Heavy metals and sulphur in mosses from southern Spitsbergen KRYSTYNA GRODZINSKA and BARBARA GODZIK Grodzinska, K. & Godzik, B. 1991: Heavy metals and sulphur in mosses from southern Spitshergcn. Polur Research Y(2I3 133140. Concentrations of Cd, Pb. Ni. Cu. Zn and S were determined in 16 nioss species collectcd from 9 localities in southern Spitsbcrgcn (mostly within the Hornsund region). Two species, Sanionia uncinrrfa and Hybcumiuni splendens, were objects of more thorough studies. I n Sanionia uncinara the mean con- centrations werc ( ~ d g ) : Cd-0.59, Pb-7.07, Ni-4.25. Cu-6.01. Zn-21.13 and s- 1.481. Hylocomium splendens accumulated similar quantities of these elements. The concentrations of metals and sulphur in mosses differed significantly ( p < 0.05) from site to site. depending on geological and climatic conditions specific to the Arctic region. The effect of remote sources of pollution reaching Spitshergen on the levels of heavy metal concentrations was taken into account, a5 well as thc effect of local emissions from the Polish Polar Station. At 1@25 metre distances from the Station. thc levels of heavy metals and sulphur werc 3-10 times higher than at a 300-metre distance. Krysryna Grodzrnska and Barbaru Godzik. W. Szafer Insfirrite of B o t a ~ i , ~ . Polish Aradertly of Sciences. Luhicz 46, 31.312 Kruk6w. Poland. Introduction The Arctic environment is influenced by chemical elements of both anthropogenic and natural origin and from remote as well as local sources (Jaworowski 1989). The Svalbard region is exposed to a greater atmospheric transport of inpurities from distant sources than some other Arctic areas (Rahn et al. 1983; Penkett 1984; Pacyna & Ottar 1985; Ottar et al. 1986; Heintz- enberg 1989; Jaworowski 1989). The island seems to be affected by airborne pollutants originating in western Europe and the Soviet Union and to a lesser extent in North America (Rahn & Show 1982; Rahn 1984; Maenhaut et al. 1989). Local sources of pollution, e.g. mines, miners' colonies and polar stations (Krzyszowska 1985a), are thought t o contribute only negligible quantities of pollutants compared with remote sources (Lan- nefors et al. 1983). The extent of environmental pollution is often assessed by employing plants of various sys- tematic groups as bioindicators (Grodzinski & Yorks 1981). Mosses have commonly been used as bioindicators of pollution by heavy metals (Riihling &Tyler 1973,1984; Ruhling et al. 1987; Grodzinska 1978; Grodzinska et al. 1990) and, to a lesser extent, as indicators for sulphur com- pounds (Winner & Atkinson 1987; Szarek & Chrzanowska in press). The aim of our study was to assess the degree of environmental pollution in a large area of southern Spitsbergen as well as the area closely surrounding the Polish Polar Station in the Hornsund area; as bioindicators, we employed various species of moss. Material and methods Sixteen species of mosses were collected in Arctic tundra ecosystems at 1-9 sites within an area of 30,000 km? in southern Spitsbergen. Eight species were collected at 1-6 sites within 10 to 300-metre distances west and east of the Polish Polar Station (Figs. 1 and 2). All the samples were taken at the beginning of June 1985, immediately after snow melting. The unwashed mosses were separated into green and brown shoots and stored in paper bags. The material was dried to a con- stant weight at 85". The samples were then wet- digested in a 4:l mixture of concentrated spectral pure nitric (HN03) and perchloric (HC104) acids on a hot plate for 3 days until all organic matter was oxidized. The solution was evaporated to 1 ml and then diluted with distilled water to 50 ml. Pyrex glassware was used for the chemical procedure. 134 Krystynn Grodziriska & Burbara Godzik I I I 1 L' 16' 18' 1 22' 2 6 - 0 25 50km u Heavy metal ( C d , Pb. Ni, Cu. Z n ) con- were(yg/g): Cd-00.01. Cu-0.01, F e - 0 . 3 , M n - 0.0. Ni - 0.02, Pb - 0.04. Z n - 0 . 1 C a - 0.6. M g - 0.2 and S - 5 . Nonparametric two-way variance analysis and H-test (Sokal& Rohlf 1969) were used to estimate the differences between element concentrations in moss species from the various sites. centrations were determined in the water solution by atomic absorption spectrophotornetry (Varian Techtron A-1000). Total sulphur was determined by the Butters-Chenery method according to Nowosielski (1968). Blanks were run in each series of samples. T h e concentrations of metals and sulphur in the blanks Heavy metals and sulphur in mosses from southern Spitsbergen 135 I i I I 77’- j I I i I i I 3. ARIEKAMMEN 4. FUGLEBERGET 5 .GNALODDEN 6.TRESKELEN 7. GASH A M N A 8,PALFFYODDE N PPS - POLiSH POLAR STATION 15’ 15’20’ 15’40’ Fig. 2 . Sites of moss sampling in the Hornsund area. Results Heavy metal Concentrations in mosses from southern Spitsbergen Considerable differences among concentra- tions were found for particular species (Table 1). The moss species can be divided into two groups as far as the accumulation of some chemical elements is concerned. Aulacomium palustre and A . turgidum, Hylocomium splendens, Sanionia uncinata and Tortula ruralis are good accumu- lators for heavy metals while Racomitrium lanu- ginosum, Polytrichum alpinum and Dicranum groenlandicum are not. The members of the first group show significant ( p < 0.05) differences in heavy metal concentrations at different sites within southern Spitsbergen, whereas moss species of the second group show more homo- geneous results (Table 2). Two species (Hylocomium splendens and Sanionia uncinata), which accumulate rather large quantities of heavy metals were chosen for assess- ment of the extent of environmental pollution. 16‘ 16’20’ Sanionia is a very common species throughout the area. Hylocomium is much less common, but it was chosen because of its widespread use as a bioindicator of environmental pollution else- where. The mean concentrations of heavy metals in Sanionia uncinata in southern Spitsbergen were as follows (pg/g): Cd-0.59, Pb-7.07, Ni-4.25, Cu-6.01 and Zn-21.13 (Table 3). Hylocomium splendens accumulates heavy metals at similar concentrations: Cd - 0.66, Pb - 6.54, Ni - 3.56, Cu - 6.08 and Zn - 23.80 (Table 4). The concentrations of heavy metals in both Sanionia uncinata and Hylocomium splendens varied among the sites (Tables 3, 4; Fig. 3). The highest quantities of cadmium in Sanionia unci- nata were accumulated at the Gnilodden site, of nickel and copper at the Treskelen site, of zinc at a southernmost Sorkapp site, and of lead at the Palffyodden site (Table 3; Fig. 3). The least quan- tities of cadmium, zinc and copper were found at the Gishamna site, of lead and nickel at the Werenhus site (Table 3; Fig. 3). When the sites are arranged in order of increas- 136 Krvstyna Grodziriska & Barbara Godzik Tobit. I Concentration\ (.>I tie,n,! metal, and total \ulphur Icig g ' d , w t ) in rno\\ch from southern Spitsbcrgen (valucs arc ineanh oi . ? - ? I \:imples). ~ Cd Ph N I Cu Z n S SPCLlC\ n x S D \ S D U S D x SD X S D Y SD Aulacomnium palustrc (Hcd* ) Schwacgr. Aulacomnium turgidum ( W h l b . ) Sch\\acgr. Brachkthccium turgidum ( H a r t m . ) B.S.G Callicrgcln \tramincum ( B r i d . 1 Kindh. Dicranum grocnlandicum Brid. Dicranum spadiceum Zett. Ditrichum Rcuicactle (Schlcich.) H a m p r Hyloconiium \plendcns ( l 3 e d w . i B . S Cj Plcurozium schrcberi Mitt. Polytrichum alpinum Hedw. Polytrichum commune Hcdu . Racomitrium ericoidc\ (Urid. 1 Brid Racomitrium lanuginosum (Hcdu.1 Brid. Sanionia uncinata H e d w . Tomcntvpnuni niten\ ( t f e d w . ) Locskc Tortula ruralis ( f l c d u , . ) G a e r t n . . Meyer e t Schsrb. 6 11.83 ( I . l X 6.69 1 . 4 2 8.31 5 4 1 13.98 I5 0.77 U.19 5.68 3 I ? 2.57 0.81) 3.31 3 1.95 I1 37 3.50 I1 74 1.81 0.45 4 . 4 2 3 0.82 OO6 4.03 11.77 7.29 0.45 6.11 8 0.46 1.12 2.93 1.36 1 7 0 0.59 3.67 8 0.59 0.21 5.70 2.16 2.41 045 3.02 3 11.44 0.13 1.60 (1.04 0.79 0.02 2.15 9 0.66 I1 I 2 6.54 1.45 3.56 1.25 6.08 6 0.63 U.14 6.MI 3 . 5 1 3 Y(l 1.65 2.92 8 0 . 4 2 KO9 3 5 8 1.87 2.33 0.71 4.34 3 I).% 0.04 lJ.94 11.78 1.71 0.21 4.76 3 0.82 lJ.07 7.115 1.30 12.56 0.56 17.69 I 8 0.31 (1.09 4.86 2.20 2 . 3 5 0.87 2.31 21 0.59 0.13 7.07 4.49 4.75 2.53 6.01 6 0.71 (1.11 6.44 L 4 Y 8 75 6.92 5.92 12 0 . X 5 IJ.4il 5 22 1.76 3.57 0.84 6.90 13.07 ?Y.(iZ 5.33 1.97 26.76 6.96 0 . i X 20.33 0.48 u.no 29.07 1.27 0.76 16.39 4.43 1.03 17.19 5.22 0.00 9.811 0.86 3.01 23.80 9.88 1.05 19.35 6.01 0.40 18.69 3.19 0.5X 24.01 0.32 1.80 42.87 2.31 1.91 13.04 4.94 4.52 21.13 4.98 7.07 26.70 17.65 3.30 31.74 14.21 903 220 1081 247 1168 314 1219 325 1190 282 1112 322 780 52 1103 297 1224 368 1238 303 1294 313 1586 37 561 164 1481 143 1256 41 1718 369 ing concentrations of heavy metals. the list starts with the Gilshamna and Werenhus sites and ends with the Treskelen. Gnalodden and Palffyodden sites (Table 3 ) . Total sulplzitr concentration in mos.res from southerti Spirshergen The concentrations of sulphur are highest in Saniotiia uncinatu, Aulacomium turgidurn and Hyloconiium splendens and many times less in Ritcomitrium lanuginosum and Polytrichum alp- inum (Tables 1 , 3 and 4). T h e r e are statistically significant (p < 0.05) differences in sulphur con- centrations in mosses between sites (Table 2). Sanionia. f o r example, accumulated the least sul- phur on the Werenhus site, the most on the Arie- karnrnen site (Table 3). I d d r 2 S t a t i m u I anal!si\ of the differences betuc.cn hc.a\! iiic.tak. and total w l p h u r conccntrations in moss species from various sit^ in w u t h c r n S p i t s h c r y n . " Specie, Aulaconiniurn turgidurn Dicranuni grr~enlandicuiii ti! locnmiuni splcndens Polttrichum alpinum Racomitriuin lanuginosum Snnionia u n c i n d i i T o r t uI;i r 11 ralk Cd U.UU.1* I1 6")"' 0.u4 I ' 11.362"' 0.457"' O.IJ21 ' O.(WJI CU ~ Zn S 0.00(1* 0.044* O.U44* 0.223"' 0.103"' 0.007 * O . l ~ O o * o.oG€* 0. om* 0.1)11* O.OO7 * (1 181"' 0.001' 0.982"' 0.022* 0.044" 0. (106 * 11.008' 0.000* 0.000' 0.011* . p '. i l 115 " Sc\cn m o b \ \pecic\ occurring in more than N O sites Here used for statistical analysis (cf. Table I ) . Heavy metals and sulphur in mosses from southern Spitsbergen 137 Table 2 . Concentration5 of hcavy mctals and total sulphur (pgg I d . w t ) in Suiiionicc uncbiatci collected from 8 sites in aouthrrn Spitahergen. Values are means of 3 samplcs cach. Site Cd Ph Ni CU Zn S U SD X SD X SD X SD X SD X SD Wcrcnhua Rotiesfjellet Fuglehergov Arichammcn Gnalodden Trcskclcn Gaahamna Palffyoddcn Smkapp Average ~~ 0.526 0.07 3.36 0.34 1.60 0.04 2.85 0.61 20.95 9.91 1330 I l l 0.679 0 . 0 8 4.99 1.08 2.37 0.(16 2.73 0.58 17.16 1.51 - 0.723 (1.817 0.582 0.406 0 502 0.576 0 598 0.12 9.48 1.55 5.06 (1.39 9.51 lI.(lO 21.98 1.31 I626 64 0.05 12.0 2.11 3.30 0.27 4.27 0.00 26.17 U.31 ~ 0.05 5.12 0.54 X.XX 0.24 14.96 1.54 2.5.00 1.92 1600 52 0.04 3.8s 0.55 2.07 - (1.22 2.(J5 0.00 12.3X 1.14 1370 0 0 . O X 16.26 0.52 6.76 0.11 6.84 0.84 22.83 0.35 - 0.115 4.6O 0.3Y 4.67 0.55 5.60 11.70 27.00 1.56 - 0.13 7.07 4.49 4.35 2 . 5 3 6.01 4.52 21.13 4.98 14x1 I43 Concentrutions of lzeavy metals mid sulphur in the surroundings of the Polish Polar Station Within 10 to 25 metre distances from the Polish Polar Station the concentrations were several times higher than those at the Ariekammen site which is about I km distance from the Station; the concentrations were also higher than the mean concentrations in Sanionia uncinatu on 8 sites of southern Spitsbergen (Table 5). Most remarkable were the differences in concentrations of zinc ( l o x ) , copper ( 6 ~ ) and lead ( 3 ~ ) between sites within 10-25m of the Station and the Arie- kammen site. The differences were less pro- nounced in the cases of nickel and cadmium (Table 5 ) . Around the station Sanionia iincinata had higher amounts of heavy metals than H y l - oconiium splendens (Table 5 ) . At 150-300 metre distances from the Station, the heavy metal concentrations did not differ from those at the Ariekammen site and the 8 sites of southern Spitsbergen (Tables 3-5). The total sulphur concentrations in mosses col- lected in the entire 10 to 300 metre zone near the Station were uniform and did not differ from those found at the Ariekammen site (Tables 3-- 5). Discussion The different concentrations of heavy metals in mosses noted from the various sites in southern Spitsbergen situated several kilometres to several tens of kilometres suggest local causes of such differences. Spitsbergen is an area with very diversified geology. The southern part of Spitsbergen con- sists mainly of Precambrian formations of Hoeckla Hoek, accompanied by rocks of Carbon. Permian and Devonian age (Smulikowski 1965). In the fjord Hornsund there are quartz, ankerite. and ankerite-quartz ore-bearing veins. These veins often contain pyrite and chalcopyrite; less often they contain pirotyne, galena, sphalerite. limonite, cuprite, malachite and azurite (Bir- kenmajer & Wojciechowski 1964; Wojciechowski Table 4 . Concentrations of hcavy metals and total sulphur (lip g - ' d . w t ) in Hyloconiiim splendcns collected from 3 sites in southern Spitsbcrgen. Values arc means of 3 samplcs cach. ~~ Cd Pb Ni C U Zn S Site X S D X SD X S D U SD X SD X S D Rotjesfjellet 0.75 0.12 6.4 0.62 3.63 0.45 1.08 0.00 17.77 3.09 730 13 Ariekammen 0.518 0.03 5.05 0.43 2.37 0.06 4.0X 0.00 36.2 2.X6 140(1 34 Fuglcbcrget 0.719 0.08 8.18 0.72 4.69 1.43 10.10 0.00 17.45 1.00 1180 40 ~~ ~ Average 0.662 0.13 6.54 1.45 3.56 1.25 6.lJX 3.47 23.X0 Y.88 Il(13 297 138 Krystyna Grodziriska & Barbara G o d z i k Pb - ppm‘ Ni,Cu.Pb - cu - - :d - Cd - L Z r - Zn - I0 20 nt 10 !3$5 6 7 8 9 Fig. 3 . Concentration of Cd, Ni, Cu. Pb and Zn (ppm d . w t . ) in Sonionio uncinara collected from different sites in southern Spirshergen: See Fig 2 for locations of sites 1-8; site 9 = Ssrkapp 1964). The rocks of Fugleberget, Ariekammen, Gdshamna and Palfyodden, where most of Zn, Cd and Pb. samples of mosses were collected, are rich in pyrite and chalcopyrite (Wojciechowski 1964). These rocks contain higher concentrations of heavy metals, mainly Fe and Cu, sometimes also Rather high concentrations of heavy metals (except Pb) in Svalbard soils are reported by Steinnes (1984) and Thomas (1986). Table 5 . Cmccntrations of hcavy mclal\ and total sulphur (118 g ’ d . w t ) in S o t t r o f ~ i o ioicitiorci ( S ) and Hvlocornium splrriclen~ ( H ) coilcctrd in variow distances from thc Polish Polar Station Vaiucs arc mcans of 3 samplcs cach. Cd Ph Ni c u Zn S S1tc T SD x S D x SD x S D i SD X S D - S 1.15 0.14 30.18 0.00 6.04 0.45 36.90 2.30 226.0 50.90 1450 0 0.h7 0.09 15.56 0 38 5.55 0.77 14.24 0.64 96.9 1.21 1146 35 I1 68 1).04 11.75 2.10 3.85 0.32 8.66 1.22 47.3 1.10 1136 11 5 I) 44 (1.12 8.98 1 . 1 1 4.53 I1.M) 7.44 0.M) 4 6 . 2 6.36 I663 35 S 0.41 (1.06 6.W 0.89 3.15 0 . 6 4 4.YX 0.00 2 1 . 3 0.77 - I 1 - S I I Y 5 0.06 2 1 . 1 1 2.03 4 5 3 IJ.IH1 ?&(I4 2.30 76.Y 0.X7 1360 69 11 - S I1 5 7 0.07 5.54 0.47 3 . 1 4 0.86 7.77 0.47 145.9 5.16 - I O O m E ,, - 1 0 m W I , 7 0 m W 150 inM’ s I1 56 11.05 x.93 0.79 3.93 0.57 X.66 1.22 73.9 8.98 - I I I1 35 1 ~ . 1 I O 8.19 0.00 2.X8 11.49 Y.90 1.56 45.7 4.11 - ~ - - - - - - - - 3oo 111 M’ ~ ~ ~ - - - - - - - - 25 m E ~ - - - - - - - - - Heavy metals and sulphur in mosses f r o m southern Spitsbergen 139 In the Arctic areas, superficial rocks are weath- ered into fine particles due to the erosive action of air and water. In southern Spitsbergen, the snow cover persists for 9-10 months. During the short 2-3-month summer, abundant waters from melting snow flow over the surface of rocks and moss mats. They carry a variety of rock fragments, minerals, and chemical compounds which can easily be absorbed by plants (Krzyszowska 1985b). Mosses have no epidermis and cuticula, therefore their cell walls are easily penetrable for metal ions (Tyler 1971, 1972). It may be supposed that there is a relationship between the levels of at least some of the heavy metals in mosses and the substrate in the southern part of Spitsbergen. The chemical analyses within this project covered only mosses; the chemical composition of soil and rocks was not determined. No data are therefore given here which could document correlations between the concentrations of heavy metals in mosses and substrate in individual sites in SOU- thern Spitsbergen. Many published studies (Rahn et al. 1983; Heintzenberg 1989; Jaworowski 1989) state that air pollutants from industrialized parts of the Northern Hemisphere reach the Arctic regions by way of long distance transboundary transport. These pollutants enter Arctic tundra via precipi- tation. Mosses, the main components of this tundra, have no organs for uptake of minerals from substrate; they obtain minerals, as well as pollutants, from the atmosphere from precipi- tation and dry deposition (Tyler 1971). Hence it may be expected that high concentrations of heavy metals and sulphur in the mosses of SOU- thern Spitsbergen are, at least, in part, caused by the long range transboundary transport of pol- lutants in gaseous and particulate form. Our data for heavy metal concentrations in mosses from southern Spitsbergen have been compared with similar data from Sweden, Iceland, and Greenland (Riihling et al. 1987). The levels of lead and zinc in Spitsbergen mosses are several times lower than those found in Sweden, but similar to those from Iceland and Greenland. However, the copper concentration in mosses from Spitsbergen was similar to that in Sweden and 2-3 times less than copper con- centrations in mosses from Iceland and Green- land. The mosses from southern Spitsbergen contained considerable quantities of cadmium and nickel, higher than found in mosses from Scandinavia, Iceland and Greenland. Our results are in a good agreement with the heavy metal concentrations in plant mat- erial collected in Spitsbergen and reported by Jaworowski (1967), Thomas (1986), and Ottar et al. (1986). Ruhling et al. (1987) demonstrated decreasing heavy metal concentrations from south to north in Scandinavia as an effect of the transboundary transport of pollutants from western Europe. Lead, zinc and copper follow this pattern in south- ern Spitsbergen; cadmium, nickel and sulphur do not. Staaland et al. (1983) found much higher con- centrations of metals in reindeer forage plants (lichen, bryophytes, forbs) from Svalbard than in plants from continental Norway. Jaworowski (1989) suggests that this might be due to the greater availability of metals in Svalbard soils, a result of intensive weathering processes. The level of heavy metals found in mosses collected within a 10-300 metre radius around the Polish Polar Station at Hornsund proved that the chemical effects from the station are local and present no threat to the Arctic tundra ecosystems. Similar conclusions have been reached by Krzyszowska (1985a). According to her assess- ment, the anthropogenic impact of the Station is rather insignificant, affecting no more than 3.5 hectares. Because of specific climatic conditions and the diversified chemistry of the substrate in the Arctic regions, the mosses should be applied as indi- cators of air pollution by heavy metals only with caution. Mosses in the close surroundings of local sources of pollution, for example polar stations, in uniform geological conditions can prove to be very sensitive indicators of local changes in the atmosphere. Sanionia uncinata, Hylocomium splendens and other species representing the first group of mosses distinguished in this study can be regarded as good indicators of pollution originating from local sources. The other group (among others Racomitrium canescens and Polytrichum alpinum) shows less diversity in heavy metal con- centrations between sites in southern Spitsbergen, being less affected by substrate composition. This group may be used for monitoring pollutants orig- inating from distant, transboundary sources. Acknowledgements. - This work was supported by the Polish Academy of Sciences, programme CPBP 03.03. 140 Krystyna Grodzinska & Barbara Godzik References Birkenmaler K . & Wojciechowski. J . 1964. On the age of ore- bearing veins of the Hornsund area. Vestspitshergen. 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