, 4959.
Killian and Coupland (2012) had reported maximum 30 wt.% oil stabilization through
the utilization of water droplets in soyabean oil. Oil stabilization by the mixture of polyglycerol polyricinoleate and stabilized water droplets was found more stable than the stabilization by the mixing of lecithin. This was attributed to the cognition of PGPR to form
elastic interfaces that slow down the rate of a coalition between several droplets (Killian &
Coupland, 2012; Marquez, Medrano, Panizzolo, & Wagner, 2010). The properties of a mixture of surfactant and stabilized water-oil emulsions were powerfully mutualist on the
lipid and emulsifier type used. The higher chemical affinity between the hydrophobic moieties of the emulsifier and the oil made the solution more stable hydro droplets. Ushikubo
and Cunha (2014) reported a study for the stabilization of water-oil emulsions in which 30
to 40 vol% of water is present, they carried out the study with three different surfactants
(namely PGPR, lecithin, and Span 80) and three different types of oils (such as, soybean oil
and hexadecane) (Ushikubo & Cunha, 2014). Higher kinetic stability ( . 14 days) and
smaller-sized water droplets (14 μm) based emulsions were found best to stabilize the oil
with the mixing of PGPR or hexadecane with Span 80. In another study, three different
types of salts (like NaCl, CaCl2 up to 0.25 M) were used to raise the kinetic stability of
PGPR and stabilized emulsions to the coalition, reducing the rate of Ostwald ripening
between oil and water phases (Israelachvili, 2015). Marquez et al. (2010) reported a study
regarding the stabilization and the effects of different salts on stabilization efficiency. A
higher degree of stabilization was found in presence of calcium salts which is basically
reduced the attractive force between water droplets. In addition to that higher adsorption
density of the emulsifier, evident by a lower interfacial tension (Marquez et al., 2010).
Israelachvili (2015) found maximum attractive force between two water droplets in the oil
continuous phase due to the same refractive indices and/or the dielectric constants of the
two phases (Israelachvili, 2015). Therefore the addition of calcium salt into the water phase
would reduce the attractive force between water droplets, reducing the collision frequency
(Israelachvili, 2015; Marquez et al., 2010). Advantages and disadvantages of all the remediation methods has been shown in Table 13.1.
C. Thermo-chemical processes
244
13. Chemical stabilization of oil by elastomizers
TABLE 13.1 Advantage and disadvantages of booms, Skimmers, and physical remediation technique of oil
spill of marine.
Booms
Advantages
Disadvantages
Curtain
booms
Oil recovery is possible, handle with all types of
oil, prevent abrasion, towing flexibility
Complex process, labor intensive, expensive,
more treatment requires for collected oil, lower
efficacy in high waves, difficulty in storage and
cleaning
Mainly comprise oil and essentially used with
different technologies, high cost, labor
comprehensive, lower constancy in strong wind
and currents, minor flexibility for towing
Fence booms Easy handling, storage and cleaning, handle
with all types of oil, probability of oil recovery,
Prevents abrasion
Fire-resistant Shoreline protection from the oil fire effect at
boom
sea,
all types of oil can be used
Lower efficacy in high waves, high cost, labor
comprehensive, low towing flexibility, oil
collected are directly burned off, difficulty in
storage and cleaning
Skimmers
Advantages
Disadvantages
Suction
skimmers
Handle with all types of oil excluding
inflammable, probability of oil recovery,
efficiently collect residue of oil
Lower efficacy in high waves, high cost,
complex process, labor comprehensive, more
treatment requires for collected oil, impossible
to use with inflammable oil products,
maintenance is needed
Wier
skimmers
Probability of oil recovery, high wave stability,
applied in low viscous, low density and
nonemulsion oil
More treatment requires for collected oil,
complex process, labor intensive, lower oil
emulsion efficacy, high cost, clogging due to
floating debris
Oleophilic
skimmers
Work well with debris or rough ice, possibility
of 90% oil recovery effective on any thickness of
oil spill in relative to water
Clogging probability due to floating debris, high
cost, further treatment requires for collected oil,
complex process, high maintenance desirable,
unable to deal with dispersants mixed oil, labor
comprehensive
Advantages
Disadvantages
Adsorption
Simple and easy process, polypropylene or
polyurethane based synthetic adsorbent have
decent hydrophobic and oleophilic properties,
all type of oil is effective as final clean up step,
maintenance is not mandatory
Selected weather conditions, labor
comprehensive, require to dispose with
guidelines, biodegradability is problematic for
synthetic adsorbents, moderate costly
Booms
Probability of all types of oil recovery
Mainly comprise oil and essentially used with
different technologies, high cost, complex
process, effective in selected weather situations,
labor comprehensive
Skimmers
Probability of all types of oil recovery except
inflammable oil
Complex process, effective in selected weather
situations, more treatment requires for collected
oil, labor intensive, costly, clogging probability
due to floating debris
Physical
remediation
method
C. Thermo-chemical processes
References
245
13.4 Future perspective for oil stabilization through chemical process
Nanotechnical engineering on emerging materials could be one of the brightest futuristic development to combat for such oil stabilization issues. Such super fine nanostructured
minute materials which are commercially employed in computational devices, can find its
applicability in cleaning of spilled oil volume because of its promising capability in
absorbing oil while repelling water. Spongy materials developed from Carbon nanotubes
(CNT) could be a strongly cited for such purposes, which looks similar as those used in
kitchens with about 1 foot length. National Nanotechnology Initiative (2016) Unlike the
kitchen sponges, such CNT sponges possess the excellent ability in repelling water molecules but reasonably high selective adsorbing efficiency towards oil, which is even about
24 times their weight within a 1/4 hour. Where the conventional adsorbents, e.g., plastic
fibrous or woolen materials show the adsorbing capacity of only about 89 times of their
mass, CNT sponges open up whole new possibilities in capturing spilled volume of oils.
This is why it has grabbed the attention of global technical and scientific research communities. Moreover, through different types of engineering modifications like the magnetic
CNT materials have also been proved to be effective in efficient isolation and removal of
oily compounds from water (Zhao et al., 2011). But, modification of CNTs in some cases
could be costly, because of which, researchers are putting immense efforts on creating less
expensive, magnetic, Fe-integrated nanostructured materials. By the addition of minute
structured magnetized constituents with coconut oil, a suspended liquid or nanofluid was
created which exhibited more than 90% effectiveness in eliminating motor oil from water
(Nabeel Rashin, Kutty, & Hemalatha, 2014). Such nano-oils adsorbs on to the target oils,
where the magnetic constituents help in removal of the magnetic particles, oil, and coconut
oil from the water.
13.5 Conclusions
Rigorous literature reviews highlight that the elastomizers could be an efficient alternative in the removal of oil spillage from marine water. With the ability to quickly capture
and immobilize spilled shells or crude oils, it can show a route toward ecofriendliness in
an economic way. Though a lot of surveys are extremely required to amplify the confidence regarding the use of such elastomer, it could be assured that the polymeric chain is
tight enough to guarantee complete binding by arresting oil droplets. Through quick capturing of spent polymers, the spilled oil volume could be reduced from the seawater
allowing proper air and sunlight mixing with marine ecosystems. Thus, the overall sustainability could be maintained from the point of view of economics and ecology by the
wise implementation of elastomizers in the treatment of oil spills from extraction sites.
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C. Thermo-chemical processes
C H A P T E R
14
Advances in burning process and
their impact on the environment
Mandira Agarwal1 and J. Sudharsan2
1
Department of Petroleum Engineering & Earthsciences, School of Engineering, UPES,
Dehradun, India 2Doctoral Research Fellow, Department of R&D, UPES,
Dehradun, India
O U T L I N E
14.1 Introduction
249
14.2 Principles
250
14.2.1 In situ burning operation
250
14.2.2 Factors affecting in situ burning 251
14.3 In situ burningtechniques & current
application
253
14.3.1 Selection of in situ burning
equipment and operation
253
14.3.2 Ignitors
256
14.3.3 Treating agents and combustion
additives
258
14.4 Environmental and health concerns258
14.4.1 Air quality
259
14.4.2 Water quality
260
14.5 Summary
260
References
261
14.1 Introduction
In situ burning (ISB) is a controlled burning process of hydrocarbon vapors arising
from oil spills. ISB technique is able to remove a larger volume of oil spill in a cost effective manner that can save the cost of collection, storage, transport, and disposal of oil
which is a typical requirement of all other oil spill response techniques (Barnea, 1995). As
it cleans up a major amount of oil quickly, it helps to restrict the oil spreading into shoreline and prevents threats to human and animal lives. In frozen arctic conditions, ISB is an
effective technique rather than mechanical and chemical methods because the ice acts as
natural barrier to prevent oil spreading and oil emulsification that allows to sustain the
Advances in Oil-Water Separation
DOI: https://doi.org/10.1016/B978-0-323-89978-9.00020-3
249
© 2022 Elsevier Inc. All rights reserved.
250
14. Advances in burning process and their impact on the environment
thickness of oil slick for longer time without any support of boom containment in order to
accomplish continuous burning. In situ burning can easily achieve oil removal efficiency
more than 90% from the water surface with maximum removal rate of 2000 m3/h. Residue
oil from ISB is less toxic compared to other oil spill responses as well as volume leftover
residue oil is also low (1%10% of original volume) (Buist et al., 1999; Buist et al., 2003;
Mabile, 2012). It also reduces the long term impact toxicity of oil spill on flora and fauna
in the sea. The generated fire remains safe and absolutely controllable throughout ISB process (Walton et al., 1999).
Environmental Protection Agency (EPA) has stated that ISB has been utilized to eliminate around 310,000 bbl of oil immediately in the area of Gulf of Mexico after the major oil
leakage into the sea environment by Deepwater Horizon (DWH) spill in 2010 (Lubchenco
et al., 2010; Schaum et al., 2010). United States Govt. provides more importance to ISB
technique for oil spill response in the sea essentially and few locations in the inland
according to National Oceanic and Atmospheric Administration (NOAA) (Ekperusi et al.,
2019; Mabile, 2012). Earlier attempts of using ISB could not produce desirable results
because of poor understanding of the process. In 1967, the attempt of using ISB technique
at Torrey Canyon incident was unsuccessful due to higher emulsification rate of oil on the
surface of water. Since then a lot of research work is being carried out to understand the
burning behavior of oil spill. The study shows ISB technique is able to remove oil contained with boom can be in the order of 50%99% (Allen, 1990). Decision makers demand
a complete understanding and assessment of ISB such as resources, feasibility, environmental conditions, and safety considerations to make a successful operation.
14.2 Principles
14.2.1 In situ burning operation
14.2.1.1 Ignition requirement
To burn the spilled oil on the surface of water, there must be three components viz.,
fuel, oxygen and ignition source. The air should be heated to the extent at which sufficient
hydrocarbons get vaporized for combustion in the air above oil slick causing the burning
of hydrocarbon vapors but not the oil spill directly, A continuous supply of vapors are
needed in order to achieve an uninterrupted burning.
14.2.1.2 Rate of heat transfer
During the burning of oil spill, Most of the heat is escaped through the combusted gas to
the environment. However small portion of heat (around 1%) must have been present in the
oil slick that will radiate the oil slick and able to vaporize them partially. This process is helpful to obtain steady state of hydrocarbon vapors quickly for the continuous burning.
14.2.1.3 Flame temperature
The temperature of flame over the oil slick must be around 1200 C and the temperature in
the interface of oil slick and water should not above the boiling point of water. Optimum temperature of the oil slick ranges between 350 C and 800 C (Fingas et al., 1995).
C. Thermo-chemical processes
14.2 Principles
251
14.2.1.4 Thickness of oil slick
If the oil slick is thicker, it can able to hold the high temperature for longer periods of
time throughout the oil spill and reduce the heating loss by preventing contact of the
water beneath the oil slick and this phase is referred as “hot zone.” When the oil slick
becomes thinner, the oil slick will lose its isolation and start to contact the water that will
stop the oil burning.
14.2.1.5 Final stage of burning
In the calm water environment after attaining hot zone phase, the thinner oil zone will
burn remaining oil droplets over the water surface quickly because the lost heat from oil
slick zone to water will keep the temperature of interface of oil slick and water above the
boiling point of water. It leads to the burning vigorously and allows remaining oil droplets
into the flame. This is called as “vigorous burning phase” and this phenomenon is not
possible if the towed boom has been used as water beneath the oil doesn’t stay longer to
get and maintain the temperature above boiling point.
14.2.2 Factors affecting in situ burning
14.2.2.1 Ignition of oil slick
The following conditions in the oil slick is needed for effective in situ burning:
• For a fresh and volatile type of oil spill, thickness of oil spill must be minimum, about
1 mm.
• If the oil spill is aged and emulsified (mostly diesel), the thickness of oil slick must be
around 3 to 5 mm.
• If the oil belongs to residual oil or Bunker “C” (fuel of electric power, space heating
etc.,) or No. 6 fuel oil (fuel for ships), the thickness requirement of oil slick is 10 mm.
Once 1 m2 area of oil spill is ignited, it is considered that ignition has been accomplished successfully.
14.2.2.2 Other factors affecting ignition of oil slick
The other prime factors that affect the ignition in addition to the type of oil are emulsification, the speed of wind and its direction, ignition strength, surrounding ambient temperature and sea waves. The wind speed must not be exceeding more than 12 m/s for a
successful ignition.
If the oil spill is weathered and oil—water emulsion is in stable condition, it can ignite
up to 25% of water whereas more water content can be ignited for meso—stable crude
(paraffinic crude) (Fingas & Fieldhouse, 1997). When the surrounding temperature is more
than the flash point of oil, the ignition will happen immediately and the flame will be
spreading rapidly.
14.2.2.3 Rate of in situ burning
The rate of oil spill burning is denoted as thickness per unit time (mm/min) which
depends on type of spilled oil, fire diameter, thickness of oil slick, sea and ambient
C. Thermo-chemical processes
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14. Advances in burning process and their impact on the environment
conditions. The diameter of fire for unemulsifed crude and diesel/jet fuel are 3.5 and
4 mm respectively.
The oil removal efficiency is influenced by the following three factors.
1. The thickness of oil slick before the ignition.
2. The thickness of remaining residue after the in situ burning.
3. How much area is covered by the flame.
The following parameters are required for the effective oil burning:
• The thickness of residue for the unemulsified oil pools must be less than 5 mm.
• When the oil spill pool is large and thicker, residue of thickness maybe higher than
5 mm.
• If the crude oil is lighter and volatile, the thickness of residue must not be exceeded
1 mm.
• When wind speed as low as 2 m/s, it is able to herd the oil to the thickness that can
support combustion.
• If the current is uniform, it can upsurge the burning efficiency and reduce the oil
residue. Excessive waves and currents over wash the oil slick that impacts the burning
efficiency adversely by increasing density and viscosity of the burn residues.
14.2.2.4 Characteristics of oil slick residue
In the case of efficient in situ oil burning (more than 85% burning efficiency) of
1020 mm thick oil slick, the produced residue looks like tar. When the oil slick is thicker
about 150300 mm, the burnt residue appears as almost solid (Ross, 1996).
14.2.2.5 Tendency of flame spreading
The flame must spread efficiently to cover a large area of oil slick and the following
two ways can yield high oil removal efficiency.
• The fire point of combustion environment can be maintained across the oil spill by
radiating the heat from flames to adjacent liquid (radiant heating).
• The hot liquid beneath oil slick can transfer the heat to cold fuel to enhance the
surrounding temperature.
The velocity of flame spreading will be reduced when oil evaporation increases or the
thickness of oil slick is reduced. If the wind speed increases, the downwind flame spreading will be also increased. Flame spreading toward upward is always slow even though
the barrier or edge breaks the cross wind speed. The regular waves do not affect flame
spreading and the steep waves restrain the flame spreading.
14.2.2.6 Flame heights
Fires with less than 10 m of diameter will produce the flame height that is almost double the fire diameter. When the fire is larger than 10 m, the almost the same size of flame
heights will be generated. If the fire is too large, the height of the flame is not possible to
estimate due to generation of high quantity of thick smoke.
C. Thermo-chemical processes
14.3 In situ burningtechniques & current application
253
14.2.2.7 Impact of emulsification
Oil spills in water environments are less likely to be combusted if emulsified and this
happens due to the presence of water in the emulsion. The water content of emulsions is
usually between 60%80% and up to 90%. The oil in the emulsion cannot exceed a temperature of more than 100 C unless the water is either boiling or eliminated. The heat
from the igniter or the adjoining burning oil is mostly used to boil the water instead of
heating the oil to its fire point.
A two-stage process is required for emulsion burning:
1. Emulsion breaking—boiling off water to produce a floating unemulsified oil layer on
the emulsion slick.
2. Eventual burning of the oil layer—performed by chemicals commonly known as
“emulsion breakers.”
The burning rate decreases significantly with rising water content for stable emulsions.
The impact of the water content on the removal efficiency of the oil water emulsions can
be outlined as below:
• Low water contents up to 12.5% by volume, have no impact on oil removal efficiency
(i.e. residual thickness);
• Water contents over 12.5% percent have a noticeable drop in burning efficiency, which
is more prominent for weathered oils.
• Emulsion slicks with water contents of 25% or more have zero burn efficiency, but
Some paraffinic crudes form meso-stable emulsions burn well at far higher water
content (Fingas & Fieldhouse, 1997)
The composition of ISB team and their work responsibilities are summarized in
Table 14.1.
14.2.2.8 In situ burning best safety practices
The best safety practices in ISB operations is attained by following the prescribed safety
protocol and safety rules and regulations. The ISB team members are required to undergo
appropriate safety training so that the team members are able to respond immediately for
a specific situation, the working personnel can be at risk from fire or flame, proximity to
excessive amounts of particulate matter, or other health and safety problems, such as operating under extreme temperatures.
14.3 In situ burningtechniques & current application
14.3.1 Selection of in situ burning equipment and operation
This section describes the different forms of major equipment that are used to respond
to oil spill for in situ burning viz., containment booms, ignitors, various treating agents,
etc. This section also describes the selection of equipment with respect to a particular
situation.
C. Thermo-chemical processes
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14. Advances in burning process and their impact on the environment
TABLE 14.1 An outline of in situ burning burning operation and personnel responsibilities.
ISB Coordinator (Responsible for the
entire burning operation)
Responsibilies of personnel
Controlling burn (Monitoring the entry
of personnel, vessel etc, and ensuring their
safety)
Boom Commander (Controlling over
the booms where it must be placed)
Traffic Control (intimating nearby the
local airport, mariners and updating them
about the burn)
Communications Unit Head
(Coordinating all ISB operations)
Locating vessels (location and movement
of vessel must be pre planned and observed
for the safer burn)
Aircraft Operation (Igniting the burn
via Helicopter)
Initiation of Ignition (Deploying the
appropriate ignitor according to the
condition of oil spill)
Safety Boat (Monitoring all vessels and
be ready with firefighting Extinguisher)
Early and Secondary fire (Avoid to
ignite unnecessarily)
Operaon during the insitu burning in the field
and organizaon
Health & Safety Officer (Responsible
of all personnel’s safety)
Planning burn (Planning the type of
vessel and ignitor deployment, sea
condition and verifying operation
checklists
Termination of Burn (Extinguishing the
fire if it harms the personnel or public
health)
14.3.1.1 In situ burning without containment
When ISB team ignite an uncontained slick, they must take safeguard that there is
no connection between the oil to be burnt and the source of the oil, such as the tanker
or oil and gas platform to keep away the fire from the source. When the oil spill
occurs from a platform or other fixed location, the part of the slick to be burnt must
be kept away from the source and the slick around the source must be separated
using the containment boom. In remote locations, shorelines, coastal sandbars or ice
may also be used to contain oil for combustion. To avoid fire spread, the shorelines
must comprise of cliffs, rocks and gravels, or sandy slopes having a reasonable gap
between the burning oil and other combustible objects such as wooden objects, forests, or vegetation cover.
C. Thermo-chemical processes
14.3 In situ burningtechniques & current application
255
14.3.1.2 Oil containment methods
Booms are used to contain the oil which also helps to maintain or increase the oil slick
thickness for the effective combustion. The various types of commercial booms are discussed in this section.
14.3.1.2.1 Conventional booms
Conventional booms cannot be used directly in burning oils because the components of
these booms are either get burnt or melted. The deployment of this boom is faster and
cheaper compared to fire resistant booms. Conventional booms may be used to restrain oil
slick before a fire resistant boom is acquired. However the boom does not stay unchanged
for a very long time once the oil starts burning. Once the boom collapses, the slick may
expand that deteriorates thickness of oil slick immediately and make them incapable to
burn. Some floating materials like logs may be used at times as temporary booms for
immediate respond.
14.3.1.2.2 Fire-resistant booms
Fire resistant booms are made of ceramic and stainless steel materials that prevent
escaping oil along with the movement of water. They are used to contain large spills in a
restricted area to burn the oil in a controlled way eliminating spilled oil spread. The top
portion of boom floats and prevents the oil escaping from the top and the bottom portion
of boom prevents the oil movement beneath water. A portion of the boom which floats on
the surface of the water prevents oil from escaping over the top, and the portion below the
surface prevents oil from escaping below the boom. The design of the boom, wind and
also wave size determine the effectiveness of the boom containing the oil.
Fire Resistant booms can mainly be categorized into four types such as Ceramic booms,
stainless steel booms, thermally resistant booms and water cooled booms. The biggest disadvantage of these type of booms is storing the heat for longer periods of time that enables
to abrade the portion of equipment. For example, during the burning of Exxon veldez oil
spill, it has been observed that flotation legs of the boom with the height of 2 m are
completely eroded due to withstand of high temperature for longer periods of time (Smith
& Diaz, 2005). In 1994, four fire-resistant booms (the American Marine (3M) Fire Boom,
the Applied Fabrics PyroBoom, the Kepner Plastics SeaCurtain FireGard, and the Oil Stop
Auto Boom Fire Model) were tested at sea by the Marine Spill Response Corporation
(MSRC) (Nordvik & Simmons, 1995). These tests aimed at evaluating the link between the
boom strength and buoyancy-to-weight, towing speed and maritime condition. At towing
speeds between 0.25 and 1.25 m/s the boom were towed in a U configuration (0.5 and
2.5 knots). It has been observed that Mechanical failure was discovered on three out of the
four fire resistant booms. It was stressed that technical stability of the booms, ease of
deployment, and recovery must be enhanced for efficient oil containment.
The USCG (United States Coast Guard) and USMMS (United States Mineral
Management Services) in a test tank, assessed the containment behavior of current fire
resistant booms and correlated their performance to previous at sea performance (Bitting,
1997; Nash et al., 2000). The study calculated the tow speeds at which the booms started to
lose oil for the initial time (“first loss”) and the speed at which, subsequent loss occurred
C. Thermo-chemical processes
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14. Advances in burning process and their impact on the environment
(“gross loss”). The study also calculated the rate of loss of oil at particular tow speeds and
the tow speed at which the boom physically collapsed and submerged.
The fire resistant booms presently in market are described as below.
a. American Fire Boom:
Its floating components are composed of rigid ceramic foam that are surrounded by
two sheets of knitted mesh of stainless steel, a ceramic textile fabric that resists high temperatures and an outside cover of PVC which also form the skirt.
b. Auto Boom Fire Model:
It’s an inflatable boom with in-built water-cooling-system. A ceramic blanket with a
stainless steel mesh is used to insulate the flotation chamber and polyurethane cloth is
used for the skirt. This type of boom can be stored and a reel may be used for its deployment. The water cooling system must be connected on a large, flat area before the boom is
placed in the water.
c. FESTOP Fire Boom:
The boom is made up of stainless steel that can withstand temperatures up to 1260 C.
d. The Hydro-Fire Boom:
It is inflatable and water cooled 150 m long boom that can be stored on a reel with 30 m
sections and deployed from the reel.
e. PyroBoom:
This is a fence boom, with a freeboard built of a patented refractory component that is
highly resistant and a skirt made of urethane coated material. Either side of the fence is
connected with hemispheric stainless steel floats. This boom can be deployed from a reel
system which is stored in a container else the boom may be stored in a container and
deployed from a large flat area.
f. SeaCurtain FireGard (Kepner Plastics):
The flotation parts of the boom are formed by a heavy stainless steel coil that has been protected by a high-temperature refractory material. A polyurethane-coated polyester or nylon cloth
is used to make the skirt. During deployment, the stainless steel coil allows the boom to self
-inflate, but recovery requires manual compacting. At present, the boomer is not actively used.
14.3.1.2.3 Backup booms
Backup booms must be set at least 200300 m behind the fire resistant booms to contain
any entrained or spilled oil during the burning. It has been noticed that oil flow out of the
fire-resistant boom will in general pool behind the boom due to eddies developed in this
region. Usually, this oil remains in this region for some time and may thus can be ignited
for the combustion. If this oil leakages from this place, it would become too thin to withstand combustion and in this case, backup boom may be used to collect the leaked oil.
14.3.2 Ignitors
A variety of ignition techniques have been used to ignite the oil slick. However the
methods of igniting oil on water have not been broadly documented (ASTM F199007,
C. Thermo-chemical processes
14.3 In situ burningtechniques & current application
257
2007; McKenzie, 1994). An ignition system must have basically two parameters in order to
be effective. The first parameter is that it should produce sufficient heat to generate
enough oil vapors to ignite the oil and then maintain it burning and the second parameter
is that it must be safe to use. Thicker, volatile and less weathered oil can be ignited quickly
and easily whereas the heavy oil, unstable emulsions take longer time to ignite to achieve
the enough vapors. Propane and butane torches were successfully used in the past to
ignite oil spills in the past. They are more successful on dense slicks, though, as the torches
likely to blast the oil away from the flame on thin slicks, thereby hindering ignition.
14.3.2.1 Helitorches
The most advanced industrial devices used for ignition of oil slicks are helitorch igniters. These ignitors are suspended from helicopter that dispense packets of burning and
gelled fuel, resulting a fire with 800 C lasting up to 6 min (Allen, 1986; ASTM F199007,
2007). The helitorch fuel is a mixture of a powdered gelling agent along with either jet fuel
or diesel/gas or gasoline. In general, Aluminum soap is used as gelling agent. When planning to use a helitorch, the gelling agent and the fuel must be combined in a safe environment away from any ignition source. In the specialized barrels with the raised hatch
opening, the fuel is mixed with the gelling agent.
The appropriate ratio between the fuel and the gelling agent mainly depends on the
fuel type and air temperature. If the flash point of oil slick is low, less volume of gelling
agent is needed. In general, unleaded gasoline is commonly used as fuel because it is readily available. For ignition, it is recommended to hook the torch in right angle to the frame
so that it helps the pilot to track the ignition cap.
14.3.2.2 Noncommercial ignitors
The other ignition techniques are use of rags, sorbent or paper soaked in oil to ignite
the oil slick (ASTM F199007, 2007), for example, plastic bags containing gelled fuel was
used to ignite the oil during Exxon valdez spill. The bag was fired and thrown out of the
boat towards the slick. Diesel becomes a better choice when compared with gasoline for
soaking materials as it burns slowly. Combustion of heavy oils is best accomplished using
a diesel fuel and kerosene, and a tiny wick such as a sorbent or a cardboard (Fingas et al.,
2003). These Igniters comprise of gelled fuel, gelled kerosene cubes and solid propellants
or mixture of these compounds that can provide fire ranging between 1000 C and 2500 C
lasting from 30 sec to 10 min (ASTM F199007, 2007).
14.3.2.2.1 The kontax igniter
It is self-igniter unit that was tested and in use since 1970 (ASTM F199007, 2007). The
device was made of a calcium carbide filled cylinder with a sodium metal bar that passes
through the center. When it was dropped into the oil slick, sodium from the bar react with
the water to produce heat and hydrogen. Furthermore, acetylene was generated when
water and calcium carbide are reacted together. The flames from burning acetylene was
maintained long enough to heat the oil and to generate the vapors that were eventually
ignited. The main disadvantage of this ignitor is that it may cause blasting, if it is exposed
with water molecules.
C. Thermo-chemical processes
258
14. Advances in burning process and their impact on the environment
14.3.2.2.2 A hand-held igniter
This type of ignitor was used for in situ burning experiments conducted in 1996 in the
coast of Great Britain (Guenette & Thornborough, 1997). This igniter consists of a bottle of
1-L “Nalgene” polyethylene packed with gasoline gel. The gel is prepared by combining
1 L of gasoline with 10 grams of gelling agent. This container and a traditional hand-held
flare are held in two polystyrene foam rings. The flare is ignited and placed onto the slick
and it burns about 60 s until the plastic container is melted and the gelled fuel is burned
to ignite the oil slick. This device is simple and easy to deploy in the field.
14.3.3 Treating agents and combustion additives
The various type of combustion supporting materials that are used to enhance in situ
burning have been listed in the Table 14.2.
14.4 Environmental and health concerns
The main environmental and health issue linked to in situ burning is the pollution
caused by spilled oil and its combustion. Thus, the most important concern during the oil
spill response is ensuring the health and safety of the people, the response crew and the
aquatic environment. Human, marine and terrestrial life are exposed to the impacts of ISB
operation mainly through inhalation of burnt particulates, ingestion and skin adsorption
TABLE 14.2 List of Additives used for ISB operation.
Classification
S. No of additives
Function of the additive
Examples
Description of the
additives
1
Ignition
promotors
Used to enhance ignitibility and
spreading of flame to unignited
oil slick area.
Fresh crude, aviation
gasoline, gasoline, kerosene
and diesel.
Must have lighter
density that would
minimize the safety
hazard.
2
Combustion
promotors
Used to improve the oil removal
efficiency during the
combustion.
Peat moss
Acts as a wick or the
insulator between oil
slick and water.
3
Smoke
suppressants
Added in oil slick to reduce the
smoke.
Lead, magnesium,
manganese, copper, iron,
nickel, boron, cobalt and
barium
Must be nontoxic
4
Sorbents as
wicking
agents
Used in smaller oil spill where it Polypropylene sorbent
must have the access of manual sheets and pads.
application of sorbent.
Must be nontoxic
5
Emulsion
Breakers
Used to break the oil—water
emulsion in situ and remove
water molecules.
Highly oil specific and
surfactant dependent.
Gamelin EB439, Vytac DM,
and Breaxit OEB-9,
C. Thermo-chemical processes
14.4 Environmental and health concerns
259
from the spilled oil and burned residue. Particulates emanated from ISB is majorly classified as PM10 (mixture of liquid droplets and solid particles 010 μm diameter) and PM2.5
(finer particles of # 2.5 μm). The particulates less than 10 μm diameter can be easily
inhaled and reached the lungs causing its damage. The United States Occupational Safety
and Health Administration developed a detailed training method for oil spill responders
under the Hazardous Waste Operations and Emergency Response Standard in 29CFR
1910.120.
14.4.1 Air quality
ISB operation for oil spills causes air emission that include smoke, particulate matters,
organic and nonorganic gases produced from combustion, unburned residue at the oil
spill site. This section focuses on the volume and the rate of air emission after an ISB operation. The primary concern is the smoke considered as toxins that is produced during ISB
operation. The major emission compounds from ISB has been listed in the Table 14.3.
TABLE 14.3
List of various compounds emitted to air from ISB combustion.
S. No Name of the compound
Description
1
Particulate matter/soot
Particulate matter emission from oil slick is at least four times higher than burning diesel.
Particulates in the form of soot contains 10%15% of smoke plume. Density of particulate
matter is more than 150 mg/m3 at the ground level.
2
Polyaromatic
hydrocarbons (PAHs)
It can be seen in the residue post ISB in the form smoke or particulates. It may harm the skin
and lungs when its concentration is more than 0.2 mg/m3.
3
Volatile organic
compounds (VOCs)
More than 140 different types of VOCs have been recognized from various ISB operation and
experiments. Because of its low concentration, it does not pose a major human and
environmental threat.
4
Carbon monoxide
Incomplete combustion produces CO which displaces oxygen from the blood affecting
hemoglobin molecules in the red cell and decreases the oxygen level of cells immediately.
The average CO level in the smoke plume has been found to be 15 ppm in some test burns
for over a period of 1530 mins and 150 m downwind from the burns,
5
Sulfur dioxide
It is toxic and irritate eyes and affect the respiratory system when its concentration exceeds
5 ppm in the atmosphere. In few test burns, the average level sulfur dioxide has been found
less than 2 ppm in the plume (100200 m downwind). It has been concluded that there is not
much threat for population from SO2 caused by ISB operations because of low concentration.
6
Nitrogen oxide
It also affects the lungs and eyes similar to SO2. Even a smaller dose of it can cause
pulmonary edema as it is less soluble than SO2 and can reach the deep part of the lungs.
7
Carbon Dioxide
Around 500 ppm concentration of CO2 emission has been noted nearby oil burn. However
this range does not impact much to any species/human kind
8
Dioxins and
Dibenzofurans
They are highly toxic and they are generated from the crude oil that possess chlorine and not
found in other type of crude oil like Diesel etc.
9
Carbonyls
They are partially oxidized materials and are produced from oil burns. They are found in
very low concentrations and causes no threat even near the oil burn. Its concentration gets
higher in case of fuel containing alcohol.
C. Thermo-chemical processes
260
14. Advances in burning process and their impact on the environment
14.4.2 Water quality
The impact of ISB operation on marine environment is very minimal and causes almost
zero threat. Most of the heat produced during a burn moves upward and outward resulting a very negligible absorption of heat by the underlying water below the oil burn. Most
of the controlled burns remove maximum amount of oil and leave only low quantity of oil
as tar like floating residue that can be easily collected and stored in a temporary storage.
However threats to the aquatic lives are extremely low for residues either thermally soluble on water or in case they sink beneath water surface.
Research has demonstrated that in situ oil burning would not release more oil components or by-products of combustion into the water column than are present if the oil is left
without burning on the water surface (Fingas & Li). Test results for the water taken from
burned-out oil field show that it does not contain any organic compounds or may contain
very ignorable volume of hydrocarbon which is not harmful to any sea plants and species
(Daykin & Kennedy PA, 1995; Fingas & Li, Fingas et al., 2005), no PAH or toxicity have
been detected in the samples. The oil burned residue consists mostly of volatile oil (Fingas
et al., 1997; Fingas et al., 2000) since the burning phase removes most of the nonvolatile
materials. The residues may possess a significant amount of metals (typically 10 to 40 ppm
nickel, vanadium and chromium) (ASTM F178808, 2008). Several researches have proved
that burned oil residue is less toxic than other weathered oil or fresh oils of the same kind
which is more harmful to marine life. Sinking of burnt residue is the major toxic pollutant
to the species. But fortunately it happened in very few burns 2 in 200 burns only
(Compilation, 1997) The residues can be easily collected by skimmers and sorbents.
Studies show that there is no noticeable rise in water temperature even in shallow water
because the oil slick layer itself insulates the water zone.
The density of burnt residue is always higher than density of oil in its spilled condition.
To understand the behavior of burnt residue, the burnt residue sample of Haven oil spill
and fire 1991 have been investigated and the results showed that the sample resembles the
characteristics of heavy oil and the burnt residues were mainly composed of highly concentrated asphaltenes, resins and metals (Moller, 1992). Sometimes residue may contain
pyrogenic and Poly aromatic hydrocarbon compounds. ISB technique has been in use to
remove the oil from some major oil spill incidents for number of years. The oil removal
efficiency of ISB has been described in Table 14.4.
14.5 Summary
This chapter has deliberated the principles of ISB, its equipment used during combustion and also highlighted the environmental impacts on air and water quality caused by
ISB operations. Though the public believes that ISB technique is not always practically
possible but the oil removal efficiency by ISB can be more effective and efficient if the
spilled site condition is well monitored and preplanned prior to conduct of the operation.
It should be kept in mind that an ISB operation can only be successful if it can assure the
safe working condition for the response personnel. More research studies need to be
carried out in developing the strategy to increase the performance and deployment of
C. Thermo-chemical processes
261
References
TABLE 14.4
Major oil spills and in situ burning responses.
S. No Name of the oil spill incident
Date of incident
Type of oil
Spilled
volume
Oil removal volume
by in situ burning
1
Trans-Alaska Pipeline, Fairbanks,
Alaska
15 February 1978
Prudhoe Bay crude oil
(API gravity 5 29 degrees)
16,000
bbls
500 bbls
2
Exxon Valdez Test Burn
24 March 1989
North Slope crude oil
(API 5 29 degrees)
257,000
bbls
350700 bbls
3
Chiltipin Creek, Texas
7 January 1992
South Texas Light crude
oil
2950 bbls
1150 bbl
4
Brunswick Naval Air Station,
Brunswick, Maine
26 March 1993
JP-5 aviation fuel
1512 bbls
500 bbls
5
Newfoundland Offshore Burn
Experiment, Newfoundland,
Canada
12 August 1993
Crude oil (API 5 36
degrees)
970 bbls
970 bbls
6
Refugio County, Texas
12 May 1997
Light and giddings steam
crude
5001000
bbls
Not exactly known
(90% volume burned)
7
‘Mosquito Bay, Louisiana
5 April 2001
Condensate (a very light
crude oil)
.1000 bbl .500 bbls
river—fire resistant booms and improving the safety of hand held ignitors such as delaying to spark time that will allow the response personnel to move comfortably after ignition. ISB is one of the best suitable technique in artic and polar regions and able to achieve
99% oil removal efficiency in the shortest time in the offshore. USCG has also appreciated
the efforts of ISB that the environmental threat is almost eliminated after conducting the
ISB rather than leaving oil over the water surface.
References
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Program (AMOP) technical seminar, 9th proceedings. Ontario, Canada, vol. 2, no. NIST SP, pp. 353373.
Allen, A. A. (1990). Contained controlled burning of spilled oil during the Exxon Valdez oil spill. Spill Technology
Newsletter, 15(2), 15.
ASTM F1788-08. (1788). Standard guide for in-situ burning of oil spills on water: environmental and operational considerations. West Conshohocken, PA: ASTM International.
ASTM F1990-07. (1990). ASTM standard guide for in-situ burning of oil spills ignition devices (pp. 19901997).
Conshohocken, PA: ASTM.
Barnea, N. (1995). Health and safety aspects of in-situ burning of oil. Seattle, WA: National Oceanic and Atmospheric
Administration, p. 9.
Bitting, K. R. (1997). Oil containment tests of fire booms. AMOP, p. 735.
Buist, I., Dickins, D., Majors, L., Linderman, K., Mullin, J., & Owens, C. (2003). Tests to determine the limits to in
situ burning of thin oil slicks in brash and frazil ice. Proc. Seventh Annual Arctic Marine Oilspill Program
Technical Seminar, Environmental Protection Service, Environment Canada, 26(2), 629648.
Buist, L., McCourt, J., Potter, S., Ross, S., & Trudel, K. (1999). In situ burning. Pure and Applied Chemistry. Chimie
Pure et Appliquee, 71(1), 4365. Available from https://doi.org/10.1351/pac199971010043.
Compilation of physical and emissions data (1997). Newfoundland Offshore Burn Experiment (NOBE) report.
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Daykin, M.M., Kennedy, P.A., A. Tang (1995). Aquatic toxicity from in-situ oil burning Newfoundland Offshore Burn
Experiment (NOBE). Ottawa. Environment Report.
Ekperusi, A. O., Onyena, A. P., Akpudo, M. Y., Peter, C. C., Akpoduado, C. O., & Ekperusi, O. H. (2019). In-situ
burning as an oil spill control measure and its effect on the environment. In Society of petroleum engineers—SPE
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Fingas, M., & Li, K. The Newfoundland offshore burn experiment-Nobe Working on new dispersion model view
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Fingas, J. V. M. M. F., & Fieldhouse, B. (1997). Proceedings of the twentieth arctic and marine oilspill program technical
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Fingas M., et al. (2000). Emissions from mesoscale in-situ oil (Diesel) fires: Emissions from the mobile 1998 experiments. In Environment canada arctic and marine oil spill program technical seminar (AMOP) proceedings, vol. 23, no.
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Fingas, M., et al. (1997). Particulate and carbon dioxide emissions from diesel fires: The mobile experiments.
Fingas, M., Lambert, P., Goldthorp, M., & Gamble, L. (2003). In-situ burning of orimulsion: Mid-scale burns
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Fingas, M. F., et al. (2005). The Newfoundland offshore burn experiment—nobe. In 2005 international oil spill conference, IOSC 2005, vol. 1995, no. 1, pp. 51915207, doi: 10.7901/21693358-19951123.
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C. Thermo-chemical processes
C H A P T E R
15
Use of chemical dispersants for
management of oil pollution
Sunil Kumar Tiwari1,2, Shashi Upadhyay3, Vishal Kumar Singh1,
Ankit Dasgotra1,2, Akula Umamaheswararao1, Harsh Sharma1
and Jitendra Kumar Pandey4
1
Department of Mechanical Energy, University of Petroleum and Energy Studies, Energy Acres,
Dehradun, India 2Department of Research and Development, School of Engineering, University
of Petroleum and Energy Studies, Dehradun, India 3Department of Microbiology, University of
Petroleum and Energy Studies, Energy Acres, Dehradun, India 4School of Basic and Applied
Science, Adamas University, Kolkata, India
O U T L I N E
15.1 Introduction
264
15.2 Hazardous effect of oil spill and its
emission
265
15.2.1 Need for controlling oil
pollution
266
15.2.2 Oil spill remediation
266
15.3 Use of chemical dispersant
267
15.4 Principle and mechanism of
chemical dispersants
269
15.4.1 Impact of chemical dispersants 270
15.4.2 Toxicity of chemical dispersants 273
Advances in Oil-Water Separation
DOI: https://doi.org/10.1016/B978-0-323-89978-9.00004-5
15.5 Effectiveness and adaptability of
chemical dispersants
273
15.6 National and international regulations
for using chemical dispersants
276
15.7 Applications of different chemical
dispersants
277
15.8 Conclusions
278
References
279
263
© 2022 Elsevier Inc. All rights reserved.
264
15. Use of chemical dispersants for management of oil pollution
15.1 Introduction
Oil pollution in general terms can be explained as a release of oil or petroleum hydrocarbons in an open environment which causes disparities in an ecosystem. Mostly oil pollution
is seen in aquatic ecosystems in the form of oil spills. Major sources of oil pollution/oil spills
are accidents in vessels, leakage from ships, accidents near oil exploration areas, etc. As
petroleum hydrocarbon is one of the most important sources of revenue, the majority of
petroleum producers transport oil/petroleum via sea, oceans, and other water bodies. While
TABLE 15.1 Major oil spills from 1967 to 2010 (Aguilera, Méndez, Pásaroa, & Laffona, 2010;
Jackson et al., 1989; Laffon, Pásaro, & Valdiglesias, 2016; Osuagwu & Olaifa, 2018; Saadoun, 2015).
S. no.
Year
Amount
Location
1.
1967
119,000 tons
Cornwall, United Kingdom
2.
1972
115,000 tons
Gulf of Oman, Oman
3.
1975
88,000 tons
Portugal
4.
1976
100,000
La Coruna, Spain
5.
197696
2 million barrels
Niger Delta, Africa
6.
1978
231,000 tons
Brittany Bay, France
7.
1979
287,000 tons
Off Tobago, West Indies
8.
1979
94,000 tons
Bosphorus, Turkey
9.
1980
100,000 tons
Navarino, Greece
10.
1983
252,000 tons
Off Saldanha Bay, South Africa
11.
1985
70,000 tons
Off Kharg Island, Iran
12.
1986
8 million liters
Caribbean Coast, Panama, America
13.
1988
132,000
Nova Scotia, Canada
14.
1989
40 tons
Alaska, United States
15.
1989
70,000 tons
Atlantic Coast, Morocco
16.
1991
6 million barrels
Gulf of Mexico, Mexico
17.
1991
260,000 tons
Angola
18.
1991
144,000 tons
Genoa, Italy
19.
1992
74,000 tons
La Coruna, Spain
20.
1992
67,000 tons
Off Maputo, Mozambique
21.
1993
85,000 tons
Shetland Island, United Kingdom
22.
1996
72,000 tons
Milfold Haven, United Kingdom
23.
1999
20,000 tons
Brittany, France
24.
2002
77,000 tons
Spain
25.
2003
37,000 tons
Karachi, Pakistan
26.
2007
2.7 million gallons
South Korea
27.
2010
4 million barrels
Gulf of Mexico, Mexico
C. Thermo-chemical processes
15.2 Hazardous effect of oil spill and its emission
265
transportation, oil spill (if occurs due to shipwreck, etc.) in water bodies not only harm
aquatic life, it also has an adverse effect on plants and humans (Tuan Hoang, Viet, Pham, &
Nam Nguyen, 2018). It damages lungs and other internal organs of aquatic animals; it also
causes air pollution once it gets evaporated; it damages plants growth and their life if it
comes into their contact. Some of the most well-known oil spills are shown in Table 15.1.
Looking into the hazardous effect of oil spill on living species and nonliving things there is
a great need of oil spill removal and its management. The most valuable and risk-free
approach to fight against the oil spill is to remove it via physical and mechanical methods
which includes removal of oil spill water zone by pumping or to stop its further physical containment. Due to the limited availability of advanced machinery and equipment, mechanical
methods covers a short part of affected spill area which results in retrieval of about 20% of
leaked oil (Lessard & DeMarco, 2000). Moreover, if this method is not acceptable due to sea/
ocean/water bodies conditions, then there comes the need of oil spill treatment. Since 1960,
dispersants have been used to control and treat oil spill in water bodies. Dispersants are a
kind of detergents which are spread on the oil spilled surface to separate and/or disperse oil
from water. The major concern with use of dispersants in oil spill is their toxic nature and
nonrecovery of spilled oil. But according to research council of United States, the major concern of toxicity for aquatic animals was with spill oil droplets not with dispersants used
(Lessard & DeMarco, 2000). Several researchers have worked on using dispersants for oil spill
remediation, and they have also gotten better results in terms of oil water separation to prevent water pollution. This chapter reflects the use of chemical dispersant for oil spill treatment
and management.
15.2 Hazardous effect of oil spill and its emission
It is well known that most of the crude oil contains hydrocarbons whose spill in waterbodies can lead to damage both aquatic and terrestrial network. Petroleum oils containing
low hydrocarbons like aromatics and alkanes evaporates in the atmosphere quickly due to
their high vapor pressure (Afshar-Mohajer, Fox, & Koehler, 2019). Concentration of these
organic compounds in oil spill zone decreases, as it is time dependent but on the other
hand it releases aromatics like xylene, toluene, benzene, ethylbenzene, etc., which are very
harmful in terms of health impacts. As per air quality guidelines WHO 2000, these
exposed fumes and chemicals cause headache, eye irritation, and can also lead to lung
cancer and mental disturbances to humans if inhaled or due to dermal interaction
(Solomon & Janssen, 2010). Once the oil is spilled, its impact on marine and human life
depends upon the fate and nature of oil spill dispersion. If oil is not dispersed in water, it
remains suspended on the surface of water and flows towards the coastal areas due to the
impact of water current resulting in harming coastal organisms including mammals and
birds. In the case that the oil gets dispersed in water, its toxic nature can harm aquatic animals if they swallow it (Saadoun, 2015). The major effect of oil spilled in the marine environment is narcosis which is caused due to oil reaching to the cells of nervous tissue and
cell membrane of aquatic animals. Moreover, cleanup operation in regard of oil spill is
also responsible for affecting marine life (Saadoun, 2015). Some of the reports on impact of
oil spill on aquatic life and human health have been shown in Table 15.2.
C. Thermo-chemical processes
266
15. Use of chemical dispersants for management of oil pollution
TABLE 15.2 Effect of oil spill on aquatic and human life.
Source
Effect on aquatic and human life
Evaporated volatile organic
compounds from oil
Throat irritation, respiratory irrigation, depression in humans, mammals
and birds
Benzene
Causes Leukemia in humans
Toluene
Malformation of an embryo in humans
Naphthalene
Causes cancer to humans, nasal tumors and cancer to animals too
Hydrogen sulfide
Acute and chronic effect on central nervous system
Heavy metals
Acute and chronic effect on central nervous system
Physical contact with spilled oil
Defatting and skin infections, also causes edema, erythema, etc., to birds
and furred mammals.
15.2.1 Need for controlling oil pollution
Petroleum oil contains a chain of hydrocarbons which is harmful for aquatic animals if spilled
in marine environment. As it is toxic in nature it can cause death to aquatic animals and indirectly
affect human health as aquatic animals are a part of the food chain. Its smoke and fumes, when
evaporated; cause air pollution too. Their contamination with other water bodies puts aquatic life
and farmlands in danger. Looking into the hazardous effect of oil spill on human health, aquatic
animals, and the ecosystem, many researchers have worked on preventing and controlling oil
spills in the marine ecosystem (Ji, Xu, & Wang, 2016; Teal & Howarth, 1984; Tuan Hoang et al.,
2018). They have used different physical and mechanical approaches to remove spilled oil from
water. But these methods are not too efficient to be used so that effectiveness can be seen in short
period of time. Some of the researchers have used different biological and chemical dispersants to
treat oil spill. It has been reported that use of chemical dispersants too has adverse effect on the
living organisms. As chemical dispersants are toxic in nature, they indirectly affect human health.
So looking into the oil spill treatment and management it has been suggested to use cellulose
nanocrystals instead of chemical dispersants (Parajuli et al., 2020).
15.2.2 Oil spill remediation
Due to the unwanted contamination of oil spill with ecosystem, it is very important to
remediate (Prendergast & Gschwend, 2014). Selection of methods to treat oil spill to promote remediation depends upon nature of oil spill, oil spill location, government regulations associated with the location, type of oil and behavior of water spilled zone. The most
common remediation approaches studies by researchers are mechanical methods, use of
chemical dispersants, and in situ burning of oil. Studies have revealed that physical and
mechanical methods are the best adopted approach to control and prevent oil spill but it
lacks in efficiency and is time taking too. Chemical dispersants have good efficiency but
are restricted in local areas by government and also contribute to the chemical contamination of water for long time and thus harms aquatic lives (Sakthivel, Reid, Goldstein,
Hench, & Seal, 2013). Carmodi et al., have confirmed that use of organoclays is able to
C. Thermo-chemical processes
267
15.3 Use of chemical dispersant
treat oil spill because of its hydrophobic nature, retention capacities and hydrocarbon
sorption property (Carmody, Frost, Xi, & Kokot, 2007). Chhatre et al., have explained that
use of bacterial consortium has resulted in better oil spill treatment as it shows effective
degradation of crude oil.
15.3 Use of chemical dispersant
The main aim of using chemical dispersants is to remove the spilled oil from the surface
of sea water. When the chemical dispersants come in contact with spilled oil, the surfactants present in the chemical dispersant significantly decreases the force of attraction
between the oil and water molecules (Wilkinson et al., 2017). This reduction in interfacial
force is achieved by positioning the interaction of hydrophobic shells with oil and hydrophilic shells with water, which automatically forms a stable microemulsion (Marzuki,
Wahab, & Hamid, 2019). This enhances breaking of oil into tiny droplets, which increases
the biodegradation of oil in sea-water (Tremblay et al., 2017). Some other studies also
stated the effects on using chemical dispersants for oil spill treatment up the marine ecosystem (Kleindienst, Paul, & Joye, 2015). This formation of microemulsion mainly depends
on the structure and type of surfactant used as shown in Fig. 15.1. According to Doshi,
Sillanpää, and Kalliola (2018) there are four types of microemulsion as listed Table 15.3.
Chemical dispersants mainly consist of surfactants, solvents, and stabilizer.
Surfactants generally decreases the formation of oil in water emulation, to spread and
Classification of surfactants used for oil spill treatment
Bioremediation of spill oil
Surfactant
Dispersants
Break the spill oil
into smaller droplets
Chemical herders
Thicken or contract
the spiil oil that can
be collected
Bioemulsifiers
Enanhance the
biodegrdation of oil
by microbes
Biosurfactants
Enanhances the
solubility
FIGURE 15.1 Classification of surfactants used for oil spill treatment (Doshi et al., 2018).
TABLE 15.3
Different types of microemulsion with their principle (Doshi et al., 2018).
Types
Principle
Type I
Oil in water microemulsion were formed in which surfactant is soluble in water but insoluble in oil phase.
Type II
Water in oil microemulsion were formed in which surfactant is soluble in oil but insoluble in water phase.
Type III
Three phase system in which middle of oil and water phases a surfactant phase will be formed that will result in oil
in water or water in oil microemulsion.
Type IV
A micellar solution with single phase which formed upon addition of sufficient amount of surfactant with alcohol.
C. Thermo-chemical processes
268
15. Use of chemical dispersants for management of oil pollution
improves the biodegradation and consists of dioctyl-sodium-sulfosuccinate (DOSS),
Tween80, Tween85, dioctyl-sodium-sulfosuccinate (DOSS) hydrolysis product α-/βethylhexyl sulfosuccinate and Span8 (Place et al., 2016). Solvent’s function is to
decreases the viscosity of surfactant, dilute the compound of chemical dispersants and
optimizes the concentration of chemical dispersants and solvents consists of petroleum
distillates, petroleum hydrocarbons, kerosene and fuel oil. Stabilizers are used for controlling corrosion, exact color and exact pH value (Dave & Ghaly, 2011). The size of oil
droplet has an important impact for reduction of interfacial force between oil and
water. A sample of Macondo oil premixed with COREXIT 9500 dispersant and coastal
Norwegian seawater shows that 10 μm sample is faster biodegradable than 30 μm dispersion (Brakstad, Nordtug, & Throne-Holst, 2015). Fig. 15.2, shows different types of
chemical dispersants.
Usually, COREXIT 9500 An and COREXIT 9500 were used as dispersants in Deepwater
horizon oil spill and they contain dioctyl-sodium-sulfosuccinate (DOSS) as a main surfactant component (Gray et al., 2014). COREXIT 9500 was the improved version of COREXIT
9527 as the COREXIT 9527 is too toxic (Mitchell & Holdway, 2000). COREXIT holds different components including polyethoxylated sorbitan, isosorbide, fatty-acid core groups,
and their monoesters, diesters, triesters, and tetraesters (Chang, 2019). An explosion on
April 20, 2010 (28 5501200 N, 88 2301400 W) resulted in the leakage of crude oil into the
Gulf of Mexico at an estimation of 11.2 million liters of oil. Which leads to the large oil
spill in the coastal waters of United States of America. A wide range of chemical dispersants were sprayed on surface and subsurface waters, approximately 3.7 million liters of
chemical dispersants were used in the response of oil spill. Among those COREXIT
EC9500A is the mostly commonly used chemical dispersant (Noirungsee et al., 2020). By
using etherification of octadecylamine along with tetraethylene glycol and quaternization
with p-toluene sulfonic-acid an amphiphilic ionic liquid was synthesized and this synthesized amphiphilic ionic liquid showed an oil spill dispersant efficiency around 80% at a
ratio of surfactant/oil- 1:25 (Atta, Al-Lohedan, Abdullah, & ElSaeed, 2016). Slickgone-NS
is one of the most commonly used and approved chemical dispersant across European
countries for oil spill response. Slickgone-NS has a dispersant to oil ratio of 1:25 (Brakstad,
Ribicic, Winkler, & Netzer, 2018). Generally, the chemical dispersants having LC-50 more
FIGURE 15.2 Different
types of chemical dispersants (Nnadozie et al.,
2017).
Chemical dispersants
Conventional
hydrocarbon
base
Water dilutable
concentrate
Generally used in
undiluted form at
a ratio of 1 part
chemical
dispersant to 2-3
part of oil
Dilution with seawater in the ratio of
1:10 and then used
at a ratio of 1 part
chemical dispersant
to 2-3 part of oil
Concentrate
Combination
Chemical dispersants
containing higher
concentraction of
surfactants
These are new
type of
chemical
dispersants
synthasized
both for water
dilutable and
concentrate
C. Thermo-chemical processes
15.4 Principle and mechanism of chemical dispersants
269
TABLE 15.4 Different chemical dispersants with their optimized ratio
of dispersant/oil (Dave & Ghaly, 2011).
Chemical dispersant
Optimized ratio of dispersant and oil
COREXIT-7664
1:3
COREXIT-9500
1:101:50
COREXIT-9527
1:201:30
COREXIT-9550
1:20
ARDROX-6120
1:25
TERGO-R40
1:20
Shell VDC
1:201:30
Neos-AB3000
1:20
Slickgone-NS
1:25
than 1000 mg/L are assumed as very less toxic. Sea-Green-805 (LC-50 5 8900 mg/L),
Hytron-3 (LC-50 5 1500 mg/L) and Neos-AB3000 (LC-50. 12500 mg/L) are the commonly
used chemical dispersants for oil spill response in the diamond grace, Tokyo Bay, 1997
these chemical dispersants have LC-50 more than 1000 mg/L (Holley, Lee, Valsaraj, &
Bharti, 2021). Some of the chemical dispersants commonly used now a day are listed in
Table 15.4. Due to the development in science and technology the chemical dispersants,
which are available are more effective and less toxic in nature. The most widely used and
accepted by many environmental organizations chemical dispersants are COREXIT-9500,
COREXIT-9500A, COREXIT-9580, ARDROX-6120, Slickgone-NS, Slickgone EW, Slickgone
LTSW, Neos-AB3000, SPC-1000, Hytron-3, Finasol-OSR-52, Shell VDC, Enersperse 700,
Nokomis 3-AA, Nokomis 3-F4, TERGO-R40, Sea-Green-805 (Brown, Fieldhouse, Lumley,
Lambert, & Hollebone, 2011).
15.4 Principle and mechanism of chemical dispersants
Oil slicks are broken up into fine droplets that settle naturally in the sea using chemical
dispersants, which are liquid mixes of surfactants and solvents. Surfactants, which are
surface-active agents with molecules consisting of opposing polarity and solubility groups;
that is, surfactants typically have both an oil-soluble hydrocarbon chain and a watersoluble group, are used in dispersants. Surfactants are also used extensively in the cosmetics and food industries. The surfactant molecules in oil spill dispersants achieve their
lowest energy state by placing themselves at oilwater interfaces, lowering the oilwater
interfacial stress and significantly lowering the energy needed to produce oil droplets in
water due to their dual existence. Furthermore, dispersant-generated droplets are usually
much smaller than those produced by the sea’s natural energy. Synthetic surfactants may
be anionic, cationic, nonionic, or amphoteric; however, crude oil dispersants are only used
C. Thermo-chemical processes
270
15. Use of chemical dispersants for management of oil pollution
with anionic or nonionic surfactants. Sorbitan esters of fatty acids, polyalkoxylated sorbitan esters of fatty acids, polyalkoxylated fatty alcohols, polyethylene glycol esters of oleic
acid, and tall oil esters are among the nonionic forms. Salts of dialkyl sulfosuccinates and
alkyl benzene sulfonic acid are examples of anionic surfactants. Sorbitan monolaurate,
ethoxylated sorbitan trioleate, ethylene/propylene oxide condensates, ethoxylated tridecylphosphate, sodium dioctyl sulfosuccinate, sodium lauryl sulfate, and isopropylamine
dodecyl benzene sulfonate are some examples of surfactants used. Other chemical agents,
such as solvents, are often added to surfactant mixtures to improve the surfactant’s dispersing efficiency (Application, Data, & Group, 1995; Cowell, 1977). Moreover, chemical
surfactants are amphiphilic compounds that accumulate at the surface of immiscible fluids
to minimize surface and interfacial tensions and improve the solubility and mobility of
hydrophobic or insoluble organic compounds. Chemical surfactants can make petroleum
components more pseudo soluble in water (Chapman, Purnell, Law, & Kirby, 2007). The
detailed mechanism for the functioning of chemical dispersants is shown in Fig. 15.3.
On the oil slick, dispersant is sprayed as fine droplets. The dispersant is best used
neat (undiluted) for maximum effectiveness, but it can also be used in aqueous carrier
systems like those used on boats. The solvent’s action and the droplet spray’s momentum help the dispersant droplets penetrate and blend into the slick. The surfactant molecules scatter around the oilwater interface as the dispersant enters the lower part of the
oil slick, lowering the interfacial stress. Small droplets of oil break free and scatter into
the upper layers of the water column. Additional surfactant in the oil process replenishes
the sticky oilwater interface as surfactant is carried away with the oil droplets. As a
result, as droplets break away and more surfactant enters the interface, the oil slick
steadily depletes. The surfactant layer stabilizes the scattered oil droplets, preventing
coalescence and resurfacing. For application efficiency and slick coverage, neat dispersant drops in the 300800 μm range are usually considered to be optimal. Winds can
blow finer droplets off-target, and larger droplets can smash through the oil slick too
easily, causing them to mix inefficiently. More oleophilic dispersant formulations can
more readily coalesce and blend with the oil slick, resulting in a higher overall application performance. Water-based carrier systems are less efficient because of their lower
affinity for oil slicks and consequent loss to sea water, and are best used on recently
spilled and low viscosity oils (Kleindienst et al., 2015; The International Tanker Owners
Pollution Federation Limited I, 2011).
15.4.1 Impact of chemical dispersants
The impact of chemical dispersants on microbial community, marine wildlife, salinity
and their composition and activity have been studied in brief. Mulkins-Phillips selected
four chemical dispersants (Corexit 8666, Gamlen Sea Clean, G. H. Woods DegreaserFormula 11470, and Sugee 2), and were tested individually and in combination with
Arabian Crude Oil (1:1) for their effects on the growth of bacteria native to local marine
waters, bacterial population composition, and crude oil biodegradation (Mulkins-Phillips
& Stewart, 1974). It has been found that the dispersants used alone supported good microorganism development, but the dispersant-oil combinations caused qualitative population
shifts. Depending on the dispersant used, the degree of degradation of the crude oils
C. Thermo-chemical processes
15.4 Principle and mechanism of chemical dispersants
271
FIGURE 15.3 Detailed mechanism of chemical dispersants (Kleindienst et al., 2015; The International Tanker
Owners Pollution Federation Limited I, 2011).
272
15. Use of chemical dispersants for management of oil pollution
n-alkane fraction differed. Only Sugee 2, which had the lowest emulsifying potential, supported n-alkane degradation in these tests as compared to the values obtained by using
crude oil alone. Rahsepar et al. reported that the use of Corexit on crude oil resulted in a
higher solubility of the oil’s aromatic compounds in sea water. This resulted in higher concentrations of these aromatic compounds, which inhibited oil biodegradation, especially
when there were no aromatic compounds degrading culture (Rahsepar, Smit, Murk,
Rijnaarts, & Langenhoff, 2016). Jawasim presented that the bacterial population structure
in salt marsh sediments was substantially altered in response to Corexit 9500A plus crude
oil treatment, and it differed from that of Corexit 9500An or crude oil treatment alone. The
addition of Corexit 9500A to crude oil had several effects on the bacterial population and
increased biodegradation rates by increasing the diversity and richness of hydrocarbondegrading species (Al-jawasim, 2020). The effects of three dispersants, Pars 1, Pars 2, and
Gamlen OD4000, on oil removal in two Persian Gulf provinces water were compared. A
total of 16 stations were chosen. The growth rate of isolated bacteria and fungi was determined using the Well process. It has been found that the growth of microorganisms on
Pars 1 or Pars 2 dispersants, or their mixtures with oil, had the highest growth rate.
However, the culture containing Pars 1 microorganisms had higher BOD and COD than
the other two dispersants (9200 and 16800 vs 500 and 960, respectively). The highest BODs
and CODs were found in mixtures of oil and Pars 2 dispersants, as well as oil and Pars 1
dispersants (Zolfaghari-Baghbaderani et al., 2012). The toxicity, effects, and efficacy of dispersants were studied before they were applied to spilled oil in nearshore environments
before the oil drifted into marshes. The result shows that the marsh plant Sagittaria lancifolia was 2080 times more resistant to the recently marketed dispersant JD-2000 than the
normal test species Menidia beryllina and Mysidopsis bahia, respectively. A small number of
studies on the impact of dispersants on plants have been performed, ranging from salt
marshes to freshwater marshes. According to some reports, dispersants like BP1100WD,
Corexit 9527, and BP Enersperse 1037 were ineffective at cleaning oiled salt marshes and
had a greater negative impact on salt marsh plants like Spartina anglica, Salicornia spp.,
Spairtina alterniflora, and Aster spp. than oils without dispersants (Lin & Mendelssohn,
2005). Liu built a Bayesian network in the German Bight, to determine and visualize the
possible benefits of using chemical dispersants to combat oil spills (Liu & Callies, 2019).
The BN focuses on the physical effect of dispersion, which alters drift paths by shielding
oil from additional wind drag. The BN offers a brief description of the major interactions
between environmental factors such as winds, tides, and residual currents, as well as the
effects of using chemical dispersants. Moles et al. found that dispersant efficiency is influenced by weathering condition, temperature, and salinity, which are all significant but not
always predictable factors. Temperature and salinity affected the ability of surfactantbased dispersants to increase petroleum dispersion in the water column (Moles, Holland,
& Short, 2002). Chandrasekar et al. investigated the effects of salinity on dispersion effectiveness in conjunction with three environmental factors: temperature, oil weathering, and
mixing energy and found that for almost all oil-dispersant combinations, salinity played
an important role in deciding the impact of temperature and mixing energy on dispersant
effectiveness (Chandrasekar, Sorial, & Weaver, 2006). Later on, researchers also developed
some efficient and environmentally sustainable dispersant for oil spill cleanup that can
maintain excellent emulsifying capability under varying conditions. The interaction
C. Thermo-chemical processes
15.5 Effectiveness and adaptability of chemical dispersants
273
between lecithin and Tween 80 is critical for improving the dispersant’s emulsifying capability. Both a modeling experiment and a molecular-level analysis were used to investigate
the mechanism of this dispersant on the oil/water interface (Jin et al., 2019). Without a
question, the best method for reacting to an oil spill is to prevent it from occurring in the
first place. It is much better to prevent a polluting incident/accident than to contend with
the resulting negative effects (Ventikos, Vergetis, Psaraftis, & Triantafyllou, 2004).
15.4.2 Toxicity of chemical dispersants
Chemical dispersants are made up of a combination of different surfactants and solvents. The majority of dispersants are proprietary, and the exact composition is rarely disclosed. Following the 2010 Deepwater Horizon oil spill in the Gulf of Mexico, chemical
dispersants used for cleanup and containment of crude oil toxicity became a major concern. The possible toxicity of chemical dispersants to humans and marine animals has
been called into question as a result of this crisis, as it is unknown if their use is reasonably healthy (Wise & Wise, 2011).
In 1997, strong C-oil spilled from the tanker “Nakhodka” severely contaminated the
long coastal line facing Japan-Sea. The impact on the early life stages of Japanese flounder
and round nose flounder were studied in the laboratory. Exposure to oil suspended in seawater at unusually low concentrations of oil caused larvae to deform and expand insufficiently. The dispersant was not particularly toxic in the absence of oil, but it became
extremely toxic in the presence of oil (OP). Since benthic species that are not harmed by
oil may be exposed to the harmful effects of dispersants, the possible ecotoxicological
effects of this transition is examined (Epstein, Bak, & Rinkevich, 2000). When dealing with
the destructive agents of oil and oil dispersants, the fragile coral reefs, and especially their
building blocks, the scleractinan corals, require extra caution. The toxicity values of different chemical dispersants on acute life are shown in Table 15.5.
Finally, oil detergents and dispersed oil are especially harmful to corals. As a result, decisionmakers should carefully consider these findings when considering the use of oil dispersants as
a method for reducing oil emissions near coral reefs. The findings of this and previous studies
suggest that any oil dispersant should be avoided in coral reefs and their environments.
Chemical dispersants can only be used in extreme cases, such as when oil slicks have reached
the shore and are threatening to suffocate the reef flats (Shafir, Van Rijn, & Rinkevich, 2007).
15.5 Effectiveness and adaptability of chemical dispersants
Chemical dispersants are mainly used to enhance the breaking of oil into tiny droplets,
which increases the biodegradation of oil in sea-water (Nnadozie et al., 2017). There are
many novel and conventional chemical dispersants used up to now based on the requirements. Due to the development of science and technology new dispersants are being synthesized to fulfill the requirements and to minimize the impact on marine environment. A
chemical dispersant will be only given permission to use when it gets approval from the
Swirling Flask Test (SFT), complete details of the test is given in Environmental Protection
C. Thermo-chemical processes
274
15. Use of chemical dispersants for management of oil pollution
TABLE 15.5 Toxicity level of chemical dispersants on acute life (Brown et al., 2011; Koyama & Kakuno,
2004).
S.
no
Dispersant
name
1.
BP 1002
Exposed for 24 h while testing on fry of sole and plaice organism; attains the value of
LC50 , 100 mg/L
2.
Slipclean
Exposed for 24 h while testing on fry of sole and plaice organism; attains the value of
LC50 , 100 mg/L
3.
Berol TL 198
Exposed for 96 h while testing on cod organism; attains the value of LC50 5 850 mg/L
4.
BP 1100 X
Exposed for 96 h while testing on cod organism; attains the value of LC50 . 688 mg/L
5.
BP 1100 X
Exposed for 24 and 96 h while testing on fingerling mullet organism; attains the value of
LC50 5 153 and 151 μL/L, respectively.
6.
Corexit 7664
Exposed for 96 h while testing on cod organism; attains the value of LC50 5 130 mg/L
7.
Corexit 8666
Exposed for 96 h while testing on cod organism; attains the value of LC50 . 940 mg/L
8.
Polycleans TS Exposed for 96 h while testing on cod organism; attains the value of LC50 . 984 mg/L
7
9.
Conco-K
Exposed for 24 and 96 h while testing on fingerling mullet organism; attains the value of
LC50 5 5.4 and 4.6 μL/L, respectively.
10.
Foremost
Exposed for 24 and 96 h while testing on fingerling mullet organism; attains the value of
LC50 5 54.3 and 52 μL/L, respectively.
11.
Corexit 7664
Exposed for 96 h while testing on grass shrimp organism; attains the value of
LC50 . 100 mg/L
12.
Hytron #3A
Exposed for 24, 48 and 96 h juvenile red sea bream organism; attains the value of
LC50 5 1500, ,870 and ,870 (mg/L), respectively.
13.
Sea green
Exposed for 24, 48 and 96 h juvenile red sea bream organism; attains the value of
LC50 5 8900, 7650 and 5150 mg/L respectively.
14.
Corexit 9500
Exposed for 96 h while testing on Oncorhynchus mykiss organism; attains the value of
LC50 5 354 mg/L
15.
Corexit 9500
Exposed for 96 h while testing on Photobacterium phosphoreum organism; attains the value of
LC50 5 0.065%
16.
Corexit 9527
Exposed for 96 h while testing on grass shrimp organism; attains the value of
LC50 . 1000 mg/L
17.
Corexit 9527
Exposed for 96 h while testing on Daphnia magna organism; attains the average value of
LC50 5 37 mg/L
18.
Corexit 9527
Tested on Gasterosteus aculeatus organism and exposed for 96 h, attains the average value of
LC50 5 77 mg/L
19.
Corexit 9527
Exposed for 96 h while testing on Oncorhynchus mykiss organism; attains the value of
LC50 5 108 mg/L
20.
Finasol OSR52
Exposed for 96 h while testing on Salmo gairdeni organism; attains the value of
LC50 5 71 mg/L
Description
(Continued)
C. Thermo-chemical processes
15.5 Effectiveness and adaptability of chemical dispersants
TABLE 15.5
275
(Continued)
S.
no
Dispersant
name
Description
21.
NEOS
AB3000
Exposed for 24, 48 and 96 h while testing on juvenile red sea bream organism; attains the
value of LC50 . 8900, 5 11100 and 5 680 mg/L, respectively.
22.
NEOS
AB3000
Exposed for 96 h while testing on Gasterosteus aculeatus organism; attains the average value
of LC50 5 320 mg/L
23.
NEOS
AB3000
Exposed for 96 h while testing on Salmo gairdeni organism; attains the value of LC50
. 5 320 mg/L
24.
Nokomis 3
Exposed for 96 h while testing on Salmo gairdeni organism; attains the value of LC50
. 5 110 mg/L
25.
Enersperse
700
Exposed for 96 h while testing on Daphnia magna organism; attains the average value of
LC50 5 50 mg/L
26.
Corexit CRX8
Exposed for 96 h while testing on Daphnia magna organism; attains the average value of
LC50 5 15.6 mg/L
27.
Dispersant G. Exposed for 96 h while testing on Oncorhynchus mykiss organism; attains the value of
E.
LC50 5 35 mg/L
28.
Dispersant G. Exposed for 96 h while testing on Oncorhynchus mykiss organism; attains the value of
P.
LC50 5 200 mg/L
29.
Dispersant G. Exposed for 96 h while testing on Oncorhynchus mykiss organism; attains the value of
T.
LC50 5 8 mg/L
30.
Dispersant G. Exposed for 96 h while testing on Oncorhynchus mykiss organism; attains the value of
W.
LC50 5 2 mg/L
31.
Dispersant G. Exposed for 96 h while testing on Oncorhynchus mykiss organism; attains the value of
Y.
LC50 5 0.71 mg/L
32.
Pennyworth
Exposed for 96 h while testing on Salmo gairdeni organism; attains the value of
LC50 5 44 mg/L
33.
Shell
dispersant
Exposed for 96 h while testing on Salmo gairdeni organism; attains the value of
LC50 5 71 mg/L
Agency—Federal Register References—(Ederal & Ection, 2011) FR 47458, 1994 Appendix
C-Part 300 (Terminal United States E Route, 2005). SFT is performed to find the effectiveness of chemical dispersant. In general the relative effectiveness of a chemical dispersant
depends on viscosity of oil, temperature, and dispersant to oil ratio. As the viscosity of oil
increases the effectiveness of chemical dispersant will decrease. Particularly CORE XIT9500 and Slickgone-EW shows decrease in effectiveness when temperature decrease and
viscosity increase (Stevens & Roberts, 2005). An experimental result of mean effectiveness
of eighteen different chemical dispersants are determined by two different testing, SDT
and Baffled Flask Test and concluded that the overall mean effectiveness of the SFT was
19.7% compared to 64.6% with Baffled Flask Test. This study was also given a pass or fail
criteria for selection of chemical dispersant (Sorial, Koran, Holder, Venosa, & King, 2005).
C. Thermo-chemical processes
276
15. Use of chemical dispersants for management of oil pollution
TABLE 15.6 Mean percentage of effectiveness of different chemical dispersants at 15 C at dispersant to oil
ratio-1:25 using Warren Spring Laboratory WSL LR 448 protocol on Crude oil and Heavy Fuels from different
sources around world (Stevens & Roberts, 2005).
Mean percentage effectiveness at 15 C at dispersant to oil ratio of 1:25
Crude oil source
CORE XIT-9500
CORE XIT-9527
Slickgone-EW
Slickgone-LTSW
TERGO-R40
Gamlen-OSD-LT
Kutubu
11
11
15
13
25
22
Barrow Island
13
15
11
17
22
22
Kuwait
45
52
34
38
17
16
Labuan
10
8
15
11
26
22
Oman residue
46
38
25
18
30
25
Taiwan
66
54
61
25
24
21
Brazil
76
63
81
11
29
25
Antwerp
39
14
41
3
1
1
New Zealand
35
15
15
9
4
Cristobel
59
56
62
7
15
17
Japan
66
48
61
16
19
17
Nagoya
58
38
58
10
6
4
Singapore
62
35
59
22
6
8
Rotterdam
51
37
49
6
5
5
Heavy fuels source
Percentage effectiveness of different chemical dispersants at different locations has been
shown in Table 15.6.
15.6 National and international regulations for using chemical dispersants
The Indian Coast Guards (ICG) which come under the Government of India, Ministry
of Defense, is the elected National Authority for oil spill response in Indian sea-water
under the National Oil Spill Disaster Contingency Plan NOS_DCP. The purview for
NOS-DCP is handled by National Disaster Management Authority, Ministry of Home
Affairs, Government of India. The ICGs is responsible for proper functioning of NOS-DCP
and also act as central coordinating agency to fight against oil pollution in different spilled
zones. Every chemical dispersant will undergo for different trials by National Institute of
Oceanography (NIO) and important information related Chemical dispersant can be found
at NIO. Some of the important policies and guidelines being followed by ICG have been
shown in Table 15.7.
Registration, Evaluation, Authorization and Restriction of Chemicals and Toxic
Substances Control Act of 1976 are the authorized agency of European Union regulation
and United States respectively for chemical dispersants approval. Every chemical
C. Thermo-chemical processes
15.7 Applications of different chemical dispersants
277
TABLE 15.7
Important policies and guidelines given by Indian Coast Guards (Response).
Policy
Description (National-India)
Policy-1
Only the chemical dispersants which are listed and approved should be used.
Policy-2
Sea oil spills should leave to biodegradable naturally unless they may cause damage to marine
environment
Policy-3
A chemical dispersant can only be used after thorough analysis on advantages and disadvantages
by Net Environmental Benefit Analysis and documented.
Policy-4
No chemical dispersants should be used in any sensitive areas or protected bays and inlets.
Policy-5
All stake holders, ports, oil handling companies, shipping companies, Coastal Refineries and Oil
Exploration and Production Organization, shall recover oil from oil spill.
Guidelines
Description (National-India).
Guideline-1
Hydrocarbon based chemical dispersants shall not be used.
Guideline-2
Water biodegradable concentrate chemical dispersants can be used in the ratio 1:2 for dispersant:
oil, which are spray by boats.
Guideline-3
Concentrate chemical dispersants can be used in the ratio 1:20 or 1:30 for dispersant: oil, which are
spray by aircrafts.
Guideline-4
Concentrate chemical dispersants can also be used with a proper authorization and advice when
they should be spray by boats.
Guideline-5
If in a case of light distillate fuels, no chemical dispersant should be used.
Guideline-6
No chemical dispersants should be used on weathered viscous emulsions at sea water.
dispersant should be gone through different test and should get approved, tests listed as
Swirling Flask Dispersants Effectiveness Test, Revised Standard Dispersant Toxicity Test,
Bioremediation Agent Toxicity Test effectiveness test and toxicity test are two main most
requested tests for many countries (Ederal & Ection, 2011). International Petroleum
Industry Environmental Conservation Association (IPIECA) is a global oil and gas industry association for environmental and social issues. IPIECA gives the guideline, polices
and approval for using different chemical dispersants. International Tanker Owners
Federation approved chemical dispersants are widely used and accepted by many countries (Coolbaugh, Varghese, & Li, 2017).
15.7 Applications of different chemical dispersants
1. Dispersants are scattered for oil spillage purposes on slicks for removing oil from the
surface of the sea, and for its dispersion in the water body. In addition, these chemical
dispersants reduce the influence on the surroundings of the split oil while spillage
remover process from the waterbody.
C. Thermo-chemical processes
278
15. Use of chemical dispersants for management of oil pollution
2. Dispersants decrease the quantity of surface oil, thus decreasing the personnel reaction
possible subjection to dangerous composites in the oil and reducing the amount of oil
met by aqueous species.
3. Dispersants augment the breaking up of the oil, helps it in removal from the aqueous
phase in the water columns as mini drops that can dilute quickly and biodegraded.
4. Dispersants can speedily and efficiently, reduce the harmful effects of pollutants to
water animals and some profound coastal sources.
5. Corexit 9500 is a kind of chemical dispersant that have catastrophic influences on
freshwater ecologies by upsetting the crucial foodstuff chain net (doi, 2016).
6. Pars 1 and Pars 2 are the most efficient dispersants, having higher depravity. These are
highly appropriate composites for the removal of oil spillage from offshore modules,
having lesser subordinate contamination (https://www.science.gov/topicpages/w/
water 1 dispersant 1 effectiveness).
7. DISPERSIT SPC 1000 is a kind of chemical dispersant that can be utilized by some
conservative techniques as aerial and boat spraying. Two to ten gallons per acre is
recommended as an application rate, and this is also reliant on the kind of oil, weather
and temperature conditions. Timely utilization guarantees the higher chances of
effective dispersal of the spillage (https://www.epa.gov/emergency-response/
dispersit-spc-1000tm#:B:text 5 Concentration%2FApplication%20Rate%3A,4840%
20square%20meters)%20is%20suggested).
8. MARE CLEAN 200 is a kind of chemical dispersant that is utilized at an
application rate of 53 to 66 gallons per ton of oil. It is an efficient dispersant
for liquors hydrocarbons (https://www.epa.gov/emergency-response/
mare-clean-200).
15.8 Conclusions
Critical conclusions drawn from the above studies have been mentioned below:
1. Oil spill has hazardous effect on aquatic animals, human health, and plants.
2. Evaporation of oil from oil spilled zones releases fumes and smokes which causes air
pollution.
3. Looking into the toxic nature of chemical dispersant and its long contamination
duration it is advised to follow mechanical, physical, and biological methods.
4. Widely used chemical dispersants for oil spill remediation are COREXIT 9500 and
COREXIT 9527. Results have revealed that COREXIT 9500 shows good effectiveness as
compared to COREXIT 9527 and is less toxic too.
5. COREXIT 9527 is a more toxic chemical dispersant tested till date.
6. Pars 1 and Pars 2 are efficient dispersants that can be used in oil spill treatment.
7. In some cases, use of chemical dispersants increases the toxicity of water bodies which
adversely affects the marine ecosystem.
8. It is always recommended to use chemical dispersant according to national and
international regulations.
C. Thermo-chemical processes
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C H A P T E R
16
Brief account on the thermochemical
oil-spill management strategies
Y. Sivaji Raghav1, Poonam Singh2, Ankit Dasgotra3 and
Abhishek Sharma3
1
CNPC BOHAI Drilling Company (BHDC), Kuwait City, KuwaitCNPC BOHAI Drilling
Company (BHDC), Kuwait City, Kuwait 2Department of Chemistry, University of Petroleum
& Energy Studies (UPES), Dehradun, India 3Department of Research and Development,
School of Engineering, University of Petroleum and Energy Studies, Dehradun, India
O U T L I N E
16.1 Introduction
283
16.2 Major oil spills incidents
284
16.2.1 Exxon Valdez oil spill (1989), and
Amoco Cadiz oil spill (1978) 284
16.2.2 Deepwater horizon oil spill
284
16.3 Oil spill treating methods
286
16.3.1 Physical remediation methods 286
16.3.2 In situ burning
288
16.3.3 Bioremediation
16.3.4 Chemical methods
16.4 Emulsifying agents
288
290
290
16.5 Impact of emulsion on ecosystem 292
16.6 Conclusion
292
References
292
16.1 Introduction
Nowadays, petroleum and other fuels are in great demand. The increase in global
demands for oil transportation and other uses leads to major environmental issues. One of
these environmental impact is an oil spill in seas during transportation. Despite several
significant measures taken to bring down these oil spill incidents with different regulations and advancements in this subject, an oil spill can occur due to a fuel leakage,
Advances in Oil-Water Separation
DOI: https://doi.org/10.1016/B978-0-323-89978-9.00011-2
283
© 2022 Elsevier Inc. All rights reserved.
284
16. Brief account on the thermochemical oil-spill management strategies
lubricating oils, undissolved gases, or any accident during transportation of petroleum
products or crude oil. The release of oils, gases, and wastes from industries into marine
leads to marine pollution. The impact of these spills can be multidimensional, which also
depends upon the chemical composition and properties of oil spilt. The properties and
behavior of individual components and their reaction with marine components can lead to
vary diverse effects on marine life and its ecosystem. When such oil spill incidents hit the
ocean, different treating agents can be used to minimize or compromise the effects that
tend to appear.
According to studies, oil spill treating agents can be classified based on their actions
like solidifiers, demulsifying agents, surface washing agents, and dispersants. Any of these
treating agents must fulfill the basic criteria. They must have long shelf life, must be nontoxic, non-polluting, biodegradable, highly active, and non-corrosive and must be easy to
apply from different mode of applications like boats, ships, helicopters, etc.
16.2 Major oil spills incidents
Many oil spill incidents happen in the course of history, that is the Amoco Cadiz oil
spill (1978), the Allantil empress oil spill (1979), Exxon Valdez oil spill (1989), the
Deepwater Horizon oil spill (2010), etc. There had been a huge number of oil spill incidents, that happened in different corners of the ocean, are subjected to major discussions
so far. Till 2020, approximately ten oil spill incidents have been reported, and some of the
major spill incidents have been opted for case discussion in this chapter.
16.2.1 Exxon Valdez oil spill (1989), and Amoco Cadiz oil spill (1978)
It is one of the major spill incidents that happened in 1989 (Peterson et al., 2003). The
spill released from 42,000 tons of crude, affected marine life and ecosystem of a very large
area of around 28000 km2 (Zhang et al., 2018). As this incident happened in the remote
high-energy area, oil was dispersed quickly. Amoco Cadiz incident happened in France
coastal area (1978), caused extensive contamination in marine life, as it was carrying
223,000 ton of crude oil. Lots of measures were taken to remove emulsion from sand and
rocks (Swannell, Lee, & McDonagh, 1996) and some of them were:
1. Cleaning compounds to restore oil from oil,
2. Chemical fertilizers,
3. Talc treated with 0.1% surfactant,
4. Bacterial and other biological remediation.
16.2.2 Deepwater horizon oil spill
It is considered to be the one of the biggest incidents that happened in the history
of the petroleum industry, in which around 500,000 ton oil got released. This
incident occurred in April 2010 and affected 180,000 km 2 area of ocean. In this spill
incident, extensive interaction of oil spilt and seawater formed plumes and spread
C. Thermo-chemical processes
16.2 Major oil spills incidents
285
throughout deep water. While having cleansing measures, 25% of the oil that spilled
got collected, 13% dispersed naturally, 23% of it got evaporated, and 13% of oiltreated using chemical methods. But despite all measures taken, 50%55% of volume
remained in the water and affected marine lives, as well as shorelines.
Biodegradation and chemical dispersants were used to minimize the effect and also
showed minimum contamination in seafood (Zhang et al., 2018).
These incidents affected the ecosystem, seafood industry, economy, future marine
and shoreline life too. Study of such events, after effects and damages caused by them,
prepare researchers to be able to deal with future incidents in term of precaution to
minimize the impact caused by them. Fig. 16.1 shows the systematic operation and
measures of an oil spill events, reveals about the key determinants (Singh, Bhardwaj,
Arya, & Khatri, 2020). It shows that factors like marine physical environment (movement of tides, connecting waterways, water currents, etc.), oil spill event/occurrence
(time, date, location, etc.), characteristics of spilt oil (concentration, composition, nature
of oil, etc.), marine biodiversity (effects on fisheries, birds, planktons, etc.), cleanup
methods and response strategies (physical remediation, chemical remediation, in situ
burning, bioremediation, etc.) and economic, social, and health impacts (fisheries,
aquaculture, tourism, recreation, etc.) are the main key determinants of an oil spill
event.
FIGURE 16.1 Systematic operation and measures of an oil spill event (Chen, Ye, Zhang, Jing, & Lee, 2018;
Singh et al., 2020).
C. Thermo-chemical processes
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16. Brief account on the thermochemical oil-spill management strategies
16.3 Oil spill treating methods
Oil spill remediation involves a great number of techniques in order to address the issue:
physical techniques, chemical techniques, thermal remediation, and biological remediation
16.3.1 Physical remediation methods
This includes manual controlling of spread of oil spilt without changing chemical or
physical properties. Some of the physical techniques are discussed below like (1) Boom (2)
skimmers (3) sorbents.
1. Boom helps to prevent the oil from spreading, so that oil can be removed using other
techniques like skimmers. Booms can be in fence-like structure that remains vertical. It is
noted that 60% of boom remains underwater and 40% remains above the surface, but they
are pretty unstable against strong wind, high waves and prove to be less efficient in such
cases. Another type of boom is curtain boom, they are flexible, foam-filled and arranged
circularly but they are also efficient in calm water bodies. Booms are also available in fireresistant types made up of fireproof material, they have great reliability to protect the
shoreline. Booms usually functional in river, streams and lake water columns (Ghaly &
Dave, 2011; Sutherland & Kendall Melville, 2015). Pictorial illustration of different
configuration of booms for oil collection is shown in Fig. 16.2.
2. Skimmers are used in recovering oil from the oil spill site. The working of skimmers depends
on the quantity of oil spilt, its properties as well as weather conditions. According to the
FIGURE 16.2 Pictorial illustration of different configuration of booms for oil collection (Azizian & Khosravi,
2019; Fingas, 2011).
C. Thermo-chemical processes
16.3 Oil spill treating methods
287
working techniques of skimmer, they can be of different types like weir skimmers as they
collect oil spilt using gravity actions. Skimmers show efficient results as they show stability
even in the presence of high waves and collect oil pretty quickly. Oleophilic skimmers
consist of oleophilic properties, resulting as they can recover up to 90% of oil, but can not
function if mixed with dispersant. Suction skimmer work for a collection of oil-based on
suction principle. Its functional range is a bit wide as it can also function to recover oil from
beaches and land area. Skimmers are more effective when the oil layer is thick and its
efficiency is affected by the viscosity of oil, wind and the current condition of oil in the water
body (Zhang et al., 2018). Pictorial depiction representing working of different types of
skimmers is shown in Fig. 16.3.
FIGURE 16.3 (A)(D). Pictorial depiction of workings of different types of skimmers (Azizian & Khosravi,
2019). (A) Weir skimmer, (B) suction skimmer, (C) elevation skimmer, (D) submersion skimmer.
C. Thermo-chemical processes
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16. Brief account on the thermochemical oil-spill management strategies
3. Sorbents are materials that absorb or adsorb oil from the ocean. These materials can be
natural or synthetic depends on the uses. They are usually functional in coastal areas, ports
and harbors to protect noncleanable area like pathways. Though sorbents are useful but their
excessive use can be problematic for further use of skimmer and also they are harmful for
the environment (Zhang et al., 2018). Natural adsorbent like mass milk ward and cottonseed
reported to absorb 85% of crude oil as per experiment, and natural absorbent are
economically more feasible. Synthetic adsorbents include polypropylene, polyester and
polystyrene, etc. Polypropylene reported to have the highest capacity. Some of them are
reusable but being synthetic, they are non-biodegradable (Ghaly & Dave, 2011).
16.3.2 In situ burning
In this method of cleaning up, controlled burning of oil in the presence of specialized equipment are involved. It is simple to implement, economic and highly efficient to use in freshwater,
salty water as well as other water bodies. This method has many benefits like low waste, low
cost and efficient elimination of oil but also have a negative side like elements from burning can
be toxic for the environment and this method can be used just when a layer of spilt oil is thick
enough to ignite. Concerning these issues, gasoline and other such light crude products can be
used for combustion (Sahai et al., 2007; Zhang et al., 2018). Some more disadvantages of this
method are that there are chances of catching secondary fire affected by wind, byproducts and
smoke that also rises the risk of toxicity for the environment and human life. Despite these disadvantages, it is a potential technique to be used in remote or restricted area (Ghaly & Dave,
2011).
16.3.3 Bioremediation
Bioremediation is the process in which microorganisms from marine ecology are used to
simulate the rate of natural biodegradation. There are lots of species in the marine ecosystem
that can work for the decomposition of organic and other chemical components. For organic
compounds present in the oil, the local microbial of the ocean do the job but for crude oil, only
consortium microbes can break them. The bioremediation method has some limitation like
availability of oxygen, certain temperature, PH and constituent matter is required. Usually, the
natural rate of degradation is very slow but it can be enhanced up to six times by the addition
of fertilizers. Similarly, in the case of Exxon Valdez oil spill event, nitrogen-based fertilizer was
used for the growth of microbes for the degradation of hydrocarbon.
Dispersants also help in degradation of oil because it provides greater surface area for
microbes to work on a faster rate. Different components of oil decompose at a different rate
by a set of microorganisms (Singh et al., 2020). For the bioremediation, process to occur in
marine system Nitrogen and phosphorus are required for the growth of microbes. It is
recorded that the use of fertilizers does not cause eutrophication or toxicity in the medium; in
fact toxicity of petroleum, hydrocarbon can be removed through bioremediation. This process
is more economic than most other remediation methods (Ghaly & Dave, 2011). Dispersion of
oil can be done through biodegradation as well sorption, which is demonstrated in Fig. 16.4.
C. Thermo-chemical processes
16.3 Oil spill treating methods
289
FIGURE 16.4 Mechanism of oil spill cleaning through chemical dispersion (Azizian & Khosravi, 2019).
FIGURE 16.5 Chemical dispersion process (Zhang et al., 2018): (1) water and oil are immiscible, (2) when dispersants are applied in the system, they align themselves in order to interact with both water and oil, and (3)
reduction in interfacial tension results in oil dispersion and formation of small droplets.
C. Thermo-chemical processes
290
FIGURE 16.6
16. Brief account on the thermochemical oil-spill management strategies
Role of different materials in oil dispersion of oil during oil spill incidents (Doshi et al., 2018).
16.3.4 Chemical methods
Dispersants can be counted in the category of surfactants work to create slurries by preventing settling, most importantly for the collection purpose (Fink, 2015; Muizis, 2013).
The working of dispersants is to break the slick of oil into minute droplets to promote
easy degradation of the marine system. To ensure that they mix well in the medium, Arial
spraying using aircraft is the best way of application. Despite being an economic method,
dispersants prove to be more capable to treat spilt oil comparatively. But one of the drawbacks is that they are hazardous for human, marine life as well as contaminate shoreline
and drinking water (Ghaly & Dave, 2011). Mechanism of oil spill cleaning through chemical dispersion, and chemical dispersion process is shown in Figs. 16.5 and 16.6.
16.4 Emulsifying agents
When seawater mixed with the oil spilt in the ocean, it forms emulsion which encouraged by surface turbulence. Usually, asphaltenes present in the oil is the key reason for
emulsion formation, which can last for several months. Surface turbulence breaks oil
layers into smaller droplets and this disturbance on the surface helps them to mix to form
an emulsion (Azizian & Khosravi, 2019). If heated under sunlight under calm condition,
emulsified oil and water can be separated. The formed emulsion can be stable, if they are
in 60%80% of water in an oil slick, semistable in 40%60% of water and unstable when
C. Thermo-chemical processes
16.4 Emulsifying agents
291
30%40% water is present in the oil slick. The emulsion can be formed with 70% of water
in it, which can lead to noticeable changes in the chemical and physical properties of the
oil. Crude oil is more likely to emulsify rather than other light oils (Zhang et al., 2018).
Thermodynamically emulsions are unstable system. Talking about oilfield emulsions, they
can be classified according to their kinetic stability (Fink, 2015): (1) loose emulsions are
very unstable that cannot even sustain for few minutes. (2) Medium emulsion- they are
semistable and can exist for up to 10 minutes. (3) The tight emulsion can sustain for hours,
a week and even for a month.
Invert emulsion is water in oil emulsion and they have desirable suspension properties.
In this case, the affinity of surfactant can be changed and can be converted into regular
emulsion, changing PH or just by protonating the surfactant (United States Patent
USOO7703527B2, 2007).
Water in water emulsion is formed when two polymers, each having aqueous solubility
but no thermodynamic compatibility are dissolved together in an aqueous medium. They
are also defined as an aqueous two-phase system. These aqueous polymer systems can be
used to create low viscous prehydrated for vigorous mixing of polymer to achieve low viscous polymer fluid (Fink, 2015).
Oil in water emulsion work to enhance the oil recovery along with that these emulsions
give stability and thinning characteristic to the system even more than water in oil emulsion could provide. According to the reports and forming condition, these emulsions used
to enhance recovery operations. Contrary to oil in water emulsions, these emulsions are
prepared by dispersing oil in water emulsion in second oil. Oil in water surfactant lower
dispersant effectiveness unlike water in oil emulsion, which increase dispersant effectiveness (Doshi, Sillanpää, & Kalliola, 2018).
Microemulsion has a small droplet the shape ranging 10300 nm in size. This thermodynamically stable emulsion would break back into oil and water over a period of time.
They come into action by increasing the dispersibility of oil based on chemicals. These
emulsions can be broken by providing a change in temperature and the addition of chemicals (Fink, 2015; Yang, 2009).
Solid stabilized emulsion—Some solid compounds (particles) having the oleophilic character or
possessing oil external emulsion can be used to stabilize the emulsion. These particles must be
oleophilic in nature to support external emulsions. These particles are majorly effective to stabilize crude oil emulsion. The standard of solidification of the emulsion can be enhanced by pretreatment of it using sulfonating agents before emulsification. Similarly, chemical treatment of
solidifying particles can be done to acquire oleophilic or hydrophilic character (Fink, 2015).
Bio treated emulsion—To stabilize the water in oil emulsion they can be treated biologically before emulsification. Same as solid stabilization this is another pretreatment using
oil-degrading microorganism. For the growth of these microorganisms, nitrogen and
phosphorus-containing nutrients are used in the presence of a sufficient amount of oxygen at 20 C70 C (moderate temperature). In this process aliphatic components oil are
oxidized to give polar ketones or acid of aliphatic chain. Because of the surface-active
properties of aliphatic components, they help in the stability of the emulsion. This also
results in changes in the aqueous phase, which after bioreaction used to make water in
oil emulsion and enhance the stability of the emulsion (Stability enhanced water-in-oil
emulsion & method for using same, 2007).
C. Thermo-chemical processes
292
16. Brief account on the thermochemical oil-spill management strategies
16.5 Impact of emulsion on ecosystem
Huge amount of oil spilled in the ocean, will definitely hit economically as well as
environmentally. The impact of materials spilled varies on the amount of oil released in an
accident and on the properties and nature of oil spilt. The amount of energy also would
get disturbed in the immediate environment because of hydrocarbon breakdown (Zhang
et al., 2018). Biodegradable dispersants possess low toxicity and prove to be highly efficient from an environmental point of view as they consist of non-ionic components and
less toxicity. Though dispersants and emulsifiers are recommended to cure the after
effects, and to recover oil. According to the status of the incidents, emulsification could
possibly increase toxicity in water and create pollution in the water body (Fink, 2015).
Accidents while transportation is very common. Most of these incidents occur due to
unexpected weather condition but ultimately it will affect marine life for very long upcoming years. Along with that, it brings different challenges and complications regarding the
environment, marine, and human life. The thickness of the layer of oil spilt one of the
major factors to be considered and affect in many ways, the toxicity of oil depends on its
sources and properties. All crude oils contain many heavy metals and PAHs, which lead
to toxicity of human and marine life (Zhang et al., 2018). These challenges also can be
addressed to some extent using different mitigation methods.
16.6 Conclusion
Technically, methods like booms and skimmers are not as effectively independent for
oil mitigation, dispersants, surfactants, and other surface-active agents are required to support these methods. As per the environmental aspect, it is always preferable to remove the
oil from ocean water, but economically these methods are costlier than the rest of the other
methods popular for the same purpose. But on the other hand, extracted oil and surfactants can be used again after processing, these surfactants from biobased resources prove
to be a better option from an economic and environmental point of view as they are more
feasible in terms of biodegradability and nontoxic, and can be regenerated.
References
Azizian, S., & Khosravi, M. (2019). Advanced oil spill decontamination techniques. Interface science and technology
(pp. 283332). Elsevier B.V. Available from https://doi.org/10.1016/B978-0-12-814178-6.00012-1.
Chen, B., Ye, X., Zhang, B., Jing, L., & Lee, K. (2018). Marine oil spills-preparedness and countermeasures. World seas:
An environmental evaluation volume III: Ecological issues and environmental impacts (pp. 407426). Elsevier.
Available from https://doi.org/10.1016/B978-0-12-805052-1.00025-5.
Doshi, B., Sillanpää, M., & Kalliola, S. (2018). A review of bio-based materials for oil spill treatment. Water
Research, 135. Available from https://doi.org/10.1016/j.watres.2018.02.034.
Fingas, M. (2011). Physical spill countermeasures. Oil spill science and technology (pp. 303337). Elsevier Inc.
Available from https://doi.org/10.1016/B978-1-85617-943-0.10012-7.
Fink, J. (2015). Petroleum engineer’s guide to oil field chemicals and fluids.
Ghaly, A. E., & Dave, D. (2011). Remediation technologies for marine oil spills: A critical review and comparative
analysis. American Journal of Environmental Sciences, 7, 423440.
C. Thermo-chemical processes
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Muizis, A., (2013). Evaluation of the methods for the oil spill response in the offshore arctic region. In Date evaluation of the methods for the oil spill response in the off-shore Arctic Region (52 pp. 1 2 Appendices). Metropolia
Ammattikorkeakoulu.
Peterson, C. H., Rice, S. D., Short, J. W., Esler, D., Bodkin, J. L., Ballachey, B. E., & Irons, D. B. (2003). Long-term
ecosystem response to the Exxon Valdez oil spill. Science (New York, N.Y.), 302. Available from https://doi.
org/10.1126/science.1084282.
Sahai, S., Sharma, C., Singh, D. P., Dixit, C. K., Singh, N., Sharma, P., . . . Gupta, P. K. (2007). A study for development of emission factors for trace gases and carbonaceous particulate species from in situ burning of wheat
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Singh, H., Bhardwaj, N., Arya, S. K., & Khatri, M. (2020). Environmental impacts of oil spills and their remediation by magnetic nanomaterials. Environmental Nanotechnology, Monitoring and Management, 14. Available from
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Stability enhanced water-in-oil emulsion and method for using same, (2007).
Sutherland, P., & Kendall Melville, W. (2015). Field measurements of surface and near-surface turbulence in the
presence of breaking waves. Journal of Physical Oceanography, 45, 943965. Available from https://doi.org/
10.1175/JPO-D-14-0133.1.
Swannell, R. P., Lee, K., & McDonagh, M. (1996). Field evaluations of marine oil spill bioremediation. Microbiology
and Molecular Biology Reviews: MMBR, 60, 342365.
United States Patent USOO7703527B2, 2007.
Yang (2009). Microemulsion containing oil field. United States Patent.
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C. Thermo-chemical processes
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S E C T I O N
D
Biological processes
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C H A P T E R
17
Use of live microbes for oil
degradation in situ
Ragaa A. Hamouda1,2, Dalel Daassi1, Hamdy A. Hassan3,4,
Mervat H. Hussein5 and Mostafa M. El-Sheekh6
1
Department of Biology, College of Sciences and Arts, Khulais, University of Jeddah, Jeddah,
Saudi Arabia 2Department of Microbial Biotechnology, Genetic Engineering and Biotechnology
Research Institute, University of Sadat City, Sadat City, Egypt 3Department of Biological
Science, Faculty of Science and Humanity Studies at Al-Quwayiyah, Shaqra University, AlQuwayiyah, Saudi Arabia 4Department of Environmental Biotechnology, Genetic Engineering,
and Biotechnology Research Institute, University of Sadat City, Sadat City, Egypt 5Botany
Department, Faculty of Science, Mansoura University, Mansoura, Egypt 6Botany Department,
Faculty of Science, Tanta University, Tanta, Egypt
O U T L I N E
17.1 Introduction
17.9 Fungal enzymes in bioremediation 304
298
17.2 Bioremediation of oil compounds
by bacteria
299
17.10 In situ—mycoremediation
305
17.11 Bioaugmentation
305
17.12 Fungi bacteria consortium
306
17.13 Biostimulation
306
17.14 Biodegradation of crude oil
by fresh algae
307
17.3 Role of bacterial oxygenases
in the oil biodegradation
300
17.4 Oil-degrading fungi
300
17.5 Marine fungi
301
17.6 Soil fungi
302
17.7 Mycorrhizal fungi
303
17.15 Effect of seaweeds (marine algae)
in biodegradation
308
17.8 White rot fungi
303
17.16 Cyanobacteria
Advances in Oil-Water Separation
DOI: https://doi.org/10.1016/B978-0-323-89978-9.00013-6
297
308
© 2022 Elsevier Inc. All rights reserved.
298
17. Use of live microbes for oil degradation in situ
17.17 Algal bacteria consortium
309
17.18 Factor affecting in
biodegradations
310
17.19 Summary
311
References
311
17.1 Introduction
In the present world, anthropogenic activities such as growth, biological, physical, economic, industrial, infrastructure growth, science, technological growth, etc., revolve around
energy. Apart from traditional sources of energy like firewood, wind power, solar power, etc.,
petroleum hydrocarbons continue to be used as the principal and adaptable form of energy.
The most important strategic resource of any country is its crude petroleum resources (Sun,
2009). All human activities are counting on the petrochemical industry to meet their energy
needs. However, these crude petroleum compounds’ use seems to have a deteriorating effect
on our environment (Xue, Yu, Bai, Wang, & Wu, 2015).
Oil pollution is one of the most important pollution affecting the world these days.
Even polar regions are not excluded from its harmful effects (Ruberto, Vazquez, Lobaldo,
& MacCormack, 2005). The sudden introduction of massive amounts of these xenobiotic
chemicals into the environment can affect the recipient ecosystem’s self-cleaning capacity,
hence resulting in the accumulation of these pollutants to a problematic level.
Bioremediation in crude petroleum, microorganisms are employed to reduce the concentration of toxic petroleum hydrocarbon compounds. Not all microorganisms have the
capability to degrade all the different petroleum hydrocarbon compounds as a result of
different environmental factors, which exhibit crucial roles in biodegradation and then the
bioremediation of these compounds (Varjani & Upasani, 2017), at the presence of
suitable environmental conditions for petroleum hydrocarbon bacterial degraders in the
lab, it will increase its capability to degrade petroleum compounds (Head, Jones, &
Röling, 2006). Due to the increase of petroleum hydrocarbon compounds in the environment, the indigenous bacteria ultimately used most of these compounds as a sole carbon
source to meet their energy requirements to fulfill their physiological activities. This is the
reason why these bacteria are found in the oil spill contamination sites, also, longer aged
oil-contaminated sites, the more numbers of microorganisms (Varjani & Gnansounou,
2017). In recent years, detoxification of contaminated sites by applying one or more fungi
species as natural agents is called “Myco-remediation.” It has become prevent, economical,
and efficient in converting toxic wastes into not/or less toxic end products or carbon dioxide and water (Yamada, Mukumoto, Katsuyama, & Tani, 2002). Fungi have advantages
over other microorganisms in that they are characterized by a robust morphology, large
hyphal network, adaptability to extreme conditions, and tolerance to a high concentration
of pollutants (Prasad, 2017). Furthermore, fungi are rapidly incorporated into the pollutants and grow in environments with low nutrient concentrations, acidic pH, and low
activity water (Mancera-Lopez et al., 2008). Also, fungal species can produce versatile
extracellular enzymes such laccases, peroxidases, and integral-membrane enzymes like
cytochrome 450 and oxidoreductases (Ostrem Loss & Yu, 2018), which interact with
D. Biological processes
17.2 Bioremediation of oil compounds by bacteria
299
various structures of hydrocarbons with a fairly high degree of nonspecific activity
(Martı́nková, Kotik, Marková, & Homolka, 2016). So that, the diversity of habitats and the
ability for secreting a multitude of specific and no specific enzymes makes fungi potential
candidates in treating a wide spectrum of petroleum hydrocarbons structures (Cerniglia &
Sutherland, 2010). Mycoremediation implicates fungal cultures’ specific augmentation to
enhance the biodegradation of spilled oil in situ or ex situ remediation. Saprophytic fungi
perform a vital role in the decomposition of organic pollutants such as petroleum spilledoil. These fungi yield various extracellular enzymes and acids that act and catalyze native
polymers such as cellulose, hemicellulose, lignin, keratin, chitin, and pectin (Lamar &
White, 2001). A widespread of fungal species have shown their possibility to degrade
petroleum hydrocarbon from contaminated spill oil areas. The most common fungal strain
recorded as a biodegrading belongs to the following genera: Talaromyces, Talaromyces,
Amorphoteca, Neosartorya, Penicillium, Aspergillus, Fusarium, Paecilomyces, Graphium,
Sporobolomyces, and Cephalosporium (Das & Chandran, 2010; Varjani, 2017). Organic pollutants can be biomonitoring, controlling by various algae from aquatic ecosystems
(Chekroun, Sánchez, & Baghour, 2014). Algae can degrade organic pollutants, which is
referred to as “phycoremediation.” Phycoremediation is a promising biodegradation technology due to ecofriendly approaches for cleaning polluted areas and are environmentally
sustainable (Baghour, 2019). Phycoremediation is a safe technology, nonintrusive, and
worthwhile in which the prospective macro- or microalgae are used to handle a huge
group of pollutants (Gupta, Ranjan, & Gupta, 2019). Suresh and Ravishankar (2004) investigated that algae positively affect the hyperaccumulation of heavy metals and xenobiotics’
degradation. Using microalgae in the elimination of colored wastewater and bioremediation of heavy metals have gained attention due to their fundamental role in carbon dioxide
fixation. Algae’s biomasses have a vital feedstock for biofuel production and are useful for
environmental sustainability (Ellis, Hengge, Sims, & Miller, 2012). Algae can absorb light
and assimilate CO2 into chemical energy (transformations) and can grow ampler than
other plants, resulting in ampler removal or biotransformation of pollutants; also, algae
can good survive under stress condition, so the possibility of treatment of polluted site by
algae is further sustainable for natural resource controlling (Gupta et al., 2019).
17.2 Bioremediation of oil compounds by bacteria
The remediation using physical and chemical methods is costly and not environmentally
friendly (Rosenberg, 1993). These methods cause raising different gas levels in the atmosphere,
such as carbon-dioxide (CO2), sulfur, and nitrogen- oxide. Increasing CO2 is the main reason for
global warming. However, these methods remove some petroleum oil contaminants but remain
serious unpredictable hazards (Johnson & Affam, 2019). Mechanical and chemical methods for
the remediation of oil contaminates become limited and expensive (Das & Chandran, 2010).
Bioremediation of crude oil polluted compounds using microorganisms becomes the ideal solution because of relatively low-cost technology, public acceptance, and often carried out on-site
(Brakstad & Bonaunet, 2006). Using N- and P- compounds for fertilizing oil-polluted sites are
high frequent than other used methods (Varjani & Upasani, 2017). Self-cleaning of oil-polluted
sites is oil-removal by the flora microorganisms in locations without using any additional
D. Biological processes
300
17. Use of live microbes for oil degradation in situ
supplements. Although the concentration of polluted oil in the contaminated sites reached 20%
or more (McKinnon & Vine, 1991), only the studies reported 1%6% of crude oil were removed
by bioremediation (Siles & Margesin, 2018). As a result of damaged wells, the oil spilled and
filled varying dimensions 50 oil-lakes, thus cause high oil concentrations and lead to high toxicity for organisms, where their life becomes nearly impossible in these conditions (Ziółkowska &
Wyszkowski, 2010) Bioremediation functions depend on biodegradation either to transfer the
complex hydrocarbon compounds into simpler compounds or by transferring into inorganic
compounds, cell protein and mainly carbon dioxide and water this what is called complete mineralization (Das & Chandran, 2010), which is cheaper than other remediation technologies
(Leahy & Colwell, 1990). The factors influencing oil degradation the limited availability to
microorganisms, where oil compounds bound to soil components, with difficulty to be released
or degraded as polycyclic aromatic hydrocarbons (PAHs) some of these compounds not be
degraded at all (Atlas & Bragg, 2009). Temperature is a significant factor for biodegradation,
where the temperature affects the chemistry of oil compounds and then affects the microbial
flora on the contaminated sites. By decreasing the temperature delayed the biodegradation of
oil compounds (Foght, Westlake, Johnson, & Ridgway, 1996). Nutrients, especially nitrogen,
phosphorus, and sometimes iron, are necessary elements for increasing biodegradation of oil
pollutants (Cooney, 1984). As a result of oil spilled in water, either marine or freshwater, carbon
increased, and the biodegradation becomes affected by nitrogen and phosphorus (Atlas, 1985).
Additions of the nutrients could be vital to increase the oil pollutants biodegradation (Kim,
Choi, Sim, & Oh, 2005), whereas the extreme concentrations of these nutrients could be the reason for inhibition of biodegradation (Chaillan, Cha^ıneau, Point, Saliot, & Oudot, 2006). Many
bacterial strains can degrade different types of aromatic compounds, as in Table 17.1.
17.3 Role of bacterial oxygenases in the oil biodegradation
Oxygenases either monooxygenases and dioxygenases play a vital role in the biodegradation
and bioremediation of oil compounds especially the aromatic compounds by increasing their
water solubility and their reactivity and also added one or two oxygen molecules to cleave the
aromatic ring, where monooxygenase added one oxygen atoms and dioxygenases incorporate
two oxygen atoms into the aromatic substrates. Oxygenases are broadly spread in nature and
indispensable for the aerobic bacterial degradation of aromatic compounds by hydroxylation of
the aromatic ring into cis-diols compounds using NADH or NADPH as a cofactor (Eltis and
Bolin, 1996), for example, the conversion of benzene to cisbenzendihydrodiol (Fig. 17.1).
Dioxygenases involved in ring cleavage (Weelink, 2008) (Fig. 17.1).
17.4 Oil-degrading fungi
The hydrocarbon-degrading fungi are ubiquitously distributed in various habitats,
including fresh or marine environment and the affected soil matrix. In oil-polluted areas,
PAHs can be susceptible to the fungal transformation when the fungi can use the petroleum compounds for their growth and reproduction. Indigenous isolates are susceptible to
the biodegradation of petroleum-contaminates sites (Das & Chandran, 2010).
D. Biological processes
301
17.5 Marine fungi
TABLE 17.1
Bacteria degrading simple aromatic compounds in oil.
Microorganism
Substrate
Reference
Alcanivorax sp. HA03
Benzene and toluene
Hassan, Nashwa,
Hefnawy, and Ahmad
(2012)
Pseudomonas sp. HA10Pseudomonas sp.
HA12Pseudomonas sp. HA140
BTEX
Hassan and Aly (2018)
Pseudomonas sp. HB01
Hassan, Eldein, and Rizk
(2014)
Rhodococcus sp. strain HA01
Dibenzofuran
Aly, Huu, Wray, Junca,
and Pieper (2008)
Pseudomonas putida F1
Benzene and toluene
Parales, Ditty, and
Harwood (2000)
Ralstonia picketti PKO1Burkholderia
cepaciaPseudomonas mendocina KR1P. putida PaW15P.
putida F1
Benzene, toluene, and phenol
Reardon, Mosteller, and
Rogers (2000)
Burkholderia sp JS150
Toluene and phenol
Rogers and Reardon
(2000)
Bacillus sp
Toluene, ethylbenzene, and oxylene
Amor, Kennes, and
Veiga (2001)
Ralstonia sp. strain PHS1
Toluene, ethylbenzene, o
xylene, m-, and o-cresol
Lee and Lee (2001)
P. putida and Pseudomonas fluorescens
Benzene, toluene, ethylbenzene,
and xylene isomers
Shim, Shin, and Yang
(2002)
Paecilomyces variotii and Exophiala oligosperma
Toluene
Estevez, Veiga, and
Kennes (2005)
P. putida
Phenol and 4-chlorophenol
Loh and Ranganath
(2005)
Pseudomonas sp. Strain H12
Benzene, toluene, hexyl
benzene, xylene and butyl
benzene
Amer, Nasier, and ElHelow (2008)
P. variotii
E. oligosperma
17.5 Marine fungi
Marine-derived fungi are important microbial resources for mycoremediation applications. Those fungi are tolerant of saline conditions, which can be used in the degradation
of PAH polluted environments, such as ocean and marine sediments. Hydrocarbon degradation using fungi from marine origin was reported by many authors (Barnes, Khodse,
Lotlikar, Meena, & Damare, 2018; Vieira, Magrini, Bonugli-Santos, Rodrigues, & Sette,
2018); however, their application still poorly studied.
D. Biological processes
302
17. Use of live microbes for oil degradation in situ
Ring hydroxylating dioxygenasesv
H
OH
OH
OH
O2
NADH
H2O
+
NAD
OH
OH
H
O2
NADH
OH
+
NAD
OH
OH
OH
OH
HO
ROC
OH
OH
HO
OH
OH
OH
OH
COOH
R
FIGURE 17.1 Initial attack on Benzene by oxygenases. Monooxygenases incorporate one atom of oxygen of
O2 into the substrate and the second atom is reduced to H2O. Dioxygenases incorporate both atoms into the
substrate.
From marine habitat contaminated with oil spill (Gulf of Mexico), fungal isolates were
performed in the crude oil biodegradation. The isolated fungi belong to Aspergillus niger
with higher activity, followed by Penicillium documbens, Cochliobolus lutanus, and Fusarium
solani. A. niger recorded the highest weight loss of 8.6%, P. documbens (7.9%), and C. lutanus
(4.7%), whereas Fusarium demonstrated the lowest weight loss solani strain 421502 (1.9%).
Vieira et al. (2018) studied the isolation of three marine-derived basidiomycete fungi and
selected Marasmiellus sp. CBMAI 1062 for Pyrene and benzo(a) pyrene (BaP) detoxification/degradation. Also, Barnes et al. (2018) reported the isolation of ten fungal isolates
from select marine substrates with an ability to degrade crude oil. The mainly genera of
isolates are Aspergillus with six strains, Acremonium with two strains, Fusarium, and
Penicilium.
17.6 Soil fungi
Soil fungi are mostly considered preferment Petroleum hydrocarbon-degrading, and
their consortia with other species ensure effectiveness biodegradation in soil-remediation.
Soil consists of a wide vary of fungi in phyla Chytridiomycota Ascomycota and Zygomycota.
Most of them are nonligninolytic saprophytes and have excellent cellulose-decomposing
capacity in nature.
D. Biological processes
17.8 White rot fungi
303
Generally, the most frequent soil fungal strains belonged to Allescheriella, Aspergillus,
Acremonium, Alternaria, Cladosporium, Beauveria, Cunninghamella, Fusarium, Engyodontium,
Geomyces, Mortieralla, Microsporum, Paecilomyces, Phlebia, Penicillium, Rhizopus, Trichoderma,
and Stachybotrys (Zafra, Moreno-Montaño, Absalón, & Cortés-Espinosa, 2014). Several
authors have made lists containing indigenous fungi genera that can degrade a broad
spectrum of PAHs, proceeding from petroleum polluted soil. Burghal, Abu-Mejdad, and
Al-Tamimi (2016) investigated the abilities of indigenous fungal flora isolated from polluted soil to degrade crude oil. In this study, four fungi species were isolated indigenously
contaminated soil for crude oil biodegradation. The species fungi belong to A. niger,
Candida glabrata, Candida krusei, and Saccharomyces cerevisiae.
The study of Zheng and Obbard (2003) reported the performance of Penicillium sp. 06 to
oxidize different structure of petroleum hydrocarbons in contaminated soils.
More than 75% of fluroanthene, acenaphthene, and fluorine were oxidized using
Penicillium sp. 06 after 30 days of treatment. The same fungus was able to oxidize 89% of
phenanthrene presents in oily effluents from the petrochemical refining industry after 28
days of remediation.
17.7 Mycorrhizal fungi
Mycorrhizae fungi have a symbiotic relationship with plant roots that have a critical role in
phytoremediation by increasing nutrition and water uptake and improved tolerance to environmental stress at contaminated-sites (Małachowska-Jutsz & Kalka, 2010; Prasad, 2017). Several
authors investigated the application of Mycorrhizal fungi genera in the bioremediation of
petroleum-contaminated soil. Małachowska-Jutsz and Kalka (2010) investigate the efficacy of
Mycorrhizal fungi associated with plant cultivation on petroleum-contaminated soil.
17.8 White rot fungi
White-rot fungi (WRF) show promise for petroleum hydrocarbon remediation. These
are the first to be applied in mycoremediation studies by 30% of the total researches
(Singh, 2006). WRF effectively suppress lignin within lignocellulosic substrates by releasing extracellular Lignin-Modifying enzyme (LME). The enzymes present in the system
employed for degrading lignin include lignin-peroxidase (LiP), manganese peroxidase
(MnP), various H2O2 producing enzymes laccase (Pointing, 2001). This ligninolytic enzymatic cluster is characterized by a low substrate-specificity that can act upon several classes of pollutants with a similar structure to lignin.
In previous studies, the extracellular oxidative ligninolytic enzymes of Phanerochaete
chrysosporium was well studied as effective enzymatic tool of bioremediation in the
removal of xenobiotic organic pollutants (Paszczynski & Crawford, 1995).
Other genera of WRF (e.g., Trametes versicolor, Pleurotus ostreatus, Bjerkandera adusta,
Irpex lacteus, and Lentinula edoles) are additionally recognized to degrade a wide range of
petroleum hydrocarbons (Singh, 2006). Recently Li, Wang, Ni, Bao, and Zhang (2020) studied the in situ remediation of Carbofuran-Contaminated Soil by Immobilized WRF.
D. Biological processes
304
17. Use of live microbes for oil degradation in situ
17.9 Fungal enzymes in bioremediation
Fungi are suited for bioremediation of crude oil in polluted sites owing to their
diverse metabolic activities. They can secrete a broad range of ligninolytic and nonligninolytic enzymes to use petroleum hydrocarbons as a carbon and energy source
and assimilate into fungal biomass (Peixoto, Vermelho, & Rosado, 2011). Many organic
pollutants enter to fungal cell through the permeable cell membrane, where its internal
enzymes break them down, for example, reductive dehalogenases (Stella et al., 2017),
cytochrome P450 (Ostrem Loss & Yu, 2018), and nitroreductases (Tripathi et al., 2017),
into simpler metabolites. Theses metabolites are followed by further metabolism, such
as β-oxidation and entry into the tricarboxylic acid (TCA) cycle (Varjani, 2017). Van
Beilen and Funhoff (2007) reported the implication of alkane oxygenases, like cytochrome 450 enzymes, integral membrane di-iron alkane hydroxylases (e.g., alkB), and
membrane-bound copper-containing methane monooxygenases and soluble di-iron
methane monooxygenases, in the biodegradation of petroleum hydrocarbons.
Ligninolytic enzymes from WRF containing laccase (EC 1.10.3.2), manganese peroxidase (MnP, EC 1.11.1.13), and lignin peroxidase (LiP, EC 1.11.1.14) (Lee & Lee, 2001)
have been investigated extensively as a biotechnological tool for spilled oil bioremediation. This ligninolytic enzymatic system makes WRF able to completely mineralize
PAHs to CO2 (Pointing, 2001). Fungal laccases are the main enzyme involved in petroleum hydrocarbons’ bioremediation (Unuofin, Okoh, & Nwodo, 2019). However,
lipases have been significantly less studied on bioremediation of PAHs (Haritash &
Kaushik, 2009). The research of Ugochukwu, Aghaand, and Ogbulie (2010) reported
the presence of the enzyme lipase as an indicator of microbial degradation of crude oil
using indigenous and exogenous soil microorganisms. Among the fungal isolates, A.
niger showed the highest lipase activity of 4.00 μ/mL. Balaji, Arulazhagan, and
Ebenezer (2014) investigated various fungal species’ ability to secrete extracellular
enzymes, like laccase, lipase, protease, and peroxidase. Enzyme-based remediation
offers several advantages over the application of microbial cells (Torres, Bustos-Jaimes,
& Le Borgne, 2003). Enzymatic mycoremediation is simpler than using the whole fungi,
especially in extreme environments. Furthermore, enzymes can avoid the implication
of genetically modified organisms or exotics in the native surroundings (Daccò et al.,
2020). Other advantages including the enzyme specificity and efficacy can be improved
and managed in the laboratory (Sutherland et al., 2004). Both whole cell competitiveness and toxic byproduct generation do not occur during enzymatic bioremediation
(Setti, Lanzarini, & Pifferi, 1997). Moreover, fungi’ enzymatic system has been recorded
as a biodegrader of hydrophobic or poorly soluble xenobiotics in aqueous solutions
like PAHs. Enzymatic oxidation can occur in the presence of organic solvents. Thus the
fungal enzymatic bioremediation can give a solution to the insolubility and the bioavailability of hydrocarbons during the cleanup bioprocess. Despite the advantages of
enzymatic bioremediation, enzymes must be stable, adapted to environmental variations, and produced at less cost. All those restrict the widespread application of extracellular enzymes for oil spills remediation (Eibes, Arca-Ramos, Feijoo, Lema, &
Moreira, 2015). Fungal enzymes are typically involved in the ex situ remediation of
petroleum contaminants.
D. Biological processes
17.11 Bioaugmentation
305
17.10 In situ—mycoremediation
Mycoremediation is considered as an environmentally biotechnological application of
such species of fungi for in situ (at the area of contamination) and ex situ (on contamination removed from the original site) restoration and cleanup of Petroleum-contaminated
areas (Strong & Burgess, 2008). Using fungi in the area of contamination provides the
ability to implement in situ biological treatments without disturbing the native ecosystem compared to physical and chemical remediation methods (Mirdamadian, Emtiazi,
Golabi, & Ghanavati, 2010).
In many Petroleum hydrocarbon-contaminated sites, even though suitable native microbial populations may be available for biodegradation of organic contaminant, environmental conditions may restrict this process (Margesin, Zimmerbauer, & Schinner, 2000). In
such cases, the addition of nutrients (biostimulation) of the degrading potential of intrinsic
microbial populations and/or the addition of selected degrading microorganisms to contaminated soil (bioaugmentation) have been effective at enhancing hydrocarbons metabolism (Das, 2012; Chandra & Singh, 2019).
17.11 Bioaugmentation
Bioaugmentation enhances the intrinsic population in the contaminated site by supplementing potential microbes to suppress pollutants (either indigenous or exogenous microorganisms). This approach is often used at high concentrations of spilled oil, where
natural degrading microbes are absent or insufficient (Crawford, 2006). Indeed, hydrocarbons compounds can delay or inhibit microbial proliferation and activities, so for effective
in situ biodegradation, bioaugmentation is important (Purohit, Chattopadhyay, Biswas, &
Singh, 2018).
Employing an indigenous microorganism consortium ensures that the organisms have a
higher tolerance to the toxicity of aromatic hydrocarbon and are resistant to variations in
the environment (Ezekoye, Chikere, & kpokwasili, 2018). Exogenous microbes are useful
with more complex hydrocarbons structures, where the rates of intrinsic biodegradation
will be the slower of hydrocarbons degradation (Barbeau, Deschênes, Karamanev,
Comeau, & Samson, 1997). Therefore bioaugmentation approaches are necessary to
enhance indigenous microbial populations’ performance several folds through the introduction of microbes with specific metabolic activities for effective in situ remediation of
polluted areas (Ezekoye et al., 2018). Conventionally, the bioavailability of pollutants, the
tolerance of microorganisms to environmental stress in oil-polluted areas, and their catabolic activities are essential for the bioaugmentation approaches (Heinaru et al., 2005).
For instance, when bioaugmentation with the soil-isolated fungi: Penicillium funiculosum
and Aspergillus sydowii strains in the hydrocarbons—polluted soil, an increase of 16% of
the total petroleum hydrocarbons was reported, compared to the treatment carried out
using biostimulation treatment without the addition of fungi (Mancera-Lopez et al., 2008).
Accordingly, Garon, Sage, Wouessidjewe, and Seigle-Murandi (2004) reported that more
than 90% of fluorene was removed after 288 h during the augmentation of a soil slurry
D. Biological processes
306
17. Use of live microbes for oil degradation in situ
system with A. Cylindrospora, while not bioaugmentated system required a longer time for
removing fluorine from polluted-soil.
The study of Byss, Třı́ska, and Baldrian (2008) demonstrated that the bioaugmentation
of creosote-contaminated soil by two fungal strains, P. ostreatus and I. lacteus newly isolated from wood-preserving plan, slightly improve the decontamination of soil. A removal
rate of 67% PAHs was observed in P. ostreatus treatments, and 36% PAHS removal was
observed in I. lacteus treatments during 120 days.
17.12 Fungi bacteria consortium
The removal of hydrocarbons from highly polluted sites is a great challenge. Some
researchers suggested the use of microbial consortia to enhance the biodegradation
rates (Rodriguez-Rodriguez et al., 2014). Recent studies reported using living monofungus or mixed-fungal cultures (Ezekoye et al., 2018) and fungal-bacterial consortia
(Ma et al., 2018) that could enhance biodegradation efficiency, especially on high concentrations of oil. Indeed, bioremediation of complex hydrocarbons usually requires
the cooperation of more than a single species because the individual microorganism
can metabolize only a limited range of hydrocarbon substrates (Al Nasrawi, 2019).
Therefore the assemblages of mixed populations with overall broad enzymatic capabilities are required to bring the rate and extent of petroleum hydrocarbon degradation
much faster (Zhong, Luan, Lin, Liu, & Tam, 2011).
Atlas and Cerniglia (1995) suggested that although the fungi can metabolize some
hydrocarbons, they do not have the enzymes required for transforming the cooxidation
products. This removal value increased up to twofold with the biostimulation treatment.
Still, the PHAs remotion was even 16-, 7- and eightfold times higher when bioaugmentation treatments with Rhizopus sp., P. funiculosum, and A. sydowii were applied, respectively.
Although some studies showed an effective degradation in the initial phase by bioaugmentation treatment, then slow removal rates were showed over time, probably due to
organisms’ competitiveness (Sabate, Vinas, & Solanas, 2004) and nutrient depletion.
According to Ellegaard-Jensen et al. (2014), the inoculation with single or consortium of
microbes (bacteria and/or fungi), had not shown improvements in the biodegradation efficiency in the high-level crude oil contaminated-sites.
17.13 Biostimulation
Biostimulation is one of the adapted strategies in situ-remediation for increasing the
petroleum hydrocarbons removal rates in contaminated areas (Garon et al., 2004). This
approach consists of stimulating the growth and the activities of the intrinsic microbial
population in the crude oil-contaminated—site by the amendments of nutrients such as
organic biostimulants, carbon, nitrogen, and oxygen (the electron acceptor)
According to Breedveld and Sparrevik (2000), inorganic nitrogen and phosphorous
stimulated microbial growth and improved the PAHs degradation efficiency in creosote—
contaminated soil in Norway.
D. Biological processes
17.14 Biodegradation of crude oil by fresh algae
307
For instance, the amendments of crude oil-contaminated soil by nutrients (nitrogen,
phosphorus, and potassium) considerably improved the biodegradation efficiency with
62% of removal hydrocarbons compared to not amended contaminated-soil that where
47% of removal rate was recorded (Chaineau, Rougeux, Yepremian, & Oudot, 2005).
In the same context, Zafra et al. (2014) studied the efficiency of the biostimulation
approach using sugarcane bagasse during the remediation of PAH-contaminated soils by
Trichoderma asperellum H15. The amount of phenanthrene degradation accomplished by T.
asperellum was 78.3% in contaminated soils with 1,000 mg/Kg after 14 days.
Alternatively, several agricultural byproducts (sugarcane bagasse, cowdung, and sawdust) are used as support and biostimulants for enhanced the bioremediation of
petroleum-contaminants (Zafra et al., 2014)
Also, some researchers reported that mycoremediation’s effectiveness might also be stimulated by generating an optimal balance of physical factors such as aeration, temperature, and
buffering of environmental pH by altering the redox state and electrokinetics state of contaminated samples (Kuppusamy, Palanisami, Megharaj, Venkateswarlu, & Naidu, 2016).
Various abiotic and biotic factors can influence the effectiveness of spilled oil decontamination, including the potential and the metabolic activities of petroleum-degrading microorganisms in the environment, competitiveness, availability, and concentration of
petroleum and nutrients, salinity, and temperature, among others (Santos et al., 2011)
Many studies showed the influence of the combined biostimulation-bioaugmentation
approach.
Biostimulation is more effective used in combination with bioaugmentation methods.
While evaluating the performance of biostimulation methods compared with bioaugmentation and natural attenuation, biostimulation’s kinetic efficiency was relatively slow compared to the bioaugmentation process (Li et al., 2020).
Recently, Li et al. (2020) studied carbofuran’s catabolism by the cobioaugmentation of WRF
(Phlebia sp., Lenzites betulinus, and I. lacteus). Corn stover, wheat straw, peanut shells, wood
chips, and corn cobs were used as biostimulants and carriers to immobilize the fungal strains
17.14 Biodegradation of crude oil by fresh algae
Petroleum-degrading Achlorophyllous alga including Prototheca zopfii have been frequently studied to degrade Louisiana crude oils (Walker, Colwell, Vaituzis, & Meyer,
1975; b). Chlamydomonas sp. proved significant hydrocarbon degradation when grown in
acetate without light (Jacobson & Alexander, 1981). Chlamydomonas reinhardtii can eliminate some of the iso-octane from diesel particulate exhaust (Liebe & Fock. 1992).
Petroleum hydrocarbon can be faster degraded by Scenedesmus obliquus (green alga), meanwhile, n-alkanes can be better removed by Nitzschia linearis (Ibrahim & Gamila, 2004).
Chlorella sp. could proficiently utilize petroleum hydrocarbons as a carbon source through
mixotrophic conditions in oil field formation water (Das & Deka, 2019). The green alga
Monoraphidium braunii can remove bisphenol A, and high levels of contaminations present
on the surface of the water (Gattullo et al., 2012). The green algae S. obliquus and Chlorella
vulgaris can grow normally in wastewater containing 40% oil products (Dogadina,
Logvinenko, & Steblyuk, 1970). Uzoh et al. (2015) reported the potentiality of Closterium sp.
D. Biological processes
308
17. Use of live microbes for oil degradation in situ
in biodegrading crude oil in the oil-polluted water at location 1 of Shell Petroleum
Development Company at Ukwugba village in Ohaji Egbema L.G.An of Imo State harbors.
Samuel, Gerald, and Joseph (2020) investigated the bioremediation activity of C. vulgaris,
which was isolated from a pond in Uwani, Enugu State. The alga utilized the following
forms of oil, crude oil heavily, kerosene moderately, and petrol minimally, as demonstrated
by the varying degree of turbidity produced during the growth in mineral salts—oil
medium. El-Sheekh, Hamouda, and Nizam (2013) documented that C. vulgaris and S. obliquus showed a greater amount of crude oil degradation in aqueous solutions.
17.15 Effect of seaweeds (marine algae) in biodegradation
Seaweeds can grow in polluted water by crude oil and hence can degrade crude oil.
Marine organisms containing phytoplankton can uptake and collect several chlorinated
hydrocarbons, resulting in decreased concentrations (Harding & Phillips, 1978). The green
and brown seaweeds Enteromorpha and Fucus grew well on granite that is heavily contaminated by oil, and also Prophyra and Ulva were growing well in the same site (Tendron,
1968). Endocldia muricata and Gigartina cristata were grown well in the second season after
coated with crude oil (Chan, 1973). Iridaea flaccida, Enteromorpha intestenalis, and Urospora
penicilliformis were grown well after coating with oil (Chan, 1972). The pentachlorophenol
PCB was accumulated in the macroalgae such as Fucus vesiculosus in as little as 24 h
(Lauze & Hable, 2017). Marine red alga Portieria hornemannii can eliminate Trinitrotoluene
from the seawater (Cruz-Uribe & Rorrer, 2006). S. obliquus was the best alga that degraded
oxamyl in soil among the other tested algae (El-Ansary, Hamouda, & Ahmed-Farid, 2020).
17.16 Cyanobacteria
Various studies have demonstrated the potential of cyanobacteria of oxidizing organic
constituents, as Agmenellum quaduplicatum, and Oscillatoria sp. which revealed oxidizing
capability naphthalene to 1-naphthol as documented by (Cerniglia, Gibson, & Van Baalen,
1980). Additional studies reviewed oxidation of biphenyl to 4-hydroxybiphenyl by
Oscillatoria sp., strain JCM as well as metabolizing phenanthrene into trans-9,10-dihydroxy-9,10-dihydroxyphenanthrene and 1-methoxy-phenanthrene by A. quadruplicatum
(Narro, Cerniglia, van Baalen, & Gibson, 1992).
Both Cyanobacteria and eukaryotic microalgae were capable of biodegrading naphthalene to a nontoxic product (Cerniglia, Gibson, & Van Baalen, 1979; Cerniglia et al., 1980).
Cyanobacteria is already present in the ocean which helps clean it and prevents the oil
spill from accumulating, so cyanobacteria are economical sources for cleaning oceans
(Turchyn, Scanlan, Smith, & Christopher, 2015). The pesticide tricyclazole was removed
faster in soils when treated with cyanobacteria (Kumar, Abbas, & Aster, 2017). Significant
growth of Skeletonema costatum, Dicrateria sp., and Phaeodactylum tricornutum was obtained
when treated oil spill-polluted seawater and improved the bioremediation (Pi et al., 2015).
Sanchez, Diestra, Esteve, and Mas (2005) suggested that cyanobacteria’s dominance to
many polluted sites, including the polluted shores of the Arabian Gulf, could be
D. Biological processes
17.17 Algal bacteria consortium
309
accountable for the biodegradation of oil components. Ichor, Okerentugba, and
Okpokwasili (2016) documented cyanobacteria’s potentiality isolated from crude oil polluted habitat, which utilizes it as carbon and energy sources. Al Hasan, Sorkhoh, Al Bader,
and Radwan (1994) studied the performance of the dominant cyanobacterial pollution in
the spilled crude oil from Arabian Gulf coasts. Microcoleus chthonoplastes showed the ability
to degrade individual n-alkanes, whereas Phormidium coriurn growth was proportional to
n-nonadecane (C19).
Successful bioremediation of oil spills was achieved by Oscillatoria salina, Plectonema terebans, Aphanocapsa sp. And Synechococcus sp., which grew as mats in aquatic environments
(Cohen, 2002). El-Sheekh and Hamouda (2014) reported that Streptomyces platensisand
Nostoc punctiforme could grow heterotrophically in deferent crude oil concentrations and
can biotransfear aliphatic compounds to aromatic compounds.
17.17 Algal bacteria consortium
Numerous studies investigated that bacterial-algae consortia are more efficient in remediating petroleum hydrocarbons than single algal culture. Many studies reported that
algae transfer more oxygen so as to enhance bacterial growth which effectively accelerates
algal biomass (Gupta et al., 2019). Microalgae are produced O2 through the photosynthesis
process required by acclimatized bacteria to biodegrade hazardous contaminants such as
phenolics, organic solvents, and aromatic hydrocarbons (Muñoz, Guieysse, & Mattiasson,
2003). Numerous studies proved that algaebacteria consortium can be employed to treat
aromatic pollutants (Borde et al., 2003). Indigenous algaebacteria consortium was considered as a possible biological method for eliminating total acid-extractable organics and toxicity reduction (Mahdavi, Prasad, Liu, & Ulrich, 2015). Subashchandrabose, Ramakrishnan,
Megharaj, Venkateswarlu, and Naidu (2013) investigated that cyanobacteria and microalgae can degrade organic pollutants and monitor organic pollutant degradation. Macroalga,
a bacterial consortium, including S. obliquus, eliminated efficient quantities of crude oil’s
aromatic hydrocarbons (Tang et al., 2010). The efficient removal of phananthrene by a consortium of Chlorella sorokiniana (green alga) and Pseudomonas migulae in phototrophic conditions without an external supply of oxygen has been observed by Muñoz et al. (2003).
Sanchez et al. (2005) reported that the cyanobacterium M. chthonoplastes lived in consortium with heterotrophic bacteria inhabited the polysaccharide sheath since Microcoleus
introduced habitat and an oxygen source and organic matter. However, this consortium
possesses the ability to grow in the presence of crude oil, decomposing aliphatic heterocyclic organo-sulfur compounds in addition to alkylated monocyclic and PAHs. Various prokaryotes constitute a microbial consortial relationship with other prokaryotic and
eukaryotic microorganisms according to their nutrient requirements, as interpreted by
Raghukumar, Vipparty, David, and Chandramohan (2001) found that marine cyanobacteria O. salina, Plectonema terebrans, and Aphanocapsa sp. possess the ability to decompose
Bombay High crude oil though, about 45%55% of crude oil. Within ten days, 5% polar
compounds, 14% aromatics, 50% aliphatics, 31% waxes, and bitumin were removed in the
presence of these cultures. Hamouda, Sorour, and Yeheia (2016) reported Chlorella
D. Biological processes
310
17. Use of live microbes for oil degradation in situ
kessleri, Anabaena oryzae, and its consortium can grow mixotrophically and promote
crude oil biodegradation.
17.18 Factor affecting in biodegradations
The interaction of the organic contaminating substance that contributed to their
chemical composition and the decomposing potential of microorganisms in addition to
the different environmental factors that affect activities of microorganisms as well as
the absence of metabolic inhibitors which may certify some active microbial populations having the capability of utilizing these hydrocarbon environmental pollutants
(Chikere & Ekwuabu, 2014). The oil biodegradation process proficiency may be controlled by many aspects such as nutrient concentration, oxygen, substrates, environment sensitivity, and the richness of oil-degrading microorganisms themselves
(Rodriguez-Blanco, Antoine, Pelletier, Delille, & Ghiglione, 2010). And also, temperature, pH, bioavailability, and toxicity of end-products, the temperature has a substantial effect on the in situ microorganisms’ ability to degrade PAHS in the most
contaminated site (Bamforth & Singleton, 2005). The degradation of PAHS was
increased by increasing temperature (Margesin & Schinner, 2001). Also, pH can influence biodegradation of PAHS in situ, Burkholderia cocovenenas isolated from a
petroleum-contaminated soil can degrade Phenanthrene in liquid culture at pH 5.5
(Wong, Lai, Wan, Ma, & Fang, 2002). Biostimulation, by adding nitrogen, phosphorus,
and surfactants, bioaugmentation by adding microorganisms, have been employed to
develop and promote bioremediation efficiency (Al-Mailem, Sorkhoh, Salamah, Eliyas,
& Radwan, 2010). The specific growth rate of C. vulgaris BS1 increased with an increase
in inoculums concentration when inoculated in oil field formation water (Das & Deka,
2019). EL-Sheekh, El-Naggar, Osman, and Haider (2000) demonstrated that the low
concentrations of crude oil motivated the growth, protein, and nucleic acids; however,
the higher concentrations reduced the growth and protein content of two Chlorella species. The results of (Talebi et al., 2016) clear that after 25 days of incubation Dunaliella
salina in different dilutions of oil field produced water and seawater as 1:1, 1:2, 1:3 and
seawater (control), the biomasses increase with increasing oil field, and also the same
results were obtained by Nocardiopsis salina CCMP 1776 when cultivated in the oil field
(Graham, Dean, & Yoshida, 2017). The nutrients and dissolved organic compounds
influence marine microalgae and marine ecosystems’ growth (Subashchandrabose
et al., 2013). Wang et al. (2020) investigated the influence of exogenous nitrogen supplementation on the cyanobacterial abundance in oil-polluted sediments in a microcosm study, the outbreak of cyanobacterial blooms in the oil-contaminated group
amended by nitrogen was significantly delayed compared with that group without
nitrogen supplementation.
The Pollution by petroleum hydrocarbons emphasizes the requirement for environmental decontamination by effective clean-up of the polluted-sites. Physic-chemical techniques
had been extensive used to eliminate hydrocarbons from oil-contaminated sites (soil or
water) such as air stripping, chemical precipitation, oxidationreduction, and electrochemical treatments, all of physicochemical techniques are not completely effective, costly
D. Biological processes
References
311
which makes them nearly abandoned and with limited prospects. Bioremediation by living or dry organisms has become a promising biological treatment for restoring petroleum
contaminated areas. It has been established as one of the efficient, economic, versatile, and
environmentally ecofriendly.
17.19 Summary
Large numbers of living organisms such as bacteria, fungi, and algae had been used for
metabolic breakdown of hydrocarbon and organic contaminants. Generally, microorganisms are selected on the basis of their metabolic diversity and performance to remove or
reduce contaminant levels. Microorganisms are extensively used for degradation of pollutants, but there are limiting factors that affect biodegradation processes such as concentrations of pollutants, low temperature, concentrations of nutrients, and these factors had
negative effects on the degradation processes by microorganisms. A biodegradation can be
efficient only where the natural conditions permit microbial growth and results in the pollutants degrade. Biodegradation has been used in different contaminated areas with various degrees of success. Further studies are needed on biodegradation in situ by different
microorganism’s bacteria, fungi, algae, and its consortium, and discover new strains that
adapt to natural conditions and able to degrade contaminants in situ.
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C H A P T E R
18
Metagenomics—an approach for
selection of oil degrading microbes
and its application in remediation of
oil pollution
Md Azizur Rahman1, Aakanksha Rajput2, Anand Prakash2
and Vijayaraghavan M. Chariar3
1
University Institute of Engineering, Department of Biotechnology Engineering and Food
Technology, Chandigarh University, Ludhiana, India 2Department of Bioscience and
Biotechnology, Banasthali Vidyapith, Banasthali, India 3Centre for Rural Development and
Technology, Indian Institute of Technology-Delhi, New Delhi, India
O U T L I N E
18.1 Introduction
320
18.2 Microbes associated with degradation
of oil
320
18.3 Metagenomics in oil degradation 321
18.3.1 Sampling
322
18.3.2 Isolation of genome
323
18.3.3 Modeling 16S rRNA and 18S
rRNA
324
18.3.4 Amplification by polymerase
chain reaction technique
324
Advances in Oil-Water Separation
DOI: https://doi.org/10.1016/B978-0-323-89978-9.00003-3
18.3.5 Sequencing
18.3.6 Phylogenetics
324
328
18.4 Application
329
18.5 Metagenomics challenges
330
18.6 Conclusion
331
References
331
319
© 2022 Elsevier Inc. All rights reserved.
320
18. Metagenomics—an approach for selection of oil degrading microbes and its application in remediation of oil pollution
18.1 Introduction
Energy resources are subjected to nonrenewable resources that are finite. Regular usage
and dependency on them causes rapid decrease in their presence. Furthermore, an increase
in the human population demands a great amount of energy consumption. Development of
any national economy is highly influenced by crude oil and uneven distribution of oil and
allied products creates huge differences in oil availability. The crude oil demand influences
the transport of several metric liter of oil to the consumer countries via different modes of
transportation. Inappropriate industrial and domestic use of oil, crude oil spill incidents, oil
degradation issues, and many natural and anthropogenic causes magnify oil contamination
and oil pollution in environment. A major portion (about 13%) of oil spills is due to transportation of oil (Chen et al., 2019). The release of untreated commercial and domestic oil in
ground, water and air become risk to marine and human life (Rathi & Yadav, 2019).
Nowadays much attention is paid to these issues, as its adverse effect influenced nature.
Extant crude oil reservoirs affect more than 600 million humans and possibly influence environment and health (Johnston, Lim, & Roh, 2019). Various techniques, methods, and treatments are used to overcome the incidents caused by oil spillage and associated pollution.
Oil booms and oil skimmer (as mechanical approaches), use of surface collecting and surface
washing agents (as chemical approaches), and bioremediation (as biological approaches) are
used as promising tools. (Safiyanu, Isah, Abubakar, & Rita Singh, 2015). Among all these
approaches biological techniques are the most effectual as nature has the tremendous properties to heal itself. Existing microorganisms and enzymes have great potentiality to remove
or degrade the pollutants. Various anaerobic and aerobic bacterial materials degrade oil contaminants naturally. For the efficiency enhancement, pathway modification and better outcomes of these bacterial resources, metagenomics is a very relevant, effective, and a fruitful
tool. Through metagenomics, microorganisms are directly extracted from their original
domain, cloned and modified for better results, as this approach not only help to make an
account of known microbes but also give us specific knowledge about the unknown
microbes. The metagenomics approach conquers the existing hurdle in evolution of diversity, proper procedure is developed, that capture undiscovered microbial diversity. For the
detection of unique biocatalysts new screening approaches have been drafted which choose
to select particular functional genes within metagenomic libraries. For proper understanding
of entire gene or operon clusters, numerous vectors containing fosmid, bacterial artificial
chromosomes, and cosmid are developed. For better and advance approaches of microbial
diversity bioinformatics tools and databases are adjoined (Singh et al., 2009).
18.2 Microbes associated with degradation of oil
Microbes with enormous potential to degrade the oil are used as a potent cleanup tool in the elimination of hydrocarbon contaminants from nature (Hazaimeh, Abd Mutalib, Abdullah, Kee,
& Surif, 2014). The microbial process used for clean up or curing the nature is broadly
placed under bioremediation. Bioremediation is defined as a natural therapy for healing the
nature. The native microorganisms and enzymes neutralize or degrade hazardous pollutants
D. Biological processes
18.3 Metagenomics in oil degradation
321
into less toxic forms (Xu et al., 2018). The microbial degradation process is a very appropriate, appealing, easeful and economical approach for hydrocarbon degradation. This
approach is not a new notion; it was traceable since the 1940s. Though in the past environmental microorganism resolve this issue, but by the passing time contamination issue
become very serious and complicated for the nature to take care of it. In the recent past efficient microbes and enzyme have been discovered by the biologist and ecologist that have
great potential for degradation of oil and its allied. To name a few, Aeromonas, Arthrobacter,
Aspergillus, Atinetobacter, Bacilli, Beijerinckia, Brevibacterium, Burkholderia, Candida, Chrobacteria,
Corynebacteri, Cyanobacteria, Flavobacteria, Fusarium, Gordonia, Mucor, Moraxella, Modococci,
Mycobactena, Nocardia, Penicillium, Pseudomonas, Rhodotorula, Sporobolomyces, Streptomyces are
some examples of common species that perform degradation under diverse environmental
conditions (Tanzadeh & Ghasemi, 2016). For the degradation of complex hydrocarbons
microbial consortium has been advocated to be more suitable than individual species as hazardous compounds cannot be converted into end product (i.e CO2 and H2O) by the single
microorganism. The development of microbial consortia had proved to surpass the limitations of single microbial application. Microbial consortia were developed with multiple
microbial species working in synergistic manner for efficient degradation of contaminants
(Poddar, Sarkar, & Sarkar, 2019). Microbial consortia are developed by combining either various bacterial species together or a cocktail of bacteria with fungus or algae. Microorganisms
that show more growth were used in the construction of hydrocarbon degraders. For construction of consortia, efficiency of two or more different bacteria or bacteria with algal and
fugal was analyzed and assure for their abilities of degradation. A consortium made by
comprising various microbes such as Bacillus sp., Corynebacterium sp., Flavobacterium sp.,
Micrococcus sp. and Pseuudomonas sp. proved to be more efficient (up to 78%) in degradation
of crude oil with compared to single isolates, which had 41%66% degradation rate
(Hamzah, Phan, Abu Bakar, & Wong, 2013). An efficacious mixed consortium of fungal and
bacteria showed high efficiency rate to degrade polycyclic aromatic hydrocarbon (PAH) contamination in soils. These microbial consortiums contain five native bacterial strains: Bacillus
cereus, Klebsiella pneumoniae, Klebsiella sp., Pseudomonas aeruginosa, Stenotrophomonas maltophilia
and four fungal strains: Aspergillus flavus, Aspergillus nomius, Trichoderma asperellum,
Rhizomucor variabilis (Zafra, Taylor, Absalón, & Cortés-Espinosa, 2016).
18.3 Metagenomics in oil degradation
Diverse nature replete with influential microorganism, some of them have been
acknowledged for oil degradation and many more remain to be recognized. The undiscovered or complex microbes which had not been reported in laboratory culture could also
influence the degradation (Singh et al., 2009). Metagenomics, a recent tool, had been developed for the discovery of unrevealed, mysterious, novel, and more effectual microbial
communities. The tool adds on as evolutionary technique for bioremediation for the elimination of oil pollutants and hazardous hydrocarbons from the water and soil. Through
metagenomics nonfamiliar microorganism had been identified and their efficiency accelerated by alteration and modification in metabolic pathways of microbes. For the cleanup
treatments of oil contaminants and pollutants in water and soil various case studies
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18. Metagenomics—an approach for selection of oil degrading microbes and its application in remediation of oil pollution
elucidate that metagenomic applications are extensively used (Devarapalli & Kumavath,
2015). Variety of biograders was traced by this novel approach which decomposed hydrocarbons in reservoirs of petroleum (Sierra-Garcia et al., 2014). Through the latest format of
metagenomics, it can be possible to have wide perspective of complex pathways correspondence to hydrocarbons degradation and surfactant production (Oliveira et al., 2017).
This appealing approach is followed in a chronological order in which initially sample is
isolated collectively, then DNA is obtained from selective community of microorganism,
followed by sequencing of gene is done and further analyzed by comparing with
sequences available in the gene libraries (Jurkowski, Reid, & Labov, 2007). On completion
of entire process a proficient metagenomic libraries is constructed and many unknown
sequences are retrieved from the environment (Panigrahi, Velraj, & Rao, 2019) (Fig. 18.1).
18.3.1 Sampling
Sampling is the first and very deciding step in metagenomics process unlike the other protocol where specific culturable specimens are isolated, in this process sampling of bulk communities is isolated. The nucleic acids in microbial community form the basic unit of
reference as it further leads to the identification of species which are present in the sample
and its relationship with other microbes of the collected sample. Extracted DNA samples contains whole genome of all possible microbial cells present in the sample material (Thomas,
Gilbert, & Meyer, 2012). Major precautions should be given to the isolated samples as they are
the main sources of the process, viability of the cell is main focal point. Different depths of the
sites are suggested to isolate the samples. Furthermore they are recommend to freeze
FIGURE 18.1
Basic schematic representation of metagenomic process in oil degradation.
D. Biological processes
18.3 Metagenomics in oil degradation
323
immediately at 280 C after collection, and temperature can be increased up to 220 C.
Freezing prevent changes in the communities of microbes until the further action perform.
Sample can also be preserved for two hours at room temperature in a stabilizing buffer, but
quick freezing is recommended if RNA is extracted, as RNA samples easily get denatured at
room temperature. Sampling method should be selected by considering various criteria like
availability, efficiency, high recovery, price range, suitability, usage, and compatibility with
other methods (Méndez-Garcı́a, Bargiela, Martı́nez-Martı́nez, & Ferrer, 2018).
18.3.2 Isolation of genome
Beside the isolation of specific DNA, whole community of genome is targeted for isolation in metagenomics aspect. Many conventional isolation methods have been followed to
get highest DNA yields in an appropriate time. In first step, extraction buffer is used to
disrupt the microbial cell wall for the cellular content is released in the buffer solution.
Selection of the extraction buffer depends on the required quantity and purity of the DNA
(Felczykowska, Krajewska, Zielińska, & Łoś, 2015). For the removal of humic contaminants, CTAB is a great option and used in buffer for SDS (Sodium dodecyl sulfate) based
DNA extraction (Zhou, Bruns, & Tiedje, 1996). Proteinase enzyme is also added to extraction buffer and incubate in a controlled temperature for a particular duration.The pellet
thus recovered after centrifugation contains DNA, is precipitated by adding Polyethylene
glycol (Verma & Satyanarayana, 2011). Collected pallet is further washed, air dried and
dissolved in TE buffer (Verma, Singh, & Sharma, 2017). Quantitative and qualitative properties of extracted metagenomic DNA are evaluated by various method such as electrophoresis, fluorometer (Guerra et al., 2018) and purity were analyzed by Nano-Drop
spectrophotometer (Kimes et al., 2013). For the development and modernization of the isolation process, various procedural aspects are adapted. Numerous isolation kits and advance
methods has been developed and available in the market that assure the accuracy of the
extraction procedure and time saving. Some of the different isolation kits for extraction of
metagenomic DNA from oil spillage sites are listed below.
• Microbial DNA Isolation Kit (MoBio Laboratories) (Guerra et al., 2018)
• ZR bacterial DNA mini prep extraction kit (Inqaba South Africa) (Ezekoye, Chikere, &
Okpokwasili, 2018)
• ZR fungal/bacterial DNA Kit (Zymo Research) (Kachienga, Jitendra, & Momba, 2018)
• Nucleospin kit (Appolinario et al., 2019)
• PowerMarxSoil (MoBio, Carlsbad, CA, United States) DNA isolation kit (Moreno-Ulloa
et al., 2019)
• Meta-G-Nome DNA isolation kit (Epicenter) (Sierra-Garcia et al., 2020)
• FastDNA Spin Kit for Soil (MP Biomedicals, LLC, Irvine, CA, United States) (Viggor
et al., 2020)
• DNeasy Power Soil Kit (Qiagen, Hilden, Germany) (Pacwa-Płociniczak, Biniecka,
Bondarczuk, & Piotrowska-Seget, 2020)
• Power soil DNA extraction kit (Qiagen) (Auti, Narwade, Deshpande, & Dhotre, 2019)
• UltraClean MegaPrep (MoBio Laboratories, Inc.) (Méndez-Garcı́a et al., 2018)
• G’NOME DNA Extraction Kit (BIO101) (Méndez-Garcı́a et al., 2018)
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18. Metagenomics—an approach for selection of oil degrading microbes and its application in remediation of oil pollution
18.3.3 Modeling 16S rRNA and 18S rRNA
Extracted samples contain massive category of genomics DNA of organisms, grouping of
organism DNA is done on the basis of kingdom with 16S rRNA & 18S rRNA sequencing method.
Specific primers are designed for disclosure of gene (primer: small single-stranded DNA
sequence found in two forms- Forward primer [F] for initiation and Reversed primer [R] for
expulsion). 18S gene primers covered a wide range detection of eukaryotic cells while 16S covered prokaryotic cells (Wang, Tian, Gao, Bougouffa, & Qian, 2014). Designing of primer is influenced by the amplification of gene of interest. 16S rRNA gene found in bacterial sources can be
analyzed by using various hypervariable regions like V1/V3 or V3/V5 or V4 regions and amplified by commonly used bacterial primers like 515F & 806R (Mason et al., 2014) and universal
primer 530R (50 -CCGCGGCKGCTGGCAC-30 ) and E8F (50 -AGAGTTTGATCMTGGCTCAG-30 ).
For targeted level analysis 338R (50 -TGCTGCCTCCCGTAGGAGT-30 ) and 27F
(50 -AGAGTTTGATCCTGGCTCAG-30 ) primers are recommended (Méndez-Garcı́a et al., 2018).
For 18S rRNA gene analysis universal reverse primers 50 -TGATCCTTCYGCAGGTTCAC-30 or 50 CTGGTTGATCCTGCCAG-30 and forward primer 50 -GACGGGCGGTGTGTACA-30 are used
(Kachienga et al., 2018). Some commercial kits are also used for taxonomic analysis of 16S rRNA
& 18S rRNA genes like Ion 16S Metagenomics Kit (A26216; manual: MAN0010799, TermoFisher)
(Moreno-Ulloa, et al., 2019), Nextera XT DNA Sample Preparation Kit (Illumina, San Diego, CA,
United States) (Appolinario et al., 2019), DYEnamic ET Terminator Cycle Sequencing Kit (GE
Healthcare) (Paixão et al., 2010). Selected genome and engineered primer further used in PCR for
amplification.
18.3.4 Amplification by polymerase chain reaction technique
Combination of specific DNA and primer further proceed to amplification DNA template. PCR is considered desirable technique for the amplification. Various model of PCR
are manufactured for the particular or preferable outcome, out of which Real-Time PCR
(Yergeau, Sanschagrin, Beaumier, & Greer, 2012) is the most acceptable category in the
case of hydrocarbons. In Real time PCR, SYBR green fluorescent dye is used for bacterial
quantification of gene copies in QuantStudio 5 real-time PCR (Thermo-Fisher, USA) (Roy
et al., 2018). PCR is conducted with the proper arrangement of temperature and time duration of Annealing, Denaturation and Extension followed by particular number of cycles
(Kohno, Sugimoto, Sei, & Mori, 2002). Reaction carries both forward and reverse primer in
master mix (blend of reaction buffer, Taq DNA polymerase, dNTP (Deoxynucleoside triphosphates) and MgCl2) with DNA template and nuclease free water through a tailored
program. Later on quality of PCR product is checked by agarose gel (An et al., 2013).
18.3.5 Sequencing
The PCR product is subjected to decoding of DNA nucleotide through sequencing techniques that are switched according to the modification of process. Over the past decade
advancement in sequencing had moved to Next generation sequencing from traditional
Sanger sequencing method (Thomas et al., 2012) for the achievement of more sequenced
base pairs. Through the sequencing process libraries are generated via cloned nucleotides
D. Biological processes
18.3 Metagenomics in oil degradation
325
and vectors. Length of base pairs is considerable tool to analysis of quality, minimal length
of base pairs approx. 200250 is the indication of high quality. Miscellaneous techniques
and computational tool are utilized for trimming or filtering of the sequence, assemble the
sequence for the validation, analysis of assembled sequence and genome, comparison of
genome sequences, detection of GC content regions, establishment of Phylogenetic trees
and database submission. Basic Local Alignment Search Tool (BLAST) is applied for recognition of the novel and oriented organisms (Kimes et al., 2013) (Table 18.1).
18.3.5.1 Trimming or filtering
In the generated sequences both high- and low-quality base pairs are incorporated, so
that trimming and filtration is applied to low quality parameter genome. Fastx toolkit
trimmer is used for the trimming of k-mer contaminants and heterogeneous GC-content
areas. Metagenomes having less than 100 sequences are discarded from the final sequence.
Now appropriate sequences will be assembled and validated by different software (Mason
et al., 2012).
18.3.5.1.1 Sequence assembly and validation of assembled sequence
After going through process of trimming/filtering, nucleotides are managed and further
processed to validation. For base calling, vector sequence removal from sequences and
quality management BioMake software is used. PHRAP assembly tool is applied for
sequence assembly; genome sequence finishing is performed by CONSED/AUTOFINISH
software. Validation of assembled sequence is carried out by BACCardI tool in which
mapping of sequences is done onto the genome sequence.
18.3.5.2 Analysis of assembled sequence and genome
Having the assembled sequence, process moves towards analysis of observed
sequence/genome. Annotation system GenDB40 is utilized for selection and annotation of
genome. GLIMMER and CRITICA help in gene prediction. For each predicted gene various database along with InterPro, KEGG, Pfam, SWISS-PROT, TIGRFAM, and TrEMBL is
used for automatic annotation that performed before the manual annotation. Eventually
by COG (Clusters of Orthologous Groups) number every gene is practically classified
(Schneiker et al., 2006).
18.3.5.2.1 Alignment
Further two steps of alignment are setup for quality evaluation, which is performed
parallel one, is domain-based database against BioSurfDB and another is generic sequence
database against the RefSeq. At this platform some specific conditions are preliminary
considered:
18.3.5.2.2 RefSeq
RefSeq is surplus database that incorporate sequences from numerous sources, such as
complete set of nonredundant protein sequences can be downloaded. Program LAST is
performed for alignment of designate sequence as it align speedy repeat-rich datasets than
traditional approach BLAST and also very much appropriate data size issues. In RefSeq
database metagenome that are aligned use the default parameters for the LAST aligner.
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18. Metagenomics—an approach for selection of oil degrading microbes and its application in remediation of oil pollution
TABLE 18.1 Detailing of various sequencing techniques.
Sr.
no
Sequencing
technique
01
Description
References
Next-generation
sequencing
technologies
NSG also known as high-throughput sequencing
which cover the sequencing range from singlegene targeted sequencing to whole-genome
sequencing and also effective for analysis of
degradation, wastewater quality, diffusion of
pathogens and to detoxify the environmental
pollutants.
Kim et al. (2013)
02
Illumina
sequencing
Also known as DNA sequencing, used to
determine base pairs series in DNA, methylation
profiling, sRNA discovery, region and whole
genome sequencing. Method involved reversible
dye-terminators by which multiple strands are
sequenced at once that enhance sequence. More
over this method only uses DNA polymerase
instead of expensive and multiple enzymes.
Deng et al. (2016), Hong et al. (2017),
Ma et al. (2015), Wang et al. (2013)
03
Pyrosequencing
Pyrosequencing rely on luminometric detection of Fakruddin, Chowdhury, Hossain,
pyrophosphate (released by primer-directed
Mannan, and Mazumda (2012),
DNA polymerase catalyzed nucleotide
Peng, Zi, and Wang (2015, 2014)
incorporation) and suitable for DNA sequencing
up to 100 bases and elaborate depiction of nucleic
acids. This technique has fringe benefit like
flexibility, accuracy, automated functioning and
parallel processing. Even more it do not required
gel electrophoresis and labeled nucleotides and
primers.
04
SOLiD
sequencing
SOLiD sequencing show high speed and accuracy Rosselli et al. (2016)
and is the only platform that use ligation-based
sequencing relies on probe recognition method.
05
Ion torrent
semiconductor
sequencing
In this technique DNA sequencing is done by
detection of hydrogen ions (released during the
polymerization of DNA). Successfully applicable
in bacterial community characterization,
filamentous bacterial communities in wastewater
treatment systems and microbial communities in
nitrifying activated sludge.
Cao, Lou, Huang, and Lee (2016),
Gwin, Lefevre, Alito, and Gunsch
(2018), Salipante et al. (2014)
06
Nanopore
sequencing
This technology include significant advantages of
nanopores include low material need, high
throughput and ultra-long reads. No need of
chemical labeling and PCR amplification is
required for sequencing of single molecule of
RNA or DNA. Electrophoresis is used to
transport unknown sample via an orifice, also
applied for characterization of carbapenemaseencoding plasmids isolated from wastewater
treatment plant.
Feng, Zhang, Ying, Wang, and Du
(2015), Ludden et al. (2017), Xia et al.
(2017)
D. Biological processes
18.3 Metagenomics in oil degradation
327
MEGAN (version5) followed by RefSeq and KEGG maps databases is used for functional
and taxonomic Binning (Tatusova, Ciufo, Fedorov, O’Neill, & Tolstoy, 2014).
Use of RefSeq in taxonomic analysis: Clusters which have been formed by water or terrestrial metagenomes are arranged by RefSef on the basis of earlier studies that provide their
influencing factor. If metagenomes have alike biotic and abiotic conditions (such as temperature, sunlight, redox and osmotic potential and oxygen level) to previous available
metagenomes then the supply of nutrients and pH should be similar.
18.3.5.2.3 BioSurfDB
BioSurfDB is an informative system in bioremediation field, with a focal point on biosurfactant and biodegradation production organisms. It contain tools that helps in alignment of metagenomes against a number of protein sequences, total 46 sample of each
metagenome can be uploaded to the BLASTx tool and BioSurfDB system. From different
pathways approximately 3956 protein sequences are in the BioSurfDB database. This system automatically performs functional and taxonomic binning, but taxonomic prediction
may be biased as BioSurfDB is a domain specific database.
Use of BioSurfDB in functional analysis: By the help of BioSurfDB, genes that followed
pathway of hydrocarbon degradation accompanying gene involved in biosurfactant synthesis are analyzed. One of the main causes is miscibility effect of biosurfactant on hydrophobic material that favored biodegradation.
18.3.5.3 Comparison of genome sequences
After the alignment of resultant sequences, comparison of chromosomal sequences is
done with the available sequences in GenDB. This availability is generated by previous
cluster analysis.
18.3.5.3.1 Cluster analysis
By the RefSeq and BioSurfDB analysis all the alignment are obtained from metagenomes and uploaded to MEGAN to evaluate Principal Coordinates Analysis and UPGMA
trees. The computational metagenomics tools involves metabolic pathways, scripts to cross
the BLASTx results, database tree and proteins. For normalization these tables are
uploaded to Genesis, followed by the calculation of hierarchical clustering for both metagenomes and pathways.
18.3.5.4 Detection of GC content regions
From yeast to humans in various organisms high percentage of meiotic recombination
is correlated with GC richness and also some mismatches like A-C, A-G, T-C or T-G are
fixed by a G-C pair formation. High GC genes also have significantly increased meiotic
and mitotic recombination rates (Kiktev, Sheng, Lobachev, & Petes, 2018). Sliding window
is the tool for the detection of genomic regions with unusual GC content. Usually 2000
base pair window size and 1000 base pair step size is used for the purpose (Oliveira et al.,
2017). GC content parameter is an important influencer to genome evolution.
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18. Metagenomics—an approach for selection of oil degrading microbes and its application in remediation of oil pollution
18.3.5.5 Phylogenetic trees establishment
Among the various taxa evolutionary relationships are diagrammatically represented
via Phylogenetic trees establishment. By BLAST analysis homologs are identified and
ClustalX 1.83 tool (Thompson, Gibson, Plewniak, Jeanmougin, & Higgins, 1997) is used in
rooted neighbor joining phylogenetic trees construction. Furthermore visualization is done
by TreeExplorer software MEGA package49 (Kumar, Tamura, Jakobsen, & Nei, 2001).
18.3.5.6 Submission of database
Results are assembled in a metadata file and uploaded to STAMP to determine correlation between the production and hydrocarbon degradation by performing the statistical
tests between metagenomes to Graphpad Prism (Schneiker et al., 2006). Now the evaluated
results are submitted to GenBank under a particular accession number, which is used for
analysis and comparison of undiscovered genome.
18.3.6 Phylogenetics
Phylogenetic assignment is a very important step in metagenomic analysis to
introduce functional properties of uncharacterized microorganisms that are encrypted by
the DNA fragments to the phylogeny (Sierra-Garcia et al., 2014). Phylogenies reflects
the progressive journey of species development by flow of time and phylogenetics is the
study of that phenomenon. Phylogenetics covers comparative genomic study ranging
from ancient time to current time. The evolutionary relationship displays via a branching
or treelike representation (i.e. phylogenetic tree). Construction of Phylogenetic tree is
done by neighbor joining method and Jukes & Cantor Model is used to calculate the
distance matrixes for single nucleotide substitution (Chikere, Surridge, Cloete, &
Okpokwasili, 2011). Phylogenetic tree is composed of nodes and branches, one branch
can only connected to two nodes and outer nodes show the leave or the operational taxonomic units (Fig. 18.2).
Innumerable computational tools are proposed for the formation and analysis of
phylogenetic tree such as: by using Phylo F3 software 16S rRNA bacterial gene
sequences observed from NCBI database (Olukunle, 2019) and Phylogenetic inference
sister
taxa
Branch
Internal
node
sister
taxa
Root
Internal
node
FIGURE 18.2
OUTs/ Leaves: - Can be populaon, genes,
species, protein sequences
Outgroup
Basic schematic representation of phylogenetic tree formation.
D. Biological processes
18.4 Application
329
package is used to determine the phylogenetic relationships of sequences observed
from dominant Denaturing gradient gel electrophoresis bands. The PhyloPythia software used for the observation of all metagenomic clones. Further by using BLAST,
analyzed data will be compared with the available data in the Gen-Bank database
that is available at http://www.ncbi.nlm.nih.gov/blast/ (Kubota, Koma, Matsumiya,
Chung, & Kubo, 2008).
18.4 Application
In ecological matrix, metagenomics is an approachable, effective, and beneficial tool to
observe and explain the configuration and dynamics of microorganisms. It also plays a
wonderful role to capture potent microbial degrader and modify detoxification and degradation properties toward the inorganic and organic contaminates at polluted sites by
altering their metabolic pathways (Zwolinski, 2007). With respect to this many effective,
promising, and novel microbial community can be recognized and preserved for the
future perspective. Numerous environmental microorganisms have effective whole
genome sequences availability which is relevant to explain the gene pool of enzymes
that are participants in anthropogenic pollutants degradation (Galvão, Mohn, & de
Lorenzo, 2005). Metagenomics is an efficacious practice to overcome the complications of
cultivation-dependent research, as isolation of nucleic acids is done directly from environmental samples (Desai, Pathak, & Madamwar, 2010). Newly, DNA microarrays are
applied for monitoring the novel population of microorganism and utilize their potency
in bioremediation (Bae & Park, 2006). A large number of researches are successfully
reported and recorded to the data base that reveals various novel microbial category and
metabolic pathways. Some of these resultant novel microorganisms and their application
are given below:
Metagenomics has paved the way to new age classification and application of microbes
for anthropogenic pollutant degradation. In a research Kim et al. (2006) used integrated
approach rely on cleavable isotope-coded affinity tag analysis, to recognize and investigate
catabolic pathways in Pseudomonas putida KT. For the advancement and modification of
technologies researchers foreground by introducing new approach like “metabolomics”
beyond the available approaches such as proteomics, genomics, and transcriptomics. A lot
of studies and researches recently used metabolome analysis in the biodegradation of
anthropogenic pollutants.
The microbial communities which are utilized to enhance biological phosphate removing efficiency by Candidatus Accsumulibacter phosphatis (a dominant polyphosphate
accumulating organism) was decoded by Martı́n et al. (2006) via generating the metagenomic libraries, they also construe metabolic and ecological activities of these microbial
communities. Metatranscriptomics/Transcriptomic approaches are preferable to observe
functional understating of environmental microbial communities activities by examining
their mRNA transcriptional status.
By implementing transcriptomics research on a cis-dichloroethene (cDCE) strain
Jennings et al. (2009) identify the category of genes that are updated by cis-dichloroethene
through DNA microarrays. When microorganisms contact with anthropogenic pollutants,
D. Biological processes
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18. Metagenomics—an approach for selection of oil degrading microbes and its application in remediation of oil pollution
the identification of proteins (present in microorganisms) that are involved in physiological response are completed by proteomics-depended investigations and also are used to
determine composition alteration and richness of proteins.
A study is explained by Keum, Seo, Li, and Kim (2008) which disclose the comparative
metabolome observation of Sinorhizobium sp. through the phenanthrene degradation.
Tang et al. (2009) work on Shewanella sp. which possesses cometabolic pathways for
bioremediation or degradation of halogenated organic compounds, toxic metals and
radionuclides.
18.5 Metagenomics challenges
Besides the incredible response of metagenomics in hydrocarbon degradation, technique also retain some gaps that should be traced and fixed rapidly, so that modified techniques give required outcomes to resolve the issues. Since the metagenomics techniques
fall in environmental domain which also has a bundle of limitations such as:
Selectivity: Nature is excessively embedded by the variety of microbial population that
have different functionality toward the different aims (Aislabie, Balks, Foght, &
Waterhouse, 2004), but it is a challenge for researchers to screen out the desired microorganism that can give right directions and results so that screening techniques required
more advancement and modification (Ghosal, Ghosh, Dutta, & Ahn, 2016).
Time duration: Technique in Metagenomics is aiming towards the novel species so no
previous information is available in most cases which lead to more time consumption in
every step for verification.
Cost: Various software and data tools are needed to includes new organism category
and their pathways. This needs sufficient funding and expertise brain. Till now, the issues
of the occupancy of unlike coverage over species, very alike sequences and constant
sequences due to horizontal gene transfer, are still to be resolved through dedicated software (Bharti & Grimm, 2021).
Manpower engagement: For implementing the metagenomics studies, new design, collection and observation of metadata and conversion of data into appropriate information
required skilled and experience statistician and bioinformatician which makes it more
complex and highly specialized field. Moreover, many specialized members are needed
for performing specific steps in the whole metagenomic analysis (Handelsman, 2004).
Result failures: The procedure has many sections to reach the final result and generate
the libraries, so the failure of any step spoils the entire process. Other Challenge is to verify the mechanism of correct gathering as subsequent downstream observation will hang
on its result (Pandey & Singhal, 2021).
In conclusion, at present time metagenomics is most remarkable, structured and relevant approach for hydrocarbon degradation and is proving to be the most preferred
method for researchers to introduce novel species category and pathways but it called for
some addition and deletion for the betterment of method (Alves et al., 2018). Current
metagenomics challenges decode by addressing two main tools:
1. Growth of novel bioinformatics tools
2. Creation of novel molecular tools
D. Biological processes
References
331
18.6 Conclusion
Every year a heavy load of hydrocarbons (as an alarming pollutant) are exposed to the
environment due to various anthropogenic activities such as incomplete combustion of
fossil fuels, petroleum spills, and by industrial waste (Jacques, Bento, & de Oliveira
Camargo, 2007) and many more; for the cleanup of this troublesome mess researchers
have turned to nature. As some microorganisms present in nature involve in hydrocarbon
degradation through the various reactions, for discovery of such reactions, pathways,
unknown microorganism and display their availability records metagenomics is a perfect
platform (Nazir, 2016). By using metagenomic approach effective category of gene and
their metabolic pathways are captured that associated in phenol and other aromatic compounds degradation of sludge sample that are collected from a petroleum refinery wastewater treatment system (Silva et al., 2013). Although the ratio of oil contaminated water
and degradation rate is very imbalanced as anthropogenic activities pointing towards the
environment safety, so there is an emergency requirement of a combine action that is control the contamination action and speedy modification to discover microbial degraders
and improve the pathways.
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C H A P T E R
19
Potentiality of enzymes as a green
tool in degradation of petroleum
hydrocarbons
Uttarini Pathak, Aastha Jhunjhunwala, Sneha Singh,
Neel Bajaj and Tamal Mandal
Department of Chemical Engineering, National Institute of Technology Durgapur, Durgapur, India
O U T L I N E
19.1 Introduction
337
19.2 Role of bacteria in enzymatic
degradation of petroleum
hydrocarbons
339
19.3 Role of algae in enzymatic degradation
of petroleum hydrocarbons
343
19.5 Feasibility and technical applicability
of enzymes in oil clean up
346
19.6 Conclusion
348
Conflict of interest
349
References
349
19.4 Role of fungi in enzymatic degradation
of petroleum hydrocarbons
344
19.1 Introduction
Petroleum and its products are in huge demand currently. The availability of oil in only
some countries has enabled them to monopolize the oil industry thereby making oil a
costly and much in demand commodity. In today’s industrialized world most of the activities are heavily dependent on oil and hence the occasional oil spill and effluents are a
major concern. The seepage of these components in soil leads to both water and soil pollution (Holliger et al., 1997) Contamination of the soil by these activities leads to the
Advances in Oil-Water Separation
DOI: https://doi.org/10.1016/B978-0-323-89978-9.00024-0
337
© 2022 Elsevier Inc. All rights reserved.
338
19. Potentiality of enzymes as a green tool in degradation of petroleum hydrocarbons
infiltration of these pollutants into plants and animals which may lead to death or mutation of the species (Alvarez & Vogel, 1991). The traditional method of cleansing the soil is
costly, ineffective, and harder to carry out on large areas all at once, hence washing, evaporation, and mechanical methods are discarded. Bioremediation is the usage of microorganisms to eliminate the pollutants attributing to their specific structural metabolism and
is a promising arena for the degeneration of various pollutants affecting the environment
and the components and effluents released from petroleum drills as well.
Bioremediation consists of various biochemical reactions, involving all biotic and abiotic natural bioattenuation processes to deflate the contamination levels. It is a good alternative as well
as the primary mechanism for reducing biodegradable toxicants and with a favored economic
effectiveness. But it is a slow mechanism where its kinetics are subjected to factors like salinity,
microbial diversity, temperature, etc. However, a wide variety of petroleum hydrocarbon remediating strains and their enzymatic metabolic pathways encourages the biodegradation
approach. The occurrence of bioremediation takes place by the following ways:
1. Naturally
2. Bioaugmentation (whole cell introduction)
3. Biostimulation (utilization of nutrients for stimulation of the native microbial community)
Also, usage of microorganisms is nonthreatening and cost-effective (April, Foght, & Currah,
2000). Hence bioremediation can be seen as a promising avenue that will mitigate the problems
the petroleum industry poses with its ecofriendly and effective outcomes (Ulrici, 2000).
During the infamous Exxon Valdez oil spill in 1989 (Atlas & Bartha, 1998) located in
the Gulf of Alaska, bioremediation came as a breakthrough as its use to clean up the oil
spill was successful which leaded to people’s interests in this arena that could open up
more greener avenues and search for bioremediation technologies increased. Many of
the present studies have focused on understanding the parameters affecting oil bioremediation and favored tests through laboratory studies (Mearns, 1997). In the peerreviewed literature only a limited number of field trials are believed to yield promising
results for bioremediation technology (Prince, 1993; Swannell, Lee, & Mcdonagh, 1996;
Venosa, Suidan, & Suidan, 1996; Venosa et al. 2002). The avenue for current application
of bioremediation is specifically bounded by a fact that majority of the research focuses
on large scale oil spills.
Aerobic degradation is a faster metabolic process with the advantage of having oxygen
availability, the latter acting as an electron acceptor. Oxidation of saturated aliphatic
hydrocarbon gives acetyl-CoA as the final product which is further catabolized during
citric acid cycle producing electrons as a result in the electron transport chain. The repetition of the chain leads to formation of CO2 as the final product. Aromatic hydrocarbons
like benzene, napthalene are also degraded under aerobic conditions. Here the first product formed by degradation is catechol, which is further degraded to CO2 by being introduced in citric acid cycle. Since it has been mentioned earlier that aerobic degradation is a
faster process compared to anaerobic digestion, it is also important to note that the latter
is a crucial factor to bioremediation process. The reason is that there are several limitations
to oxygen availability conditions as that in aquifers and sludge digester systems. The
anaerobic metabolism of aromatic compounds results in formation of Benzoyl-CoA.
Nitrates, sulfates act as terminal electron acceptors which can be used based on
D. Biological processes
19.2 Role of bacteria in enzymatic degradation of petroleum hydrocarbons
339
FIGURE 19.1 Schematic diagram for
aerobic degradation of hydrocarbons by
microorganisms (Das & Chandran, 2011).
environmental conditions (Das & Chandran, 2011; Peixoto, Vermelho, & Rosado, 2011).
Fig. 19.1 showcases the mechanism of aerobic degradation of hydrocarbons by
microorganisms.
Apart from using microbes, enzymes too are seen as a promising arena due to their
added advantages. Enzymes cannot be rendered inactive by inhibitors of microbial metabolism. They also come handy in extreme conditions where microbes’ effectiveness
decreases. Enzymes are efficient even at low pollutant concentrations and also in the presence of microbial predators. They act against a given substrate and are more active than
microorganisms because of their miniature dimension (Peixoto et al., 2011). These added
advantages make enzymes environmental-friendly catalysts. Fig. 19.2 gives a schematic
view of the enzymatic reactions during hydrocarbon degradation.
This paper aims to provide detailed research on degradation driven by microorganisms
of effluents released from petroleum products and oil spill pollution using bacteria, fungi,
and algae incorporating enzymatic technology that would work for a better study on the
future of bioremediation technology and a step toward an ecofriendly globe (Table 19.1).
19.2 Role of bacteria in enzymatic degradation of petroleum hydrocarbons
Microbial degradation is a prominent mechanism by which the hydrocarbon pollutants
of the environment containing petroleum can be cleaned. Bioattenuation of alkyl aromatics
D. Biological processes
340
FIGURE 19.2
19. Potentiality of enzymes as a green tool in degradation of petroleum hydrocarbons
Schematic diagram of enzymatic reactions during hydrocarbon degradation (Das & Chandran, 2011).
in marine segments by organisms such as Arthrobacter, Burkholderia, Rhodococcus have been
studied by a few scientists. Efficiency of biodegradation has been found to range from
0.13% to 50% for soil bacteria, 6%82% for soil fungi, and 0.03%100% for marine bacteria
(Nakamura, Tomita, Abe, & Kamio, 2001)
Bacteria have been found to be the most active agent in degrading the spilled oil in the
environment. Few specific bacteria have been found to feed exclusively on hydrocarbons.
Isolated bacterial species such as Aeromicrobium, Brevibacterium, Burkholderia, Dietzia,
Gordonia, and Mycobacterium found from petroleum contaminated soil emerged to be effective for hydrocarbon degradation (Nannipieri et al., 1991).
However, bacteria have the potential of degrading different petroleum components
under different aerobic and anaerobic conditions at varied pH and salinity. A sequential
enzymatic metabolism is responsible for petroleum degradation. In this process, the genes
involved are either located on chromosomes or on Plasmid DNA (Nicell, 2001).
Through various research studies, it has been found that Pseudomonads are one of the best
bacteria which are capable of utilizing hydrocarbons and producing surfactants. Pseudomonads
and P. aeruginosa has been widely studied for producing glycolipid type biosurfactants. These
bio surfactants tend to increase the oil surface area. The role of Pseudomonas sp. in bio surfactant production during uptake of hydrocarbons has been represented in Fig. 19.3.
Another bacterial species of the genus Bacillus are also of great use because of their
capability of producing endospores, which enables them to remain in dormant state when
the environment is not favorable.
D. Biological processes
19.2 Role of bacteria in enzymatic degradation of petroleum hydrocarbons
341
TABLE 19.1 A summary of enzymes responsible for degradation of petroleum hydrocarbons by bacterial and
fungal species.
Name of the enzyme
Bacterial species
Fungal species
References
Soluble methane
Monooxygenases
Methylococcus
Methylosinus
Methylocystis
Methylomonas
Methylocella
McDonald et al. (2006)
Dioxygenases
Acinetobacter sp.
Maeng, Sakai, Tani, and Kato (1996)
AlkB related
Alkane
Hydroxylases
Pseudomonas
Burkholderia
Rhodococcus
Mycobacterium
Jan et al. (2003)
Bacterial P450
Oxygenase system
Acinetobacter
Caulobacter
Mycobacterium
Van et al. (2006)
Eukaryotic P450
Candida maltosa
Candida tropicalis
Yarrowia lipolytica
Iida, Sumita, Ohta, and Takagi (2000)
Cytochrome 450 hydrolases
Candila apicola
C. Tropicalis
C. Maltose
Cerniglia, Gibson, and Van Baalen (1980), Gamila et al. (2003)
Apart from the species mentioned above, the third important one is Rhodococcus. A
member of this species, including both pathogens and non pathogens can be found in soil
and marine ecosystems and are found to metabolize harmful environmental pollutants
like various hydrocarbon compounds. The reason for their degradation capacity getting
enhanced is that their hydrophobic surface can get attached to the hydrocarbon chains
(Rubilar, Diez, & Gianfreda, 2008; Sánchez, 2009).
Species like esterases, anudases, and proteas are capable of breaking down esteric, amidic and peptidic bonds which leads to formation of nontoxic products. For example, bacterial hydrolases such as carbamate have been successfully used in transformation of
pollutants such as carbofuran, coumaphos, etc. (Sheldon & Van, 2004). Several bacteria are
also capable of producing carbohydrases, proteases which helps in the transformation of
insoluble materials like carbohydrates, plastics, and proteins. A few examples of hydrolases are anudases and proteases.
Obligate hydrocarbonoclastic bacteria (OHCB) are the bacteria that use hydrocarbons as
carbon source (Atlas, 1981). They have a low abundance in sea water. When due to any
reason, hydrocarbon input increases in the seawater, OHCB increases in abundance, the
reason being that they have higher efficiency in utilizing hydrocarbons as their carbon
source. Hence, they have an important role to play in eliminating the water body of such
pollutants. Examples of OHCB are Marinobacter, Cycloclasticus.
Both aliphatic and aromatic compounds bioremediation can occur under the conditions
mentioned above (Atlas, 1984). The aerobic degradation is catalyzed by oxygenase
enzymes which introduce oxygen atoms in the hydrocarbons, while the anaerobic one is
catalyzed by sulfur reducing bacteria.
D. Biological processes
342
FIGURE 19.3
19. Potentiality of enzymes as a green tool in degradation of petroleum hydrocarbons
Role of Pseudomonas sp. in bio surfactant production during uptake of hydrocarbons (Das &
Chandran, 2011)
Different petroleum contaminated sites have been found to be restored by bioaugmentation and biostimulation processes (Atlas & Bartha, 1992). They minimize the impact of
petroleum spills. However, like every other process, these also come with their advantages
and disadvantages. For example, the competitiveness of inoculated strains is the main factor to the success of bioaugmentation in different environments. Petroleum degradation
efficiency can also be increased by genetically modified organisms. Environment where
indigenous petroleum hydrocarbon degrading microorganisms exist, biostimulation comes
handy. Research will find alternative biological strategies to enhance the effectiveness in
the environment. New improvements in the development of products and methods by
reducing industrial costs have been opened by biocatalysis. Enzymatic remediation is a
simpler process than working with whole organisms (Foght & Westlake, 1987;
Vandermeulen and Hrudey, 1987). Toxic by products are not formed when isolated
enzymes are used.
PAH detoxification is an example of enzymatic bioremediation involving the use of laccases (Mearns, 1997). Organic solvents are the prime agents for the occurrence of enzymatic oxidation. This is an advantage in case of xenobiotic enzymatic bioremediation
which are mainly hydrophobic or poorly soluble in PAH. However, the disadvantage is
that they can be unstable in organic solvents. A recent study based on an enzyme based
product like TrzN showed that this strategy can effectively detoxify aquatic systems contaminated with herbicides (Prince, 1993).
D. Biological processes
19.3 Role of algae in enzymatic degradation of petroleum hydrocarbons
343
Rhoder is a mixed hydrocarbon degrading bacteria consisting of R. Ruber and R.
Erythropolis showing 99% and 94% efficiency for aquatic and land surfaces respectively
(Swannell et al., 1996). It can even grow in a low oxygen concentration environment
because of their microaerophilic respiration capacity.
The main aspect to be kept in mind for selection of an enzyme for bioremediation is
that it should have the capability to degrade the pollutant to less or nontoxic products.
Secondly, it should not depend on cofactors as that would inflate the process expense
from the commercial point of view. The third stage comprises of identification of the gene
that encoded the selected enzyme, and to improve enzymatic production (Venosa et al.,
1996). On a large scale, these are produced by fermentation where the unwanted cells are
eradicated during downstream processing.
19.3 Role of algae in enzymatic degradation of petroleum hydrocarbons
“Phycoremediation” is the process of elimination and degradation of organic contaminants by algae. In addition to being sustainable, ecofriendly, and cost effective the process
generates byproducts with useful applications. Biofuels generated as part of this bioremediation process serve as a sustainable source of bioenergy which has the potential to meet
the demands for energy in the future (Vassilev & Vassileva, 2016). There are two major
processes by which algae eliminate intoxicants: Biosorption: a passive process where the
pollutants bind to nonliving biomass from an aqueous solution and Bioaccumulation: an
active process where organic pollutants are removed by an organism’s metabolic activity
(Ben et al., 2014; Baghour, 2017; Davis, Volesky, & Mucci, 2003) Algae adopt other strategies for bioremediation as well, these include biodegradation, biotransformation and
biomineralization (Baghour, 2019; Martinez et al. 2019) In recent times algae have been
seen to play a promising role in the degradation of organic compounds due to their low
environmental impact, fast growth rate, low water intake, land requirements and adaptability. Both microalgae and macroalgae fall under the umbrella term algae. Microalgae
are unicellular algae that constitute the bulk of the existing algal species. Macroalgae are
multicellular algal species that are classified on the basis of the pigment coloration as
brown, red and green seaweed respectively (Baghour, 2019). Arthrospira, Botryococcus,
Chlamydomonas, Chlorella, Cyanothece, Desmodesmus, Phormidium, Nodularia, Oscillatoria,
Scenedesmus, Spirulina, etc., are few of the species of microalgae used for remediation of
organic compounds (Dubey, Dubey, Mehra, Tiwari, & Bishwas, 2013; Rawat, Kumar,
Mutanda, & Bux, 2011) Ulva lactuca, Kappaphycus alvarezii, etc., are some macroalgal species
used for detoxification. It is observed from literature that the studies related to the accumulation of organic xenobiotics and degradation in the green algae have come to be of
much significance due to the widespread occurrence of the species in agricultural regions
causing it to be a major issue in the marine ecosystem (Jin et al., 2012)
There has been a recent surge in the usage of algae for water quality assessment via biomonitoring. Biomonitoring involves the deployment of organisms as bioindicators to evaluate a change in the environment. Seaweeds possess great potential as bioindicators due
to their widespread distribution, availability in polluted media, physical properties which
D. Biological processes
344
19. Potentiality of enzymes as a green tool in degradation of petroleum hydrocarbons
make them easy to identify, ability to accumulate pollutants, rapid growth rates and short
life spans make them well suited to study short term impacts (Omar, 2010).
Algal remediation is one of the many methodologies used to treat petrochemical wastewater. The hydrocarbons serve as the carbon and energy source for metabolic activity of
algae, thereby rendering the toxic contaminants harmless by their degradation. Literature
suggests that Chlorella vulgaris and Scenedesmus obliquus thrive in heterotrophic conditions
and efficiently degrade low concentrations of oil. Further Scenedesmus obliquus can be used
for biodegradation of crude oil by means of an artificial microalgal-bacterial consortium
(El-Sheekh, Hamouda, & Nizam, 2013).
Thus algae provide a potential solution for removal of pollutants either by directly bringing
about the transformation of the contaminant or by acting as a catalyst and expediting the degradation. They lower the carbon dioxide levels in the atmosphere, thereby reducing the effects
of global warming. The biomass generated from this process has a wide variety of applications such as use as animal feed, extraction of products such as carotenoids, production of
renewable energy in the form of biofuel in addition to providing reusable clean water thereby
minimizing the use of fresh water (Rawat et al., 2011). Fig. 19.4A and B represents the biotransformation of napthalene and phenol by algal species.
19.4 Role of fungi in enzymatic degradation of petroleum hydrocarbons
The fungi species used for the degradation of hydrocarbons depend on the nature of the
hydrocarbon. Some fungi such as Amorphotheca, Aspergillus, Graphium Cunninghamella, Fusarium,
Neosartorya, Penicillium, Paecilomyces, Talaromyces are used for degradation of recalcitrant pollutants. Several other species as reported in the literatures have been represented in Table 19.2.
Bioremediation of pollutants is governed by several environmental factors, the most important
being the restricted availability of microbes in the environment. The activity of these microbes is
affected by other factors such as temperature, pH, bioavailability, salinity, oxygen, and nutrients.
The hydrocarbons act as the source of both carbon and energy for their own biodegradation.
Further the degradation of the hydrocarbon is also dependent on the medium, that is, there is
distinction between the degradation of hydrocarbons in soil and degradation in water. Oil spills
call for remediation in water. The biodegradation is recumbent on the chemical and physical
properties of oil and the particle nature which in turn depends on the mobility and dispersion
of oil in water (Al-Hawash et al., 2018). The mechanism of interaction of fungal cell with the
various complex hydrocarbons has been outlined in Fig. 19.5.
The rate of degradation of hydrocarbons is impacted by the temperature being directly proportional in nature. Due to reduced enzymatic activity at low temperatures, degradation is
lower at lower temperatures and higher at higher temperatures (Bisht et al., 2015). Oxygen level
and the presence of nutrients are also regulators of biodegradation. Oil spills often lead to
increased carbon levels in the aquatic environment thus resulting in lower concentrations of
nitrogen and phosphorus, thereby resulting in the need for addition of nutrients to promote biodegradation. At the same time an excess of nutrients isn’t conducive to the microbes as well
(Hesnawi & Adbeib, 2013). Salinity adversely affects the bioremediation process; this is due to
its impact on microbial activity, i.e., metabolic rate of enzymes decreases with increase in salinity of the surrounding medium. Furthermore it can be observed from literature that most
D. Biological processes
19.4 Role of fungi in enzymatic degradation of petroleum hydrocarbons
345
FIGURE 19.4 (A) Mechanism of biotransformation of Napthalene by algal species as proposed by Semple, Cain, and
Schmidt (1999), (B) Mechanism of biotransformation of phenol by Ochromonas danica
as proposed by Semple et al. (1999).
D. Biological processes
346
19. Potentiality of enzymes as a green tool in degradation of petroleum hydrocarbons
TABLE 19.2 Degradation of petroleum hydrocarbons by different fungal species (Li, Liu, & Gadd, 2020).
Species
Hydrocarbons Formula Structure
Removal
efficiency
(%)
Penicillium
sp.
Decane
C10H22
49.0
28
Govarthanan, Fuzisawa,
Hosogai, and Chang (2017)
Aspergillus
sp.
N-hexadecane C16H34
86.3
10
Al-Hawash, Dragh, et al.
(2018)
Fusarium sp.
N-octadecane
C18H38
89
60
Hidayat and Tachibana (2013)
Phomopsis
liquidambari
Phenanthrene
C14H10
77.4
10
Fu et al. (2018)
Irpex lacteus
Anthracene
C14H10
60
25
Drevinskas et al. (2016)
Pleurotus
ostreatus
Anthracene
C14H10
56
23
Drevinskas et al. (2016)
Ganoderma
lucidum
Pyrene
C16H10
99.6
30
Agrawal,LVerma, and Shahi
(2018)
C18H12
65
30
Hadibarata, Tachibana, and
Itoh (2009)
Polyporus sp. Chrysene
Treatment
length (d)
Reference
enzymes prefer to thrive in a neutral to alkaline environment. Although fungi in general are tolerant to acidic conditions the neutral conditions with sufficient availability of water allow the
microbes to flourish thereby favoring biodegradation (Pawar, 2015). Thus the degradation of
hydrocarbon pollutants is influenced by a variety of biotic and abiotic factors which promote
the growth of the biological species and thereby expedite biodegradation (Fig. 19.6).
19.5 Feasibility and technical applicability of enzymes in oil clean up
The existing treatment techniques for oil clean up involve the introduction of deleterious chemical agents into the environment, whereas the technology described in this work
provides a safer and more environmental friendly alternative. The enzymatic agent itself is
biodegradable; therefore this process produces no harmful remnants and doesn’t waste
energy. This process relies on the natural biological cycle of certain microorganisms to
clean up oil spills. The enzymes present within the microorganism break down the toxic
pollutants into nontoxic substances, thereby rendering them harmless. Bioremediation is
flexible in nature and can be carried out both in-situ and ex situ. In situ remediation
involves making use of the indigenous microorganisms which naturally occur at the site,
whereas ex situ treatment involves transportation of the contaminated material to a treatment site different from where the pollution takes place (Atlas & Philp, 2005).
Bioaugmentation and biostimulation methodologies are currently seen as methods that
could aid in restoring various sites that are currently contaminated with petroleum and
thus can reduce the effects of petroleum spills. These varied options should be carefully
D. Biological processes
19.5 Feasibility and technical applicability of enzymes in oil clean up
347
FIGURE 19.5 Mechanism of fungal cell enzymatic interaction with petroleum hydrocarbons (Li et al., 2020).
FIGURE 19.6 Growth potentiality of fungal species under different concentrations of crude oil (Mohsenzadeh,
Chehregani, & Akbari, 2012).
D. Biological processes
348
19. Potentiality of enzymes as a green tool in degradation of petroleum hydrocarbons
researched and planned for specific types of contaminant and environmental conditions,
as they come with their own set of pros and cons. For example, effectiveness of bioaugmentation is seen to depend on the competitiveness of the inoculated strains in different
environments and biostimulation can be meticulously used in environments where indigenous petroleum-degrading microorganisms are found (Durkee, 2016). Researching on
alternative bioremediation pathways is vital to increase their effectiveness manifolds and
applications at varied locations. Bioaugmentation is another organic treatment methodology wherein nonindigenous microorganisms are procured and added to the contaminant
site. Bioremediation has a wide variety of applications in the present day. In addition to
being implemented to treat oil spills, it can be used for treating industrial wastewater,
mines, groundwater, contaminated soils, and fly-ash disposal sites. Although the search
for an alternative strategy to bioremediation is crucial, their effectiveness can be increased.
Bio catalysis has reduced industrial costs, and improved product development. It is contributing to minimize the fossil fuel damage. It has a favorable cost-benefit ratio. This is
because of the recent application of molecular tools to it.
Enzymatic biodegradation is different because it works in a systematic way, and is not prone
to conditions. The enzyme, in this process works by itself, without the need of any chemical.
Research and lab testing data have shown that once the biodegradation starts, it finishes with
the complete reduction of toxins and bacteria. Once the decontamination is done, the enzyme
starts biodegrading itself, and eventually no toxic substance is leftover. Considerable success
has been achieved by researchers and scientists to break down harsh toxic pollutants with the
help of bioremediation. Bioremediation involving enzymes finds use in metal biorecovery and
in the production of useful biominerals. However, bioremediation often involves the degradation of crude by a combination of different bacterial species, since each group acts on certain
specific hydrocarbons only (Kohli, 2019). Further bioremediation cannot be put to use at sites
with high concentrations of chemicals that are toxic to most microorganisms. These can sometimes prove to be a bottleneck in the application of microorganisms for waste treatment.
Enzymatic degradation due to its versatile nature can often be combined with other
treatment methodologies such as electro kinetics to find solutions for enhanced removal of
hard to remove compounds such as herbicides, byproducts in chemical manufacturing,
petroleum by products, etc. Thus bioremediation due to its ability to provide a cost effective and viable environmental friendly solution is gaining ground fast.
19.6 Conclusion
The use of enzymes for removal of intoxicants in the form of petrochemical oil has
come to be of much importance in recent times due to its sustainable nature.
Bioremediation using enzymes secreted by microbes such as bacteria, fungi, and algae
have gained prevalence due to their environmental friendliness, cost effectiveness, and
their role in reducing the effects of global warming; the enzymes regulate the carbon dioxide levels in the atmosphere by using it as a source of energy for their metabolic activity.
Furthermore they have a pivotal role to play in recovering the marine ecosystem such as
the endangered and sensitive coral reefs. In addition to providing clean water, bioremediation provides for byproducts such as biofuels which are renewable sources of energy and
D. Biological processes
References
349
mitigate the use of exhaustible fossil fuels. However, this process relies heavily on the
availability of microbes. Further analysis could be carried out to study the efficiency of different microbial species in treating oil spills.
Conflict of interest
On behalf of all authors, the corresponding author states that there is no conflict of interest.
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C H A P T E R
20
Bioremediation: an ecofriendly
approach for the treatment of oil
spills
Sudipti Arora1, Sonika Saxena1, Devanshi Sutaria1 and
Jasmine Sethi2
1
Dr. B. Lal Institute of Biotechnology, Jaipur, India 2Entrepreneurship and Career Hub,
University of Rajasthan, Jaipur, India
O U T L I N E
20.1 Introduction
20.1.1 Oil spills
354
354
20.2 Catastrophe
20.2.1 Hydrocarbon pollution
355
356
20.3 An approach to eliminate oil spills 357
20.3.1 Bioremediation and its
techniques
358
20.4 Factors affecting the biodegradation
efficiency
363
20.4.1 Nutrient availability
364
20.4.2 Temperature
365
20.4.3 Oxygen limitations
365
20.4.4 pH
365
Advances in Oil-Water Separation
DOI: https://doi.org/10.1016/B978-0-323-89978-9.00012-4
20.4.5 Bioavailability of hydrocarbon 366
20.4.6 Restriction of physical contact
between microorganism and oil
spills
366
20.5 Role of microorganism
367
20.6 Novel approaches
20.6.1 Substance addition
20.6.2 Genetic engineering
368
368
369
20.7 Case studies
369
20.8 Conclusion and future prospects
370
References
370
353
© 2022 Elsevier Inc. All rights reserved.
354
20. Bioremediation: an ecofriendly approach for the treatment of oil spills
20.1 Introduction
Industrialization is the backbone of the country’s growth, but industry-induced pollution is a
major concern worldwide. Globally, pollution from crude oil and its derivatives have become
an important environmental issue. Due to its widespread usage and its related disposal operations and accidental spills, environmental pollution by crude oil is relatively common. The term
petroleum refers to a highly complex mixture of a large range of hydrocarbons of low and high
molecular weight. It has been estimated that at least 0.08%0.4% of the oil produced globally
has been released into the aquatic environment as pollutants. Increasing amounts of spilled oil
are often received annually by the terrestrial and atmospheric ecosystems, imagining how
severe this environmental problem is. Petroleum hydrocarbons, polynuclear aromatic hydrocarbons (such as naphthalene and benzopyrene), and solvents are among the most common chemicals involved in oil pollution. Inadvertent or intentional discharge of crude oil and its
derivatives pose problems of increased magnitude (Okoh & Trejo-Hernandez, 2006).
Furthermore, these problems are more aggravated because of the expensive disposal methods
(Rahman et al., 2003; Das & Mukherjee, 2007).
20.1.1 Oil spills
Oil spill refers to the release of liquid petroleum hydrocarbon into the environment,
especially on water which could be due to the climatic factors or natural disturbances or
anthropogenic activities causing environmental pollution. This problem is of major concern in sea and fresh water bodies like rivers, land, lakes etc. The main anthropogenic
sources of oil spills over the natural waters include the following:
20.1.1.1 Accidental spills during
1. Storage
Oil and oil products may be stored in a variety of ways including underground and
aboveground storage tanks (USTs and/or ASTs, respectively); such containers
(especially USTs) may develop leaks over time.
2. Handling
During transfer operations and various uses, oil leakage or spillage may occur and
pollute the land or water.
3. Transport
During the transportation oil spills (up to million and hundreds of million gallons)
on water or land through accidental rupture of big transporting vessels (e.g., tanker
ships or tanker trucks) are often observed. For example, Exxon Valdez spill was a
massive oil spill off the Alaskan shoreline due to ship in late 1980s (Jain et al., 2011).
Smaller oil spills through pipelines and other devices also happen in large numbers and
their impact is huge.
4. Offshore drilling
The world is currently experiencing the massive oil spill in the Gulf of Mexico with
its hard to predict consequences on environment, marine life and humans as the spill
continues since April 22, 2010 and it may take a while until a solution is implemented.
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5. Routine maintenance activities
Routine activities like cleaning of ships may release oil into navigable waters. This
may seem insignificant, however due to the large number of ships even few gallons
spilled per ship maintenance could build up to a substantial number when all ships are
considered.
6. Road runoff
Oily road runoff adds up especially on crowded roads. With many precipitation
events, the original small amounts of oil from regular traffic would get moved around
and may build up in our environment
7. Intentional oil discharges
Intentional oil discharges such as those through drains or in the sewer system
includes regular activities such as changing car oil, if the replaced oil is simply
discharged in a drain or sewer system.
8. Indirectly through burning of fuels, including vehicle emissionsIt would release various individual components of oils and oil products such as variety
of hydrocarbons.
20.2 Catastrophe
The first oil spill occurred in 1907 and, as a result, 7400 tons of paraffin oil reached the
United Kingdom’s sea and coastline. After that, about 140 big spills occurred, and a total
of seven million tons of oil reached the atmosphere. More than 90% of oil emission, however, is either natural, such as runoff from land-based sources, or has anthropogenic
sources, such as regular ship activity and deballasting and tank washing (not necessarily
accidents) (Mapelli et al., 2017). The Gulf War, Deepwater Horizon (DWH), Ixtoc 1 oil
well, Amoco Cadiz, and other prominent oil spills occurred in the sea in the largest oil
spills in history (Lim, Von Lau, & Poh, 2016). In 1978, the Amoco Cadiz disaster dumped
227,000 tons of crude oil and bunkers into the sea and polluted 320 km of shoreline length
to a depth of 20 inches (Lim et al., 2016).
In 1988, the Ashland oil spill happened when a four million gallon diesel oil tank collapsed and the oil was spilled into the Monongahela River (Miklaucic & Saseen, 1989). In
1989, when an Alaska reef crashed by a tanker that poured thousands of tons of oil into
the sea, the Exxon Valdez oil spill occurred (Jain et al., 2011). Pollution of the water and
coast resulted in substantial environmental impact to the local inhabitants (Atlas, 1995).
More than 250 thousand seabirds have been estimated to have died as a result of the leak.
The largest inland oil spill happened in Uzbekistan’s Fergana Valley in 1992, when an oil
well spewed 88 million gallons of oil onto the countryside. This spill was absorbed by the
earth, and there was no way to clean it up. In 2002, the sinking of tankers and affected
kilometers of the coastline caused a prestige tragedy, resulting in a loss of up to 66% of
the region’s species richness (Bovio et al., 2017). The DWH accident that took place during
the drilling rig explosion in the Gulf of Mexico in 2010 was one of the most prominent oil
spills. More than 700,000 tons of crude oil was released into the Gulf of Mexico during this
catastrophe (Mapelli et al., 2017). The biodiversity of the vertebrates and metazoan
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TABLE 20.1 History of oil spills.
Year Event
Reference
1978 The Amoco Cadiz disaster dumped 227,000 tons of crude oil and bunkers into the sea
and polluted 320 km of shoreline length to a depth of 20 inches.
Lim et al. (2016)
1988 The Ashland oil spill, a four million gallon diesel oil tank collapsed and the oil was
spilled into the Monongahela River.
Miklaucic and
Saseen (1989)
1989 Alaska reef crashed by a tanker that poured thousands of tons of oil into the sea, the Jain et al. (2011)
Exxon Valdez oil spill.
1992 Uzbekistan’s Fergana Valley inland oil spill, 88 million gallons of oil was released into
the land from an oil well. This spill was absorbed by the ground, and no cleaning
was possible.
Tan (2009)
2002 the sinking of tankers and affected kilometers of the coastline caused a prestige
tragedy, resulting in a loss of up to 66% of the region’s species richness
Bovio et al. (2017)
2010 The Deepwater Horizon (DWH) accident during the drilling rig explosion in the Gulf
of Mexico where more than 700 thousand tons of crude oil released.
Mapelli et al. (2017)
meiofauna was diminished by this event. It was estimated that the cleaning expense of
that spill was 10 billion USD (Alessandrello, Tomás, Raimondo, Vullo, & Ferrero, 2017).
The world witnessed this as the worst oil spill in history (Ng et al., 2015). The table below
shows the history of oil spills (Table 20.1).
20.2.1 Hydrocarbon pollution
Oil pollution occurs as a result of oil exploration, extraction, refining, transportation,
and storage in both terrestrial and marine environments. Oil spills have become a global
concern since the early 1900s, when the oil industry first emerged. The risk of accidental
and purposeful spills has increased as the oil industry and worldwide demand have
grown. Petroleum is a dangerous combination of organic chemicals, heavy metal traces,
and hydrocarbons, which includes numerous persistent volatile organic compounds and
polycyclic aromatic hydrocarbons (PAHs). Oil exposure harms critical activities in organisms, such as reproduction, physiological and chemical process regulation, and organ
function. Crude oil is a highly complex combination of tens of thousands of hydrocarbons
(aliphatic and aromatic) and nonhydrocarbons (sulfur, nitrogen, oxygen and a number of
hydrocarbons) and metals from trace. The oil composition varies according to its sources
(Singh, Kumari, & Mishra, 2012). There are different groups of hydrocarbon which is
responsible for the contamination in oil spills are described below with the Fig. 20.1.
20.2.1.1 Aliphatic group
Hydrogen and carbon, which can be linear, branched or cyclic, are made up of aliphatic
hydrocarbons. It is possible to saturate or unsaturate the aliphatic compounds. There are
many forms, including alkanes, alkenes, and alkynes, of aliphatic hydrocarbons. The most
common components in crude oil are alkanes which are the first ingredient to be degraded.
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FIGURE 20.1 Different group of hydrocarbons responsible for contamination in oil spills.
20.2.1.2 Aromatic group
PAHs are a category of approximately 10,000 air, water, and surface contaminants comprising
one or more aromatic rings (Hassanshahian, Abarian, & Cappello, 2015). Benzene, toluene, and
xylene have been well established and studied among monoaromatic compounds. PAHs are highly
resistant to deterioration and remain persistent in the environment due to their complex structure
such as naphthalene, anthracene, and phenanthrene (Ghosal, Ghosh, Dutta, & Ahn, 2016).
20.2.1.3 Heterocyclic group
Heterocyclic compounds are recalcitrant organic compounds containing at least one
heterocyclic ring which consists of compounds having common heteroatoms incorporated (oxygen, nitrogen, and sulfur) into an organic ring structure in place of a carbon
atom. It includes polar compounds such as nitrogen (quinolines), sulfur (dibenzothiophenes) and oxygen (xanthene) atoms.
20.3 An approach to eliminate oil spills
The rapid deployment to the spill leads to a better chance of avoiding and stopping
leakage (Helmy & Kardena, 2015). Rather of controlling pollutants and allowing natural
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attenuation, the purpose of the reaction to the oil spill is to minimize the spill’s negative
impacts. The primary concern in reacting to an oil spill is to regularly monitor the source
and prevent the oil from spreading. The solution might be any policy, technique, technology, or equipment for managing the spill and resolving its negative consequences.
Stewardship, in addition to swift action, is necessary to track and forecast the movement
of oil. Mechanical spill recovery equipment such as skimmers, booms, barriers, and sorbents, as well as dispersants and controlled in situ burning, are among the reaction
approaches (Walker, 2017). Environmental treatments and remediation techniques are
aimed at degrading and transforming pollutants into less toxic and even harmless compounds; treatment is carried out, if not necessary, by restricting the movement and migration of contaminants to avoid their dissemination to uncontaminated areas. The toxicity of
pollutants do not improve with this method, but the likelihood of their further distribution
to the ecosystem is decreased.
There are many therapies and solutions to oil spills, including physical, chemical, and
biological strategies (Jain et al., 2011). While physical and chemical methods are often used
to extract spilled oil (Kuiper, Lagendijk, Bloemberg, & Lugtenberg, 2004; Wang, Zhang, Li,
& Klassen, 2011), they are mostly neither cost-effective nor environmentally friendly.
Incineration contributes to air pollution, for instance, and land-filling leads to groundwater contamination. The spilled oil is simply burned for incineration, with the result of
raising levels of ambient carbon dioxide, nitrogen oxide, and sulfur oxide. It is understood
that the present issue of global warming is due to CO2 accumulation in the atmosphere. It
can be argued that bioremediation often contributes to bacteria releasing CO2. In fact, only
one portion of the oil’s carbon is released by bacteria during energy (ATP) processing,
while the other portion is retained as bacterial cell content in the soil. The acidic rain due
to nitrogen and sulfur oxides is known to degrade the quality of land and water while
affecting the aquatic ecosystems and groundwater table. Land-filling of the contaminants
has been reported to generate dangerous leachates in the form of gases and liquids that
can toxify groundwater (Radwan, 2008; Sverdrup, Nielsen, & Krogh, 2002). Certainly,
these methods have contributed in the elimination of a large proportion of the spilled oil
with the unpredictable risks associated and undoubtedly severe obstacles to their implementation (Johnson & Affam, 2019). Therefore there is a need of such techniques which
are ecofriendly and cost-effective and can play a vital role in sustainable development.
20.3.1 Bioremediation and its techniques
The term bioremediation refers to the degradation of environmental pollutants using
biological agents like bacteria and fungi for the breakdown of complicated chemical molecules into simpler ones. Bioattenuation is a term used to describe naturally occurring bioremediation (Mrozik & Piotrowska-Seget, 2010). Natural attenuation, but after an oil spill,
is typically too retarded to satisfy the immediate needs of the environment. It is based on
the catabolic activities of microorganisms and their ability to convert pollutants into less or
nontoxic compounds by converting them into carbon and energy sources. Depending on
many variables, such as site conditions, form and concentration of contaminants, various
bioremediation techniques are implemented. The physical removal of the polluted land for
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the treatment process requires ex situ approaches. In situ procedures, however, include
handling the infected substance in place.
Therefore by various improved methods, attempts have been made to increase the productivity of the method. Bioremediation methods have often been referred to as biorestoration (Testa & Winegardner, 1991; Wilson, Leach, Henson, & Jones, 1986). This include
land-farming, composting, bioreactor use (Zouboulis, Moussas, & Psaltou, 2019), bioventing/biosparging, pumping and treatment strategies, bioslurping, biostimulation, and
bioaugmentation (Boopathy, 2000). Compared to other oil spill management methods, bioremediation is often considered to be a cost-effective (involves the use of ubiquitous oleophilic microbes) and ecofriendly (which breaks down crude oil into nontoxic products and
intermediates) clean-up process (Furukawa, 2003; Okoh & Trejo-Hernandez, 2006; Pieper
& Reineke, 2000). Bioremediation has often received criticism of being ineffective in cleaning up heavy crude oil components and is often constrained by abiotic factors such as
availability of nutrients, temperature, and concentration of oxygen (Boopathy, 2000). This
present review is therefore intended to define the key challenges associated with the use
of bioremediation to clean up crude oil emissions in terrestrial and marine ecosystems, as
well as to establish guidelines that are likely to form the basis for new lines of research on
how to resolve these challenges.
Several chemical and physical hydrocarbon treatment approaches have been investigated such as incineration, chlorination, UV oxidation, and solvent extraction (Ghosal
et al., 2016), but are often ignored due to lower removal efficiency and higher environmental and health associated risks. The biological approach, meanwhile, are more efficient in hydrocarbon removal and can be distinguished into (1) phytoremediation
strategy which uses plants for decontamination purposes and (2) bioremediation which
involves the use of microbial population for the cleanup of contaminated sites. There are
two broad approaches of the bioremediation viz, In situ and Ex situ as illustrated in
Fig. 20.2. The in situ method of treating is based on site excavating while Ex situ is treating contaminant off site (Boopathy, 2000). The bioremediation efficiency depends mainly
on the microbial structure, the sites to be decontaminated and the environmental conditions. The natural bioremediation process is influenced by physicochemical conditions
like temperature, pressure, pollutant surface area, oxygen content, nutrient availability,
pH, salinity, oil composition, etc. There are two main approaches available when applying bioremediation as a response to the oil spill, which are biostimulation (increasing the
availability of nutrients, mostly nitrogen and phosphorus, to initiate growth and speed
up biodegradation) and bioaugmentation (inoculation of microorganisms with enhanced
ability to degrade petroleum hydrocarbons in order to facilitate the process). There is
also a new approach, however, which is bioaugmentation with genetically engineered
microorganisms (GEM bioaugmentation) (Jafarinejad, 2017; Lahel et al., 2016). It has
been reported that bioaugmentation effects can be observed much more quickly than
biostimulation (Pontes et al., 2013). The most promising approach, however, is to combine biostimulation and bioaugmentation with additional of biosurfactants.
20.3.1.1 Bioaugmentation
Bioaugmentation is an approach that is used when pollutant mixtures like petroleum
are insufficient to be degraded by the native microbial populations. This method is opted
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FIGURE 20.2
20. Bioremediation: an ecofriendly approach for the treatment of oil spills
Approaches to bioremediation.
when the degradation process is limited by the number of hydrocarbon degrading bacteria
or the absence of such bacteria. Polynuclear aromatic hydrocarbons, for example, are usually hard to degrade (Jafarinejad, 2017). In this approach, to supplement the naturally
available microbes, microorganisms with enhanced biodegradation ability are added to
the polluted environment.
It is commonly used to add nonindigenous microbes from other polluted environments
to the target site (Jafarinejad, 2017). Alternatively, in laboratory conditions in bioreactors,
microbes from the target site are separated, mass cultured and are used as an inoculum to
the target site. This technique is called autochthonous bioaugmentation and refers to cases
where bioaugmentation is performed after enrichment by the native microbes of the contaminated site to be reapplied to the site (Lim et al., 2016). The selection criteria for the
microbes added are based on their physiology and metabolic capacity (Lim et al., 2016). In
order to start biodegradation, the seeding of microorganisms at the contaminated site can
reduce the lag time. The adaptation problem is avoided when the seeding is carried out by
the enhanced indigenous organisms taken from the target site (Jafarinejad, 2017).
Under controlled conditions, bioaugmentation has been successfully performed on the
bench scale. It must, however, be considered that conditions may be uncontrollable in real
fields (Jafarinejad, 2017). It has been suggested that prior to in situ application of the
microorganisms, primary laboratory tests for microorganism selection may increase the
chance of successful bioremediation. In the work of Szulc et al. (2014), in addition to
Xanthomonas sp., Gordonia sp., Stenotrophomonasmaltophilia, and Rhodococcus sp., the most
effective consortium (Pseudomonas fluorescens and Pseudomonas putida mixed with
Aeromonashydrophila and Alcaligenesxylosoxidans) for bioaugmentation was selected in the
laboratory based on the quantity of CO2 and dehydrogenase activity (Szulc et al., 2014).
Researchers claim that, taking into account the specific nutritional needs and limitations,
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commercial bacterial blends can be produced with customized properties for each specific
site and type of spill pollution.
20.3.1.2 Biostimulation
Biostimulation is the process of nutrient-enhanced bioremediation to improve the indigenous rate of biodegradation of petroleum hydrocarbons, particularly organic pollutants,
by providing the contaminated medium with the limiting nutrient material (Soleimani,
Farhoudi, & Christensen, 2013). The nutrients include carbon, phosphorus, and nitrogen,
and some other cosubstrates that limit growth. During biostimulation, it is also possible to
modify the conditions, including temperature and aeration. All of these operations are carried out in order to accelerate the growth and activity of oil degraders. This strategy can
be called fertilization or the enrichment of nutrients (Jafarinejad, 2017).
Due to the supply of nutrients, microbial metabolic activity is enhanced. Electron acceptors and donors can be used to activate the oxidation and reduction mechanisms. Their
inclusion, however, must be managed carefully. The nutrients must be readily available
and in touch with microbes (Balba, Al-Awadhi, & Al-Daher, 1998). The circumstances for
increasing natural biodegradation may be altered by altering numerous parameters such
as the administration of fertilizers, nutrients, biosurfactants, and biopolymers.
Biostimulation is the manipulation of all of these characteristics in order to increase natural bioremediation (Lim et al., 2016). The bioventilation process, which is the application
of oxygen to porous soil in order to improve the growth of microorganisms and the metabolism of organic matter by providing aerobic conditions, is another practice used to
improve conditions, especially aeration. Bioventilation has been shown to increase the bioremediation rate to 85% from 64% in the natural attenuation process (Lim et al., 2016). In
marine environments or generally open systems, it is quite difficult to add Nitrogen and
Phosphorous. Uric acid, which is the waste product of animals, is thus added instead
(birds, reptiles, insects, etc.). Low water soluble, uric acid can bind to petroleum hydrocarbons and can be used by bacteria as a source of nitrogen or both nitrogen and carbon. It
has been observed that nitrate addition is more effective than ammonia in seawater for
light crude oil degradation, whereas ammonia addition is more effective than nitrate in
salt-marsh soil. Fortunately, nitrogen supplementation has not shown any adverse effects,
such as algal blooms (Jafarinejad, 2017). Using this approach, good results have been
obtained on the cost of sediments contaminated after the Exxon Valdez spill in Alaska,
and the biodegradation rate increased three to five times by the addition of fertilizers such
as iron, phosphorus, and nitrogen.
20.3.1.3 Biosparging
In biosparging, air is introduced into the pollutant site to promote the microorganisms’
degradation efficiency. In contrast to bioventing, the air inside the saturated area is incorporated, causing volatile pollutants to move upwards. The efficacy of biosparging relies
on the permeability that determines the availability of pollutants to microorganisms and
the biodegradability of the pollutant (Godheja et al., 2019). Biosparging has been widely
applied to the treatment of aquifers polluted by oil derivatives, mainly kerosene and diesel, which have good biodegradation of the BTEX group and naphtalenes (Kao, Chen,
Chen, Chien, & Chen, 2008). It is possible to use aerobic bacteria to break down mineral
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oils, BTEX, and naphthalene. The deepest layers of soil and groundwater, however, are
principally anaerobic. Oxygen is injected into the soil and groundwater by injection filters
to promote the development of aerobic microorganisms. This direct supply of bacteria
with oxygen increases their efficiency to degrade these contaminants.
20.3.1.4 Phytoremediation
In order to promote biological, biochemical, physical, microbiological, and chemical
interactions to attenuate the toxicity of contaminants, phytoremediation refers to the
use of plants in polluted sites (Godheja et al., 2019). It occurs through various mechanisms depending on the type of pollutant, namely biodegradation, vaporization, filtration, among others. Elemental contaminants, such as heavy metals or radioactive
elements, are mainly extracted, processed and sequestered, whereas organic contaminants are mainly removed by rhizodegradation, biodegradation, vaporization or stabilization (Kuiper et al., 2004).
1. Phytoextraction: The use of plant or plant part (e.g., root, stem or leaf) by accumulation
or extracting out the pollutant from the soil (Sidhu, Bali, Singh, Batish, & Kohli, 2018).
2. Phytotransformation or Phytodegradation: The toxic components are transformed or
degraded by the plants (Park, Kim, Kim, Kang, & Sung, 2011).
3. Phytovolatilization: The plant removes the pollutant from the soil and then manages to
convert it into a volatile product, releasing it into the atmosphere.
4. Phytostimulation: The enhancement of soil microbial activity for the degradation of
organic contaminant (Borriss, 2020).
5. Phytostabilization: This process consists in the immobilization of pollutants in the soil,
thus avoiding erosive processes and allowing the association with humus and lignin
(Shackira & Puthur, 2019).
6. Rhizofiltration: The adsorption or precipitation of dissolved compounds onto plant roots
or absorption into the roots. Rhizofiltration usually addresses contaminated
groundwater (Awa & Hadibarata, 2020).
7. Rhizodegradation: The degradation of the organic pollutant by the means of the root
(Cristaldi et al., 2020).
20.3.1.5 Landfarming
Landfarming is a soil bioremediation approach that includes mixing hydrocarboncontaminated soil. Biodegradation is also used for biological, physical, and chemical processes in the soil. The technique has been used since the 1980s due to its simplicity and
cost-effectiveness. It is a “low-tech” oil spill remediation procedure designed for oilpolluted top soil surfaces (Genouw et al., 1994). It can be carried out in situ or ex situ, but
it is more common to use the latter method. Contaminated soil is often transferred to a
treatment site where aerobic microbial degradation is spread over a prepared soil surface
and periodically tilled to occur (Zouboulis et al., 2019). This simple technology, however,
faces inherent challenges, such as the inhalation of hydrocarbon volatiles by humans and
the risk of other hydrocarbon contaminants leaching into the groundwater region through
the soil profile.
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This challenge has been managed in recent times by providing the treatment site with a
layered polythene material about 250 μm in thickness, which is laid at the bottom of the topsoil in order to prevent the leachates from seeping to the groundwater zone. In addition, by
building a greenhouse to limit the extent of diffusion, the dispersed hydrocarbon volatiles
have been controlled (Maila & Cloete, 2004). A number of hydrocarbon compounds have
been successfully degraded by land farming as most oleophilic microbes are confined to the
superficial soil layer, 1530 cm deep. The major challenges faced during land farming are
that it is a very slow process of biodegradation and has been unsuccessful in degrading
PAHs with high molar mass. However, in terms of the biodegradation of light PAHs, a
number of successes have been recorded. For example, Picado et al. reported a 63% reduction of mostly low molar mass PAHs after three months of landfarming; Bossert and Bartha,
1986 recorded an 80%90% reduction of low molar mass PAHs after three years. Although
the latter report is quite dated compared to the former, the fact that landfarming is indeed a
very slow process of bioremediation is still revealed. The nonavailability of petroleum
hydrocarbons to the oleophilic soil biota has been attributed to the slow nature of land farming. The use of surfactants such as detergents has therefore been suggested to help improve
bioavailability. Adsorbents such as straws can, on the other hand, help mop up the soil’s
nonbiodegradable heavy hydrocarbon residues (Maila & Cloete, 2004).
20.3.1.6 Bioslurping
Bioslurping is a relatively new in situ bioremediation strategy that combines bioventing
with a free-product recovery system. This method of remediation achieves two aims
simultaneously—aerobic microbial biodegradation of the vadose zone through air injection
and soil vapor extension and the removal of the light nonaqueous phase liquid saturates
(NAPLS—free-phase petroleum pollutants) from the capillary fringe and water table via
dual-pumps (through gravity-gradient, the first pump forces the flow of petroleum from
the vadose zone into the well and the second pump skims off the petroleum to the
surface).
20.3.1.7 Bioreactor
A bioreactor comprises of a reaction chamber equipped with a mixing mechanism, oxygen and nutrient supply system, influential and effluent pumps. It is an ex situ bioremediation technology that provides the direct control of environmental/nutritional factors
(such as oxygen, moisture, nutrients, pH and even microbial population) that control biodegradation (Zouboulis et al., 2019). Hydrocarbon-polluted soils are incorporated to the
bioreactor chamber and mixed along with the periodic input of oxygen and nutrients to
boost biodegradation. This makes the technology more accurate than most bioremediation
in situ technologies in which it is not easy to control the variables affecting bioremediation
at the spill site.
20.4 Factors affecting the biodegradation efficiency
The rate of hydrocarbon degradation is affected by diverse physical and chemical factors. The nature and quantity of hydrocarbons, the type of polluted matrix (soil, sediment,
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water and effluent), the environmental conditions, and the activity of the microbial community can be cited among many. The environmental factors include nutrient availability,
temperature, water or humidity content, oxygen, pollutant bioavailability, and pH as
shown in Fig. 20.3 (Breedveld & Sparrevik, 2000; Haritash & Kaushik, 2009; Silva-Castro
et al., 2012).
20.4.1 Nutrient availability
For microbial metabolism, inorganic sources such as nitrogen, phosphorus, potassium,
hydrogen or oxygen are essential and affect the growth and activity of microorganisms,
whereas micronutrients such as zinc, manganese, iron, nickel, cobalt, molybdenum, copper, and chlorine are necessary. The carbon/nitrogen or carbon/phosphorus ratios are
considered to be a determining factor in biodegradation rates and are high in contaminated hydrocarbon sites that limit and affect the rate of degradation (Garon, Sage,
Wouessidjewe, & Seigle-Murandi, 2004). Significant effort has been made to develop nutrient delivery systems that overcome the washing problems characteristic of open sea and
intertidal environments; the use of slow-release fertilizers and/or oleophilic nutrients can
provide polluted environments with a continuous source of nutrients. Slow release fertilizer typically consists of solid-form inorganic nutrients coated with a hydrophobic compound such as paraffin or vegetable oil. Oleophilic biostimulants are a successful
alternative that solves the problem of rapid dilution and washing out of water-soluble
FIGURE 20.3
Factors affecting bioremediation.
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20.4 Factors affecting the biodegradation efficiency
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nutrients containing nitrogen and phosphorus. Oleophilic additives remain dissolved in
the oil phase and are thus available at the oil-water or oil-sediment interface, where bacterial growth and metabolism are enhanced.
20.4.2 Temperature
The hydrocarbon degradation capacity of microorganisms is significantly affected by
temperature. Solubility, bioavailability, distribution of hydrocarbons and diffusion rate are
increased at high temperatures, promoting the capacity of microbial biodegradation and
improving the rate of biodegradation. Very high temperatures, on the other hand, decrease
oxygen solubility and limit the biodegradation of aerobic microbes (Leahy & Colwell,
1990). In addition, Boopathy (2000) confirmed that pollutant degradation is better and
more efficient at mesophilic temperatures than very low or high temperature degradation.
However, it was reported that microorganisms are able to metabolize PAHs at extreme
temperatures: for example, a high degradation rate of PAHs occurred in seawater at low
temperatures (low as 0 C) and at 50 C. Bargiela et al. (2015) have derived the correlation
between the relative percentage of genes encoding enzymes involved in biodegradation
and temperature at oil-polluted sites.
20.4.3 Oxygen limitations
The initial steps in the catabolism by bacteria and fungi of aliphatic, cyclic and aromatic
hydrocarbons involve the oxidation of the substrate by oxygenases for which molecular
oxygen is needed. Although it has been shown that anaerobic biodegradation occurs in
various ecosystems, including marine environments, its ecological significance has generally been considered to be minor and the rate of biodegradation is rather low (Ghosal
et al., 2016). In aquatic sediments and soils, oxygen restriction conditions normally exist.
Oxygen depletion can occur in the presence of easily utilizable substrates that increase
microbial oxygen consumption. In several instances, the concentration of dissolved oxygen
can be close to zero, leading to practically zero aerobic biodegradation rates. Although
oxygen can be successfully delivered (in various forms) to soils and groundwater polluted
with hydrocarbons, boosting biodegradation rates, this is not the case in marine environments, as such deployment is very difficult to execute technologies. Thus oxygen represents a very significant and potential factor which limits the rate of hydrocarbon
degradation.
20.4.4 pH
In aquatic environments, the pH variations are not commonly observed, and most
hydrocarbon-degradable bacteria and fungi require a neutral pH. Microbial activity is, in
general, affected by extremely low or high pH. Bamforth and Singleton et al. (2005) have
reported that for Burkholderia cocovenenans, 40% of phenanthrene degradation was
observed at pH 5.5. The degradation at neutral pH, however, was 80% under the same
conditions. Furthermore, Leahy and Colwell (1990) reported that microbial degradation of
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naphthalene decreased at pH 5.0, compared with the highest rate of degradation observed
at pH 7.0. In addition, the efficacy of some microorganisms, such as Pseudomonas, to
degrade hydrocarbons at alkaline pH has been described in other reports. PAH degradation has been reported by indigenous microorganisms in an acid-contaminated environment (pH 2). The suitable pH depends on the microorganisms that are to be used for the
process of bioremediation.
20.4.5 Bioavailability of hydrocarbon
The bioavailability is defined as the rate of substrate mass transfer into the microbial
cells. It is regarded as one of the most important parameters for the rate of degradation
of hydrocarbons. PAHs are characterized by low bioavailability as a result of their low
aqueous solubility. That is why they are reported to be resistant and environmentally
persistent to the degradation process. Unsuccessful remediation of PAH-contaminated
sites has been reported due to the low bioavailability of PAHs. Hydrocarbon bioavailability has been reported to decrease over time (Ghosal et al., 2016). Although the photooxidation increases the biodegradation of petroleum hydrocarbon by increasing its
bioavailability, hence promoting microbial activity (Maki et al., 2003). Hydrocarbons,
and particularly PAHs, become more bioavailable when dissolved or evaporated. The
bioavailability of pollutants in contaminated environments may be increased through
the application of surfactants.
20.4.6 Restriction of physical contact between microorganism and oil spills
The rate of biodegradation in the environment is generally limited due to the hydrophobicity and low water solubility of most petroleum hydrocarbons. This is because the first
step in the petroleum oil degradation process often requires the involvement of bacterial
membrane-bound oxygenases, which require direct and effective contact between bacterial
cells and substrates of petroleum hydrocarbons.
The primary factors restricting the biodegradation efficiency of petroleum hydrocarbons are: (1) limited bioavailability of petroleum hydrocarbons to bacteria, and (2) the
fact that bacterial cell contact with hydrocarbon substrates is a requirement before
introduction of molecular oxygen into molecules by the functional oxygenases.
However, countermeasures against petroleum contaminants have been developed by
bacteria, such as improving the cell’s adhesion capacity by altering its surface components and secreting bio emulsifiers in order to improve their access to target hydrocarbon substrates. Bacteria with such functions are often tested for use as environmental
remediation agents, accelerating the removal from the environment of petroleum
hydrocarbon pollutants (Krasowska & Sigler, 2014). The efficient biodegradation of
hydrophobic hydrocarbon substrates requires bacterial surface properties.
Although bacterial adherence may improve hydrophobic hydrocarbon biodegradation,
it is not necessary to attach bacterial cells to targeted substrates. This is because bacteria
with high surface hydrophobicity are easily aggregated and biofilms are formed in some
instances, creating potential risks such as diseases. Indeed, not only hydrophobic bacteria
can biodegrade hydrophobic pollutants; several solvent-resistant hydrophilic bacteria are
D. Biological processes
20.5 Role of microorganism
367
also capable of metabolizing such pollutants (Heipieper, Neumann, Cornelissen, &
Meinhardt, 2007), which can be attributed to the modification of lipopolysaccharides or
porines of the outer membrane of the bacterial surface (Krasowska & Sigler, 2014) also
reported the first colonization and dominance of solvent-resistant bacteria for pollutant
removal. This is due to the fact that bacteria with a high surface hydrophobicity can easily
combine and biofilms can form in some cases, posing health dangers. Several solvent-resistant hydrophilic bacteria can also biodegrade hydrophobic contaminants (Heipieper,
Neumann, Cornelissen, & Meinhardt, 2007), which can be linked to the change of lipopolysaccharides or porines of the bacterial surface (Krasowska & Sigler, 2014) was also the first
to report the colonisation and domination of solvent-resistant bacteria in the pollutant
removal process. Hydrophilic microorganisms appear to be more useful than hydrophobic
microorganisms in the remediation of hydrocarbon contaminants (Obuekwe, Al-Jadi, &
Al-Saleh, 2009).
To enhance the bioavailability of petroleum hydrocarbons, one promising approach is
the application of surfactants (Kleindienst et al., 2015), which may enhance dissolution or
desorption rates leading to the solubilization or emulsification of petroleum hydrocarbon
pollutants. Chen and Li (2007) found that Bacillus sp. adhered to in the presence of rhamnolipids, hydrocarbon DQ02 increased 44% and n-hexadecane degradation increased
11.6% compared to treatment in the absence of rhamnolipids. However, certain surfactants, such as Corexit 9500, have been reported to have adverse effects on oil-degrading
bacteria (Kleindienst et al., 2015) because of surfactant toxicity and competition with
hydrocarbon substrates. Hence, the selection of suitable surfactant is crucial for the remediation of pollutants while preventing secondary pollution.
Bioemulsifier-producing bacteria, which have attracted much attention, generally have the
following two physiological aspects: (1) the ability to enhance the complexation and solubilization of nonpolar substrates, thereby promoting the bioavailability of substrates, and (2) the ability to improve affinity between cell surfaces and oil-water interfaces through metabolism,
promoting deformation of the oil-water interface film. Ayed et al. (2015) reported that the bio
surfactant produced by Bacillus amyloliquefaciens An6 was an alternative to chemically synthesized surfactants because it showed a high efficiency of solubilization towards diesel oil (71.54%
at 1 g/L) better than SDS and Tween 80 and could improve the efficiency of the An6 strain degradation of diesel oil. However, not all the biosurfactants produced by bioemulsifier-producing
bacteria can effectively enhance the degradation rate of pollutants. Indeed, whether various bio
surfactants stimulate or inhibit the bioremediation of pollutants is dependent on the physicochemical properties of the surfactants, types of pollutants and physiological characteristics of
the functional microorganisms. Therefore a database of petroleum hydrocarbon pollutants and
bio emulsifier-producing bacteria must be established, which is conducive to the targeted selection of suitable petroleum hydrocarbon treatment bacteria.
20.5 Role of microorganism
More than 200 different bacterial, fungal, and yeast species have been reported to be able to
degrade petroleum hydrocarbons. Naturally, these microorganisms can be found in the sea,
freshwater and soil. The biodegradable compounds of hydrocarbons range from methane
D. Biological processes
368
20. Bioremediation: an ecofriendly approach for the treatment of oil spills
compounds to C40 compounds. Nearly 79 bacteria, 9 cyanobacterial genera, 103 fungi, 14 algae,
and 56 leaves are capable of degrading hydrocarbon pollutants for classification (Jafarinejad,
2017). Various compounds of petroleum hydrocarbons can be degraded by different groups of
indigenous soil bacteria. These bacteria comprise soil-isolated Pseudomonas strains and reservoirs
to degrade PAHs (Atlas, 1995). Other microorganisms with the ability to degrade petroleum
hydrocarbons are Yokenella sp., Alcaligenes sp., Alcanivorax sp., Microbulbifer sp., Sphingomonas
sp., Micrococcus sp., Cellulomonus sp., Dietzia sp., Roseomonas sp., Stenotrophomonas sp., Gordonia
sp., Acinetobacter sp., Corynebacterium sp., Flavobacter sp., Streptococcus sp., Providencia sp.,
Sphingobacterium sp., Capnocytophaga sp., Bacillus sp., Enterobacter sp., and Moraxella sp. (Jain
et al., 2011). Alcanivorax sp. bacteria and Cycloclasticus sp. can use aliphatic and aromatic hydrocarbons, as their carbon source, respectively. Some bacteria can help to produce biosurfactants
which can enhance the bioremediation by reducing surface tension and increase of crude oil
uptake. However, factors such as supply of nutrients and nature of oil impurities are influential
in degrading the petroleum hydrocarbons (Bovio et al., 2017). Some fungi are also capable of
degrading hydrocarbons from petroleum. However, for effective degradation, they need more
time. Fungus from Aspergillus sp., Amorphoteca sp., Penicillium sp., Graphium sp., Neosartorya sp.,
Paecilomyces sp., Fusarium sp., and Talaromyces sp. They are among the microorganisms capable
of degrading hydrocarbons from petroleum. Compounds such as polychlorinated biphenyls
(PCBs) and PAHs are reported to be able to degrade white rot fungi. Some yeasts including
Candida sp., Pichia sp., and Yarrowia sp. also reported to have the potential to degrade the compounds available in oil contaminants (Jain et al., 2011). Some researchers suggest that in specific
circumstances, fungi can degrade petroleum better than bacteria (Bovio et al., 2017). However,
for fungal bioremediation of marine contaminated sites, there really is not much information
available. Genetic manipulation of microorganisms to enhance their ability of oil degradation
still requires investigation.
20.6 Novel approaches
Current research into the bioremediation of oil spills focuses mainly on new materials addition for biostimulation, using genetically modified microorganisms for bioaugmentation and
integration of different physicochemical and biological approaches for oil spill treatment. The
new methods for the bioremediation of oil spills are enlightened in the following section.
20.6.1 Substance addition
In novel approaches biowastes, inorganic materials, polymeric materials, etc. are added
to enhance the bioremediation. Another material that has recently gained attention in the
bioremediation studies of oil spills is the addition of biosurfactants. Biosurfactants are produced by various microorganisms, including leaves, bacteria, and filamentous fungi, extracellularly or as part of the cell membrane. Microbial activity in the case of biosurfactant is
due to the enhancement of extracellular biosurfactant (e.g., trehalose lipids produced by
Rhodococcus species) or cellular biosurfactants (e.g., mycolic acids) which cause the microbial cells to be linked to hydrophobic phases. There is a broad structural diversity of biosurfactants, including lipopeptides, glycolipids, fatty acids, lipoproteins, neutral lipids,
D. Biological processes
20.7 Case studies
369
phospholipids, and polymeric biosurfactants. Two groups of biosurfactants, which are lowmolecular-weight surface active materials with the ability to lower the tension (both surface
and interfacial) efficiently and polymers with high molecular weight (bioemulsifiers) that
are used for stabilization of emulsions (Bezza & Chirwa, 2015) are available. Biosurfactants
have less toxicity, biodegradability, and ecological acceptability than chemical surfactants. In
comparison to chemical ones, biosurfactants act more effectively at different pH, temperature, and salinity (Bezza & Chirwa, 2015) with superior biodegradability and ecofriendly
nature (Szulc et al., 2014). For bioremediation, especially for the biodegradation of hydrophobic compounds, biosurfactant-producing microorganisms are of interest.
20.6.2 Genetic engineering
In 1970, the first GEM was developed with the name “superbug” and was capable of
degrading oil. This was done with plasmid transfer to utilize some toxic hydrocarbons
including hexane, octane, toluene, xylene, camphor. After improving genetic engineering
methods and thorough research on the metabolic capabilities of microorganisms, the
development of GEMs became more significant in the early 1980s. It was in 1981 that the
first two genetically modified strains were patented. The two strains containing genes that
give them the ability to degrade naphthalene, salicylate, and camphor are Pseudomonas aeruginosa (NRRL B-5472) and P. putida (NRRL B-5473). The development of GEMs with
enriched capacity for biodegradation of organic compounds is possible since the degradative method, the enzymes, and the relevant genes are documented and biochemical reactions are thoroughly explained. The limitation of this method is, on the one hand, the
survival of GEMs in the environment and, on the other hand, public acceptance, which
hampers their broad application (Jafarinejad, 2017). Different genetic engineering methods
are available for bioremediation purposes, including improving the specificity and affinity
of the enzyme, the design and regulation of the metabolic pathway, and the expansion of
the substrate range for existing pathway, preventing the accumulation of waste intermediates that inhibit the carbon flow redirection pathway, improving the genetic stability of
catabolic activities, identifying genetically modified bacteria by marker gene in the polluted environment, and using biosensors for monitoring specific chemical compound. The
most common method for creation of GEMs is engineering of one gene or operons and
construction of pathways and modification of the existing genetic sequence.
20.7 Case studies
An unintentional oil spill due to the rupture of crude oil trunk line was reported near
the city of Gujarat (western India) in June 2008. The oil spill site was also immediately barricaded by the oil company and the spread of crude oil was also stopped. The oil company
recovered large amounts of crude oil collected at the spill site in a low lying field. After
these primary actions by the oil company themselves, they approached ONGC TERI
Biotech Ltd which is a joint venture company between ONGC and TERI (New Delhi,
India), http://www.otbl.co.in.
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20. Bioremediation: an ecofriendly approach for the treatment of oil spills
The contaminated site was treated with Oil zapper (crude oil degrading bacterial consortium of four species) for the degradation of TPH in oil polluted soil after dumping of
oil-soaked soil in a protected bioremediation trap. The nutrient formula was also sprayed
on oil-soaked soil after application of Oil zapper (74.5 tons) and then tilling of oil- soaked
soil was performed at regular intervals. Samples from the bioremediation site were collected and checked in the laboratory to monitor the rate of degradation. After completion
of bioremediation (TPH reduced to 5000 ppm), toxicity of bioremediated soil was checked
in laboratory approved by Ministry of Environment and Forest, Government of India.
After fish toxicity test, soil after bioremediation is used in green belt development.
20.8 Conclusion and future prospects
The occurrence of oil spills is not a new issue and has been a problem for more than a
century. Whether it occurs in water or soil, this problem is a huge threat to the ecosystem,
fauna, and flora. Due to their high toxicity to human and environmental health, petroleum
hydrocarbons are one of the most alarming pollutants. Bioremediation of petroleum
hydrocarbon-degrading bacteria is widely considered to be environmentally friendly and
effective. A large amount of bacterial species with petroleum hydrocarbon-degrading ability have been exploited and applied in bioremediation. Nevertheless, different problems
that slow down the effects of biodegradation have been identified during the practical
application process. Bioremediation is a more efficient approach without disrupting the
polluted environments compared with physicochemical methods (application of skimmers,
booms, barriers and sorbents, dispersants, and controlled in situ burning). This method is
based on the presence of catabolic genes and enzymes, which allow microorganisms to utilize hydrocarbons as carbon and energy source. There are various factors that affect the
effectiveness of bioremediation, such as oxygen, pH, temperature, and the availability of
nutrients. Although several aspects of this approach have been studied by various
researchers and a relatively high rate of hydrocarbon removal has been reported, particularly on a laboratory scale, real-field applications are still under review (Sihag, Pathak, &
Jaroli, 2014). New fields of research for the bioremediation of oil spills are still a topic of
research including the addition of novel materials, the use of GEMs and the integration of
electrochemical strategies with biological methods for a better removal of toxins from the
contaminated sites.
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