ELSEVIER Environmental Pollution 89 (1995) 73-80 Elsevier Science Limited Printed in Great Britain 0269-7491/95/$09.50 0269-7491(94)00042-5 CORRELATION BETWEEN ALTITUDE AND HEAVY METAL D E P O S I T I O N IN THE ALPS Harald Gustav Zechmeister Department of Vegetation Ecology & Biological Conservation, University of Vienna, Althanstrafle 14, A-1091 Vienna, Austria (Received 20 December 1993; accepted 3 June 1994) Abstract Mosses have been collected from transects along altitudinal gradients on five mountain ranges within the northern and eastern Alps. The location of the sampling points on steep slopes provides results depending on altitude rather than on horizontal distance. As, Cd, Co, Cr, Cu, Fe, Hg, Ni, Pb, V, Zn and S concentrations in moss shoots for 198~ 1991 have been determined The results of several multivariate and regression analyses show a remarkable increase of Pb, Cd, Zn and S concentrations with rising altitude. High levels of precipitation are strongly correlated with heavy metal deposition, and seem to be the main source of heavy metal fallout at higher altitudes. Larger amounts of wind blown, indigenous particles must also be considered for several heavy metals (e.g. V). There are only a few local pollutors situated throughout the Alps, and the investigation shows that pollution by heavy metals in alpine regions is caused mainly by long range transport. a very distinct geomorphology, these maps and the conclusions deduced from them should be viewed with suspicion. As this study formed part of an international 'survey of atmospheric heavy metal deposition using bryophytes as bioindicators' (Rtihling, 1994), investigations on differences in heavy metal deposition in respect to different altitudes seemed to be necessary. Generally it is known that there is a strong correlation between orography, the amount of wet deposition and rainfall composition (e.g. Fowler et al., 1988; Dore et al., 1990; Weston & Fowler, 1991; Fowler et al., 1993). Nevertheless there are only a few investigations on this topic concerning heavy metals and these studies show very controversial results (e.g. Groet, 1976; Herman & Stefan, 1992; Solt6s, 1992). None of these previous investigations, regardless of the results, have been done by surveying a well orientated transect along an altitudinal gradient. In this investigation the location of the sampling points on rather steep slopes provided results that show a distinct relation to altitude rather than to horizontal distance along transects. Two aims are set up for this paper: (i) the correlation of heavy metal deposition in relation to altitude; and (ii) possible reasons for such a correlation. Keywords: Heavy metals, altitudinal transect, mosses, precipitation, Alps. INTRODUCTION Mosses have been used for monitoring heavy metal deposition all over Europe (e.g. Riahling & Tyler, 1971; Ellison et al., 1976; Pakarinen & Tolonen, 1976; Steinnes, 1977; Pilegaard et al., 1979; Gydesen et al., 1983; Rt~hling et al., 1992) and North America (e.g. Glooschenko, 1989) for a long time. The methods for sampling, preparation of the samples, and analyses have evolved in that time and have been improved in many cases. The literature on this topic is extensive, and surveys are given for example by Little and Martin (1974), Martin and Coughtrey (1982), Maschke (1981), Brown (1984), Rao (1982), Tyler (1990) or Zechmeister (1994a). As the method is rather easy to handle and of fairly low cost, it is frequently used nowadays for monitoring large areas, even nations, thus providing deposition maps of heavy metal pollution of an area (e.g. Ellison et al., 1976; Riahling et al., 1987). None of these maps take into account the topography of a country, possibly because this is of minor importance in the hitherto investigated areas. However, in countries or areas dominated by high mountains (e.g. the Alps, the Pyrenees or the Tatra) and therefore with MATERIALS AND METHODS Moss sampling These investigations were carried out on five mountain ranges, which are representative of the different climatic conditions and geological subsoils of the northern and eastern Alps. On each of these ranges sampling points were established at nearly every 200 m (in altitude), starting at the valley bottom up to the peak of the mountains. Between four and eight sampling plots were arranged on a single mountain representing differences in altitude (between 750 m and 1 600 m). More data on the sampling sites as well as their locations can be seen in Tables 1 and 2. Further details on the sampling plots can be given on request. Sampling of mosses has been done mainly by following RfJhling et al. (1987). Below the treeline, the sampling plots were situated in clearings within forests, with a distance of at least 5 m to the next tree, and no cover of any shrubs or tall herbs was accepted. In the valley bottoms, mosses in grasslands which had been cut twice a year without the use of fertilisers were also 73 H. G. Zechmeister 74 Table 1. Data on sampling sites No. 1 2 3 4 5 Name Coordinates Altitude (m) Plots" Species Achenkirch Zillertal Gasteinertal Schoberstein Stuhleck 47°34'/11°38' 47° 14'/11°50' 47°09'/13°04 ' 47055'/14020' 47035'/15046 ' 900-1 660 650-2 260 1 000-2 150 350-1 250 1 000-1 760 4 8 7 4 5 Hylocomium splendens, Ctenidium molluscum Pleurozium schreberi Hylocomium splendens Hylocomium splendens Hylocomium splendens ~Plots means number of sampling points at a single location. taken in some cases. Above the treeline, mosses were collected from open sites with no shelter from bigger rocks or dwarf-shrubs. Small terraces on steep slopes were accepted as sampling points in this study, in contrast to the regulations set up for the international survey of atmospheric heavy metal deposition (Rtihling, 1994). Nevertheless, dripping wet ground was avoided and therefore ground water effects can be excluded at any sites. There were distances of at least 100 m from houses or roads. The samples at each point represent the sum of at least five subsamples within 50 m 2, to avoid differences caused mainly in micro habitats. The collected amount was 0.5 litre of moss at each point (if possible) and plastic gloves were used while sampling. The mosses were stored in paper bags and were dried immediately after collection. Most of the samplings took place in September 1991 but on one mountain range (Achenkirch) there were three collections (July 1991, 1992, and September 1991) to investigate the possible dependency of heavy metal accumulation on the season (Zechmeister, 1994b). In this paper only results from the collection in September 1991 are reported. The mosses used for this investigation were Hylocomium splendens, Pleurozium schreberi, Hypnum cupressiforme and Ctenidium molluscum. Each of these mosses receive water and nutrients only by atmospheric deposition and uptake from soils or litter can be excluded (e.g. Tamm, 1953; Rtihling et al., 1987). In most cases only a single moss species was used for each profile. If this was not possible conversions of concentration data from one moss to another have been made, following conversion data given by Zechmeister (1994a). Table 2 shows the converted data. The nomenclature of the mosses follows Frahm and Frey (1987). Precipitation data Precipitation data are given for the period of sampling heavy metal deposition (1989-1991). The data on the precipitation at different sites were provided by the 'Zentralanstalt for Meteorologie und Geodynamik', Hohe Warte, Vienna. Data on the increase in precipitation with altitude at various sampling points have mostly been calculated by use of the precipitation map (1:50000; Hydrographisches Zentralbtiro des BM ftir Land- und Forstwirtschaft). Preparation of the mosses The mosses were reduced by hand to the shoots which had been growing during the period from 1989-1991, so that the determined concentrations were related to the heavy metal deposition in that period. Following the works of Tamm (1953), Longton and Green (1969, 1979), Rtihling et aL (1987) or Zechmeister (1994a) this could be done easily with a very small error rate. After this, the shoots were cleaned from obvious soil particles. Following the advise of A. Riihling and L. ThSni (personal communications), who had done investigations on this topic, the samples were not washed. The unwashed samples were dried at 40°C. Chemical analyses The following 11 heavy metals were determined: As, Cd, Co, Cr, Cu, Fe, Hg, Ni, Pb, V and Zn. As sulphur (S) is a good indicator for the burning of fossil fuels, and is itself an important pollutant, it was also determined. Before the analyses were done, all samples were dried once again at 70 ° over 12 h. Then they were pulverized by a Retsch-Titan-mill and 2 g were mixed with a mixture (5 to l) of nitric acid and perchloric acid. The decomposition was done in two ways: (i) by heating block with open vessels; (ii) by heating block with reflux system. The extracts were made up to a volume of 100 ml. Variant (ii) was used for volatile elements such as Hg or S. All other elements were determined by using method (i). S, Fe, Zn, Cu, Pb, V were detected on a plasma emission spectrometer (Plasma II, PerkinElmer). Cr, Ni, Cd and Co were determined by an atomic absorption spectrometer with a graphite furnace (Perkin-Elmer 5100 Zeeman-PC). Hg and As were detected by atomic absorption spectrometry (Perkin-Elmer 5000) using a Mercury-Hydride-System MHS 20. Several standard reference materials were used to check the accuracy of the methods (e.g. material from the International Plant Analytical Exchange IPE, Dept. Soil Science and Plant Nutrition, Wageningen; or reference samples (mosses) from the Dept. Vegetation Ecology, University of Lund). Statistics Regression analysis was performed to relate the heavy metal content of the samples with the independent variables, altitude and precipitation. Regressions were calculated for each site. For Sites 2 and 3, calculations have been done both with and without rejecting outliers. Outliers were defined by altitude. Sampling points up to 500 m above the valley bottom were rejected, as they are strongly influenced by local emission sources 12.6 12.1 15.1 13.0 10.8 15.4 17.9 19.9 15-2 6-9 11-5 8.6 12.0 13.2 18.8 17-2 23-0 16.9 22.8 14-4 3.1" 3.2* 3.3* 3.4 3.5 3.6 3.7 3.8 3.9 4.1 4.2 4.3 4.4 4.5 5.1 5.2 5.3 5.4 5.5 5.6 0.8 1.0 0.5 1.4 0.6 1-0 1.8 1.7 1.2 1.4 5-9 5.4 2.4 2.1 2.5 1.6 1.7 1.8 1.7 3.1 1.3 1.4 2.8 3-7 5-2 6.5 1.4 1.6 0-6 0.7 0.9 1.4 0.9 1.6 V 1 147 1074 914 880 783 887 970 1086 988 922 990 1216 1099 1237 1011 1096 1023 1080 1 157 899 833 832 1 169 1211 1304 1317 1018 1071 1 125 1004 981 1044 1033 1 149 S 29-9 33.7 27.4 26.8 25.6 24.5 39.1 36.9 35.1 28.1 64.0 35.3 33.0 39.6 38.0 40.1 41.6 38-2 38.9 29.9 29.5 25.0 36.0 51.5 42.2 64.2 37.6 41.4 29.4 38.1 36-0 30.5 32.4 70.5 Zn 672 503 288 391 369 336 717 613 609 368 2087 1248 1 144 392 470 477 527 466 355 1970 215 235 453 479 931 1239 844 952 230 394 273 364 322 521 Fe Cr Ni 5.4 5.6 5-4 6.3 5.2 5.8 5-9 6.6 6.5 4.4 7.7 6.2 6.9 6.3 6.3 4.9 7.4 5.9 7.3 4.8 5.3 5.2 6.0 5.2 4.7 6.6 5.6 6-1 5.6 5.8 5.6 5.9 5.4 5.9 3.0 1-7 1.5 1.6 1.8 1.5 3.4 2.6 1.2 2.3 5-3 4.6 2.7 1-5 1.8 1-3 1.9 1.7 1.4 6.2 0.9 0.4 1.6 1.5 2.4 2.7 1.5 1.7 0-3 0.5 0.8 0.9 1.0 1.0 2.3 3.8 2-1 1.9 3.3 2.1 2.6 2-1 3-0 2-2 6.9 7.0 4-0 1.8 1.9 1.4 2.2 1.9 1.9 4.6 1.1 0.3 2.2 1.7 2.4 2-0 2-2 2.7 0.7 1.4 1.4 1-3 1-5 3.2 (/zg g i dry weight) b Cu *Indicates sampling points excluded by outlier rejection analysis. aSampling point according to Site no. in Table 1. bSum of 1989-1991. 11.1 9.8 15.2 31.3 14-5 29.7 12-0 7.8 8.1 18.9 12-6 24.3 18.7 24.5 Pb 1.1 1.2 1.4 1.2 1.3 1.4 2.1" 2.2* 2.3 2.4 2.5 2.6 2.7 2.8 Sampling point a 0.2 0-3 0.2 0.2 0.2 0.2 0-2 0-2 0-3 0.3 0.4 0.3 0.4 0.4 0.3 0.5 0.4 0.5 0.2 0-3 0-3 0.3 0.5 0.6 0-5 1.0 0.4 0.5 0.4 0.4 0.5 0.3 0.4 0.7 Cd 0.6 0.5 0.3 0-4 0.5 0.3 0.6 0-4 0.5 0.1 1.t 1.1 0.9 0-2 0.3 0.5 0-2 0.3 0.1 1.1 0-2 0.1 0.2 0-2 0.4 0.5 0.8 0.5 0.2 0.2 0.2 0.2 0-3 0.4 Co 0.03 0.02 0.02 0.02 0.02 0.02 0.04 0.03 0.04 0.03 0.05 0.06 0-04 0-04 0.04 0.03 0.05 0.04 0.04 0.04 0.04 0.04 0.05 0.06 0.09 0.11 0.09 0.09 0.05 0.05 0.04 0.04 0.04 0.05 Hg 1.33 0.59 0.39 0.63 0.66 0.29 0.64 0.75 0.80 0.21 0.84 0-82 0.69 0.48 0.40 0.36 0.52 0.39 0.77 1.19 0.30 0.23 0.46 0.54 0.71 0.81 0.94 0.95 0.34 0.42 0.29 0.34 0.24 0.54 As Table 2. Heavy metal concentration in mosses 1000 1250 1 550 1450 1650 1 850 2100 2050 2150 350 550 750 1 100 1250 1000 1200 1300 1440 1600 1 760 900 1 100 1660 1 100 1400 1660 650 1000 1250 1550 1750 1950 2130 2260 Altitude (m) 3555 4000 4500 4360 4 720 5080 5530 5440 5620 4263 4500 4800 5400 5 500 2681 3050 3250 3600 3750 4120 3855 4200 5 100 4200 4800 5100 3060 3 560 4010 4490 4850 5 210 5540 5900 Precipitation (mm) b Hylocomium splendens Hylocomium splendens Hylocomium splendens Ctenidium molluscum Ctenidium rnolluscum Ctenidium molluscum Hypnum cupressiforme Hypnum cupressiforme Pleurozium schreberi Pleurozium schreberi Pleurozium schreberi Pleurozium schreberi Pleurozium schreberi Pleurozium schreberi Pleurozium schreberi Hylocomium splendens Hylocomium splendens Hylocomium splendens Hylocomium splendens Hylocomium splendens Hylocomium splendens Hylocomium splendens Hylocomium splendens Hylocomium splendens Hylocomium splendens Hylocomium splendens Pleurozium schreberi Hylocomium splendens Hylocomium splendens Hylocomium splendens Hylocomium splendens Pleurozium schreberi Hylocomium splendens Hylocomium splendens Species e~ E" H. G. Zechmeister 76 ' ' ' I ' , , , ' ' . ' ' , ' ' ' I ' ' 40 1 " 1 - ......: : ~ " :: 1"4 ~'1 | ...............: i "i:13.2 ............ i: ........... i ~ i ................... 32 ....... : " ........ i 2,8 3.7• .~: 36 ....... : ; ........ " : 2.2 : i :Ei--.!.- ' [] : ~, ........ ~, i ............ i : ........... : ............ :-,..D....;:. .......... :::............ :i ............ i ":!s.~, ~ ..... ~: :: ...~.'~ :~ • m1.2 o 3 ! ........... ; ................. "o 7 r:: ;...... ~ 3.4:: 1 /).. 28 0,8 [i .............. .... 24 ...... i........... i .... 1000 1288 1400 1600 (a) 1800 ...... ..... 2000 2280 0,6 ..: ............ _ . _ _ ,....iE)/~-..-..._-_.,. ; ........ 600 900 1200 1500 (b) altitude 1800 2100 2400 =Itit~de Fig. 1. Outlier rejection for (a) Zn (Gasteinertal) and (b) V (Zillertal). Altitude in m; concentrations in/~g g 1 dry weight. (a) Correlation factor -- 0.82008; points deleted = 1,2,3; (b) correlation factor -- 0.80447; points deleted = 1,2. Dotted lines represent the regression-line without outlier rejection. a n d a t m o s p h e r i c i n v e r s i o n s (see below). T h e p l o t s (Fig. 1) s h o w the fitted line for r e g r e s s i o n s b o t h w i t h a n d w i t h o u t outliers. T h e c o r r e l a t i o n coefficients c a l c u l a t e d b y r e g r e s s i o n a n a l y s i s were tested for significance (p = 0.05). Correlation analysis and principal components analysis ( P C A ) are m u l t i v a r i a t e m e t h o d s w h i c h r e d u c e d a t a d i m e n s i o n a l i t y b y f o r m i n g l i n e a r c o m b i n a t i o n s o f the i 0.62 i i i i i i i i i i i i i i i i i i i i i i i ............................................................................... o r i g i n a l v a r i a b l e s . T h e use o f b o t h P C A a n d P e a r s o n s c o r r e l a t i o n coefficient a s s u m e s t h a t a l i n e a r r e l a t i o n s h i p exists, d i s t o r t i o n s (Orloci, 1974) c a n n o t be i n t e r p r e t e d b y these m e t h o d s . F o r e a c h p r o c e d u r e , the d a t a m a t r i x c o n t a i n e d the h e a v y m e t a l d a t a o f all s a m p l e s o f Hylocomium splendens a n d Pleurozium schreberi a n d the additional variables on altitude and precipitation at each sampling point. i I 5.3 :'- l l i i l i i i i i i I ................................................................ l l l : ................. • i : Zn !Zn [] 8.42 .................................... S": . . . . . . . . E]I [] ............ !Pb : E] .......... :: Cd:: °c 0.22 3.3 SL : rn:: [] i i i i : ! ! i : i i ; : :: :: Pb i ! i [ ] Cu, I,N : Cd Hg SL : PR ! • :: i i ~.. 1.3 "1 Hg i i Hi i i i Fe . -8.7 -.;............... ::............. ~ . . . . V [] 8.02 -': ......................... ~ ........................... '. . . . . . . . . . ~ .............. i E]Ni i iFe ii--I As Flco -8.18 .:n L, -0.42 (a) :: ; : i i ! i : -8.32 .... i .... -0.22 i .... i .... -8.12 co,p .... -0.02 t I • :: ? i i i i : i i ..... i ............ i ............ :............ i ............ ! ............ : , .c.~l Co i : i .... 0.08 _~.~ ................. i , 0.18 -7.3 (b) . ' " ~ • i . i :.............. ~.............. ;.. ! CP . -5.3 , , , i -3.3 • : " ? : i ....... 7....... ::. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . i !• , , -1.3 , i i', , I 0.7 ........ i , . , i 2.7 Comp.... t 1 Fig. 2. Principal components analysis: (a) plot and (b) biplot for the first two components; Component 1 (37-5%), Component 2 (18.6%); data matrix according to all samples of Hylocomium splendens and Pleurozium schreberi including altitude (SL) and precipitation (PR) at each sampling point. Correlation between altitude and heavy metal deposition in the Alps Table 3. Significant regressions (p = 0.05) between altitude and heavy metal concentrations (including sulphur) at different sites Site 1 2 3 4 5 As Cd Co Cr Cu Fe Hg Ni Pb X* X* X* X* X X X X S V Zn X X X* X* X X indicates significant regression analysis; X* indicates significant regression after elimination of sampling points at the valley bottom (using outlier rejection). Data and moss species used for calculations are given in Table 2. For Site 1 only Hylocomium splendens has been taken Correlation analysis was performed by calculating the Pearson product-moment correlation coefficient. This has a range from -1 (perfect negative correlation) to +1 (perfect positive correlation). The calculated coefficients were tested for significance (Student's ttest). The eigenvalues calculated by PCA which correspond to the axis are given in the text. In Fig. 2 a plot of the component weights and a biplot are given. The ordination of the variables within the axes (plot of component weights) as the length of the vectors and the angle between them (biplot) give information on the contribution of the variables to the principal components, as well as on the correlation between them. In factor analysis, factor weights are scaled, rotation of the matrix was performed by using Varimax rotation. All statistical methods involved were performed by using the statistical package 'Statgraphics' on a PC system at t h e University of Vienna, Institute for Plant Physiology. R E S U L T S AND D I S C U S S I O N Data on the concentrations of heavy metals in mosses (/~g g ~ dry weight) at each sampling point are given in Table 2, They represent the concentration in the moss shoots which grew in the years 1989-1991 (total of 3 years). Distribution patterns At Site I (Achenkirch) the heavy metal concentrations show a clear increase with altitude in most metals. In Hylocomium splendens a remarkable difference in nearly all heavy metal concentrations was found between Sampling Point 1.1 and Sampling Point 1.4 and an even ~;tronger difference in concentration was found between Sites 1.2 and 1.4. The slight decrease of heavy metal concentration from Sampling Point 1.1 to Point 1.2 was probably due to the more sheltered habitat of Plot t.2, and to Site 1.1 being slightly influenced by a nearby main road. The results given for the moss CtenMium molluscum are very similar, even though the tested sampling points are not exactly the same. The increasing rates are small in correspondence to the 77 increases in altitude. Similar results were found on other sampling times (Zechmeister, 1994b). Sites 2 and 3 can be treated as one, as they show rather similar patterns in the distribution of heavy metal concentrations. At both sites there were fairly high concentrations in mosses collected at the valley bottom (2.1, 2.2 and 3.1, 3.2, 3.3). This is probably due to intensive traffic and local house fires (Riicker & Peer, 1988; Bolhar-Nordenkampf, 1989). These influences reach up to 500 m above the valley bottom. Up to this level the vegetation is also influenced by atmospheric inversions, which are fairly common in many parts of the Alps (Kaiser, 1992). Above this line a slight decrease in concentration was found, followed by a constant increase in concentration with ascending altitude. Concentrations in the highest areas were mostly as high as or even much higher than in the valley bottom. Using regression analysis with outlier rejection and therefore excluding the sampling points at the valley bottom, a very distinct, and for many cases significant, increase of heavy rnetal concentration with ascending altitude could be seen (see also Table 3 and Fig. 1). Figure 1 gives two characteristic examples (Zn, V) and shows significant regressions, which might not have been that clear without outlier rejection. More plots of these regressions are available on request. The concentrations at Site 4 show a very typical distribution pattern for nearly each heavy metal. There was a sharp rise in heavy metal concentration at Point 4.2 followed by a more or less constant decrease. The increase of heavy metal concentration is mainly due to a small scale local metal processing industry. Only Cd, Pb and S show higher concentrations at the top of the mountain, probably depending on long range transport from not too distant steelworks, which is also confirmed by the results of multivariate methods (see below). Site 5 is also in the vicinity of an extensive area of local steelworks. Nevertheless, the highest As, Co, Cr, Fe, Ni and V concentrations could be found on the top of the mountain, which is the sampling point furthest from the steelworks. Maybe this was a result of the emission by high chimneys, as well as of long range transport. Apart from the peak in concentration at the top of the mountain no obvious deposition pattern could be found. Correlation of heavy metal concentration and precipitation The obvious increase of heavy metal concentration with ascending altitude in many cases could be put down to various factors. In alpine meadows there is, of course, a higher amount of wind blown particles arising from indigenous soils, as the cover of vegetation is sparse. According to Chamberlain (1966) or Clough (1975) heavy metals spread as small particles and show a deposition closely related to windspeed, which increases above the tree line. In predominantly dry areas, vegetation cover and windspeed might then be major factors in the deposition of heavy metals (e.g. Bourcier et al., 1980). With the high amounts of precipitation in the H. G. Zechmeister 78 Table 4. Correlation coefficients (Pearson product--moment correlation) between heavy metals (including sulphur), altitude and precipitation Precipitation As -0.13 Cd 0.02 Co 0.02 Cr 0.01 Cu 0.11 Fe 4).01 Hg 4).22 Ni 0.16 Pb 0.16 S 0.08 V 0.04 Zn 0.12 Altitude 0.6* Precipitation 1.00 Altitude Zn 4).11 0.00 4).23 4).22 0.03 4).26 4).30 4).23 0.64* 4).02 0.36* 0.04 1.00 0-17 0.63* 0-24 0-18 0-48* 0.38* 0-39* 0-39* 0-3* 0.42* 0.45* 1-00 V S 0.33 0.21 0.12 0.41" 0.65* 0.08 0.741"0.03 0.45* 0.36* 0.77* 0.08 0.29 0.33 0.78* 0.16 4).13 0.21 0.28 1.00 1-00 Pb Ni Hg Fe 4).12 0.55* 0.29 0.67* 0.11 4).01 0.51" 0.06 4).27 0.84* 0.25 0.89* 4).18 0.81" 0.04 0.89* 0.34 0.33 0.21 0.28 4).19 0.83* 0.32 1.00 4).13 0 . 1 4 1.00 4).22 1.00 1.00 Cu Cr Co Cd 0.23 0.64* 0.7* 4).19 0.02 4).21 4).03 1.00 0.15 0-82* 1.00 0-16 1.00 1.00 As 1.00 *Indicates significance. northern and eastern Alps, however, the main source of heavy metal deposition seems to be rain. As in the Alps the precipitation rises more or less constantly with increasing altitude, a correlation is obvious. To test this theory, regressions between precipitation and heavy metal concentration have been calculated for each site and each metal. Significant correlations (p -- 0.05) can be seen in Table 3. These results show only the correlation between the total quantity of rain and concentration, not considering the fact that there may be also a strong impact by the frequency or the intensity of a single rainfall event (e.g. Martin & Coughtry, 1982). Dry deposition might occur as well, even during periods of rain. The dispersion of indigenous heavy metals may be recognised by higher amounts of Fe, Cr and V. In this investigation, only V shows a slight increase at higher altitudes. Ti might be a very good indicator for the detection of indigenous particles (Brown & Brown, 1990), but it was not analysed in this study. As the quantity of precipitation is calculated in most cases as a variable dependent on altitude, there always has to be a strong correlation between precipitation and altitude in the data in Table 3. To avoid this side effect, multivariate methods have been used without respect to sampling sites. For these analyses only data from Hylocomium splendens and Pleurozium schreberi have been used, as they have fairly high and equal accumulation capacities for heavy metals. Ctenidium molluscum has a much higher accumulation capacity and was excluded for this reason. These results are given in Table 4 and Fig. 2. In Table 4, the Pearson product-moment correlation coefficient and significances are given. Pb and V show a significant correlation to altitude. As this analysis only reveals relationships between pairs of species, the effect of other variables (hidden influences) cannot be detected. The plots in Fig. 2 show the graphs according to principal components analysis (PCA). The eigenvalue for component 1 is 5.25, for component 2 it is 2-56. Nevertheless component 1 (37.5%) and 2 (18.6%) represent only 56.1% of the total variance. But even the rotation of the matrix (Varimax) in factor analysis does not change the results too much, from those given by the first two components of PCA. The results given by PCA are also fairly similar to Pearson correlation coefficients in many respects. Each PCA component is hardly explained by a single factor, though there seems to be a strong relation to altitudinal distribution (Component 1) and common emission sources (Component 2). Two more or less distinctive groups could be detected. Group 1 (Fe, Ni, Cr, Co, V, As) which also shows strong internal relations by calculating Pearson correlation coefficients, could be released by steelworks, but shows a close relation to indigenous soils and therefore to windblown particles too. The contrasting ordination of Group 1 and altitude illustrates the minor correlation between elements of Group 1 and altitude. This is partly in contrast to regression analysis and Pearson correlation coefficients. The ordination of precipitation (PR) shows little relevance to Component 1 and should not be considered in explaining Component 1. This is in sharp contrast to other mathematical approaches. Group 2 (Pb, Cd, S, Zn) shows very similar ordination within Component 2. Elements of this group derive mainly from fossil fuel combustion, e.g. traffic (Adriano, 1986; Vernet, 1991), but might not be associated to this source alone. Anyway these elements are mainly released as a consequence of human activities. Nevertheless, the small particles released from various high temperature processes reach the atmosphere and are subjected to a wide distribution (Galloway et al., 1982). CONCLUSIONS In general, the results show a high correlation between altitude and heavy metal concentration in mosses for Pb and to a lesser extent for Cd. These heavy metals are mainly accumulated and spread by human beings and have a very low content in rural sites and unpolluted Correlation between altitude and heavy metal deposition in the Alps soils or plants (e.g. Galloway et al., 1982; Glooschenko, 1989; Schmid-Grob et al., 1991). According to multivariate methods and regression analysis, an altitudinal related increase also occurs for S, Zn and V. These results are similar to those obtained in an investigation done by Mutsch (1992), who analysed soils in Austrian woods. He found an increase of heavy metal concentrations, mainly for Pb and Cd, and put it down to external long-range transport. Solt6s (1992) found similar correlations for Pb in the Tatra. Groet (1976) correlated Zn and Cd contents with increasing altitudes in the United States. Riacker and Peer (1988) found higher concentrations of Pb, Cd and Zn in soils of alpine regions than of woods below. Ross (1990) and Rfihling et al. (1992) suspect that higher amounts of Zn are also partly related to indigenous soils. Correlations between precipitation and heavy metal concentration in mosses are given by Ross (1990) for Cd, Cu, Fe, Pb, Zn and V. R0hling and Tyler (1971) found this relationship only for Pb. Both investigations have not been performed on an altitudinal transect and so may be related to other factors as well. Contrary to this, the results of Herman and Stefan (1992) and Herman (1992), who analysed soils, spruce needles and barks in Alpine valleys, did not show any altitude relationship, nor did Schmid-Grob et al. (1991), who put it down to the fact that their transects covered too small a range in altitude. The results of this work are based on the assumption that tLg g~ heavy metal (dry weight) is determined mainly by atmospheric input. Differences resulting from different growth patterns at various altitudes do not explain the increase of heavy metal content of the moss samples. Despite the fact that the annual biomass of the individual moss stems and leaves decreases with increasing altitude, the population density increases at higher altitude (Zechmeister, 1995). Therefore the area covered by the analysed moss, as well as the biomass which cover this area is almost constant under various climatic conditions. R~hling (1985) confirms this assumption for Swedish populations of Hylocomium splendens (113 g m 2) as well as Zechmeister (1994a, 1995) for populations of Hylocomium splendens and Pleurozium schreberi at various regions and altitudes within Austria. Nevertheless, some alpine populations of these two species which are related to 'forma alpina' show greater biomass per area than populations with ordinary growth patterns at lower altitudes. In the current investigation, two samples were taken from 'forma alpina' species. In these cases (Sampling Points 3.8 and 2.8) the actual concentrations ate underestimated compared to the other samples. In consequence, the increase of heavy metal concentration is probably higher than shown for example in Fig. 1. But area related data on growth measurements are still too few to calculate conversion values between these two growth forms. The increase of heavy metals with altitude can be observed clearly only in areas with a rather weak local influence of pollutors. In areas with a strong local 79 pollution these results can not be confirmed for obvious reasons. Although only a few local pollutors are situated throughout the Alps, the investigation demonstrates that there must be an unrelated high pollution by heavy metals in alpine regions caused mainly by long-range transport. 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