Research Note Cladina stellaris (Opiz) Brodo as a bioindicator of atmospheric deposition on the Kola Peninsula, Russia K R Y S T Y N A GRODZINSKA, BARBARA GODZIK and PIOTR BIENKOWSKI Grodziriska. K . , Godzik. B. & Bierikowdi, P. 1999: Clutlinu .vte/luris (Opiz) Brodo as a hioindicator of atmospheric deposition on the Kola Peninsula, Russia. Polur Reseurch 18(1). 105-1 10. Concentrutions of 16 elements (Al, Cd. Co, Cr. Cu. Fe. Mn, Ni, Ph, Zn. C. N. S . P, Ca, Mg) were determined in the lichen Clatlina src4laris (OpiL) Brodo collected from 26 localities on the Kola Peninsula. Concentration5 were higher closer to the emission sources. In Arctic regions affected by local emissions. lichenz, c:in he recommended ti\ seiisitive indicators of atmospheric pollution. K . Grod:insku d; B. God:ik. W . S s r f r r 117.uitiite of Botany, Poli.rh Acudetny of Sciences, Liihic: 40, 31 -512 Kruk(iw, Polund; P. B i e i k o i u k i . Institute of E c o / o , y y , P o l i s h Acadeniy o / Sciences, Dziekunciv Les’tiy iieur W u t x a i v t r . 0.i-092 toniiuriki. Poliiriil. Introduction The Kola Peninsula is one of the areas in the northern hemisphere polluted by heavy metals and sulphur (Kozlov et al. 1992; Tikkanen et al. 1992: Makinen 1994: Ruhling 1994; Alexeyev 1995: Baklanov et al. 1995; Glazov et al. 1995; Kelley et al. 1995: Moiseenko 1995). The primary sources of pollution are: copper-nickel smelters located near the towns of Monchegorsk (Severonickel smelter) and Zapolyami (Pechenganickel smelter). Other operations on the Kola Peninsula include an aluminium smelter in Kadalaksha, iron and apatite mines in Kirovsk and Olenegorsk, and coal burning and naval installations in Murmansk (Fig. 1). The Kola Peninsula is also affected by long-range transport of pollutants; however, that contribution is negligible compared with local sources. Yearly copper emissions on the Kola Peninsula exceed two thousand tonnes (Severonickel two thousand, Pechenganickel 180 tonnes) and nickel emissions exceed three thousand tonnes (Sever- onickel three thousand, Pechenganickel 300 tonnes) (Makinen 1994; Jaffe et al. 1995). Total SO2 emissions are approximately 600 thousand tonnedyear (Jaffe et al. 1995). The regional depositions of Cu and Ni are: 0.15 and 0.35 k g h d y e a r respectively (Alexeyev 1995). Average sulphur deposition on the Kola Peninsula is approximately 0.7-1 .O g/m’/year, and near the local sources is even as high as 30glm’lyear (Moiseenko 1995). Sulphur depositions are higher than critical values across most of the Kola Peninsula (Koptsik & Koptsik 1995). The Kola Peninsula is part of the Fenno- Scandian Crystalline Shield, built of Palaeozoic granitoids and metamorphic crystalline shields (Skiba 1994). Podzol soils and weakly formed soils are most common. They are acidic (pH about 4). with about 50% organic matter and a C/N ratio of about 30. The concentration of heavy metals is high (iron max. 18,000 pg/g d.wt, copper max. 2000 pg/g d.wt., nickel max. about 2000 pg/g d.wt. (S. Skiba 1994, unpubl. data). The topography of the Kola Peninsula varies considerably. While areas along the coast of the White and Barents Seas are below 2 0 0 m a d . , most of the land is between 200 and 500 m a.s.1. Mountains, with the highest peak at 1208 m a d . , cover a small area in the middle of the peninsula. Smelter complexes are located at altitudes of 100- 350 m a.s.1. (Makinen 1994). The peninsula lies mostly within the cool temperate zone; only the north-eastern part is included in the polar zone. The average summer temperature is about 8 - 1 4 T . Annual precipitation averages approximately 400 mm. The growing 3 2' 36' season is short (120-125 days). South-westerly winds predominate during the winter; i n summer they are often north-easterly (Luzin et al. 1994; Makinen 1994). The vegetation belongs to the northern boreal and arctic alpine zones and is represented by forest tundra (spruce, Scotch pine, birch) or treeless tundra and mires. Close to the industrial areas the vegetation is seriously da- maged: dying forests are common (Makinen 1 994). Because of their anatomical structure, lichens and mosses have a great ability to accumulate various chemical elements, including air pollu- tants, making them useful for assessing environ- mental contamination (Markert 1992). Various lichen and moss species have been used as indicators of environmental pollution i n Arctic areas by Ruhling et al. (1987), Grodzinska & Godzik (1991), Heino et al. (1992), Grodzinska et al. (1993). Makinen (1994). Steinnes et al. (1994) and Glazov et al. (1995). Cladina stetluris (Opiz) Brodo (= Cladonin alpestris [L.] Rabenh.) has been used as a sensitive bioindicator of heavy metal pollution several times (Pakarinen et al. 1978; Nuorteva et al. 1986; Kortesharju et al. 1990; Nuorteva 1990: Glazov et al. 1995). According to Folkeson & Andersson- Bringmark (1988), this species is an especially effective accumulator of Cu and Zn. The aim of this study was to determine the 40' F i g . 1. The Kola Peninsula: major urban and industrial sources. concentrations of 16 elements, mostly pollutants, in C. sfelluris, which is common in the area. Methods During summer 1992, lichen samples were collected along two transects which were located along the road network, and spanned forest tundra and treeless tundra ecosystems. The first transect (ca. 200 km) ran southward from Zapolyarni (the location of the Pechenganickel smelter), via Murmansk, to Monchegorsk (Severonickel smel- ter). The second (ca. l50km) ran eastward from Murmansk to Dalnye Zelentsy (Fig. 2 ) . The sampling density was about one composite sample every 10-15 km. No samples were collected within 5 km of the smelters. Sampling sites were no less than 150 m and no more than 200 m from the roads. At each sampling site. three subsamples were taken within an area of 20-30 m2, and then combined in one collective sample of 20-25 g d.wt. Sampling and sample handling were per- formed without polyethylene gloves. The samples stored i n the field i n polyethylene bags were transported to the laboratory and cleaned of litter and other debris. Unwashed samples (whole lichen) were dried at 600'C, then homogenized. Samples of 0.5-0.6 g d.wt (ICP-AS) Claditza stellaris (Opiz) Brodo CIS a bioindicator of atmospheric deposition 107 Fig. 2. The study area with sampling sites. North-south (sites 1-15) and west-east (sites 16-26) transects. or 5-10 mg (elemental analyser CHNS-0) were digested in the mixture of spectral pure concen- trated acids (HNO3/HC1, proportion 2: 1) i n microwave CEM-MDS 2000. Digestion samples were then diluted to about 50 ml i n bidistilled water. Thirteen elements (Al, Cd, Co, Cr, Cu. Fe, M n , Ni, Pb, Zn, P, Ca, Mg) were analysed by plasma mass spectrometry (ICP-AES, model POLYVAC) and the other three elements (C, N, S) by elemental analyser (CHNScO, FISONS Instruments, model 1108). The analyses were done at the Institute of Ecology, Polish Academy of Sciences, in Dzieka- n6w. Results The concentration of heavy metals in C. stelluris varied among the sites (Fig. 3). Ranges were as follows (pg g-I): Cd: DL-2.86; Co: 0.61-19.90; Cr: 0.79-10.2; Cu: 5.34-428; Fe: 255-5648; Mn: 6.48-266: Ni: 9.08-486; Pb: 1.8245.6: Zn: 11.4- 57.6; and Al: 214-1665. The greatest variation among sites was observed with Cu, N i and Mn. There was much less variation with Pb, Fe, Cd, Co and Cr, and the least with Zn. The maximum concentrations of most of the metals were found i n lichen collected close to the Monchegorsk and Zapolyarni smelter complexes (Fig. 3 . sites 1 . 1 1 - 15). High values of Cd, Pb and Co were also found in samples from sites located closer to the Barents Sea (Fig. 3, sites 23-26). The concentration of Zn and Cr in C. stelluris was less dependent on the distance from emission sources than other ele- ments. Such dependence was not found for Al. The carbon content in the lichen ranged from ca 32-50%. depending on the site, and nitrogen content from 0.44 to 0.94%, with the highest values found near Monchegorsk (Table I ) . The mean C/N ratio was 66 & 1 1 (min. 45.10. max. 93.18). Sulphur concentrations in C. stelluris were the highest near the smelters i n Monchegorsk (max. 982 pg g-I). Calcium accumulation in the lichen was clearly higher near the smelters (2000 pg g-', max. 3781 pg g-'), while at other sites i t generally remained 1000 pg g-' (min. 3 12 pg g-'). Phosphorus concentrations fluctuated from 264 to 101 5 pg g-' and magnesium from 235 to 1180 pg g-' without a clear dependence on distance from emissions sources (Table 1). Discussion I n this region air pollutants are transported up to 100 km, with the wind blowing from the south- west in summer and the north in winter. The samples of C. stelluris collected along the north- 108 K . Grudziriskn et 01. TRANSECT N - S 200 ::: I-:-+ an,-.- j- - n 0 0 I 2 3 4 5 6 7 a 9 1 0 1 1 1 2 1 3 1 4 1 5 6QQ cu 400 1 n I 2 3 4 5 6 7 a s 1 o 1 1 1 2 1 3 1 4 1 5 ::: 100 LILL 0 ~ , c l 0 - 0 0 n 0 il 1 2 3 4 5 6 7 8 9 1 0 1 1 1 2 1 3 1 4 1 5 6000 I Fe r-i 1 2 3 4 5 6 7 8 9 1 0 1 1 1 2 1 3 ~ 4 1 5 n 1 2 3 4 5 6 7 8 9 1 0 1 1 1 2 1 3 1 4 1 5 3 I n Cd 1 2 3 4 5 6 7 8 9 1 0 1 1 1 2 1 3 1 4 1 5 1 2 3 4 5 6 7 8 9 1 0 1 1 1 2 1 3 1 4 1 5 TRANSECT W - E o---------- 16 17 18 19 20 21 22 23 24 25 26 nlnooo,a17n-o 16 17 18 19 20 21 22 23 24 25 26 ,n,n,n,n 0 0 El 0 n CI - 16 17 18 19 20 21 22 23 24 25 26 16 17 18 19 20 21 22 23 24 25 26 16 17 18 19 20 21 22 23 24 25 26 1 2 3 4 5 6 7 8 9 1 0 1 1 1 2 1 3 1 4 1 5 16 17 18 19 20 21 22 23 24 25 26 1 2 3 4 5 6 7 8 9 1 0 1 1 1 2 1 3 1 4 1 5 n 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 Cladilia stellaris (Opi:) Brodo CIS a Oioindicator of atniosplieric depositiori 109 Tc7blr I . Concentrations of essential elements (% and pg g I d. wt) in Clclditicl srel1uri.s collected along north-south (nos. 1-14) and west-eat (nos. 1 6 2 6 ) transects on the Kola Peninsula. S Ca ME P Locality N 9 C% CIN I V € I P€ g~ ' pg g - ' P€ €-I 1 2 3 4 5 6 7 X 9 10 I I I 2 13 14 16 17 18 19 20 ? I 26 7 7 -_ 0.44 0.54 0.69 0.62 0.72 0.59 0.65 0.6') 0.64 0.65 0.75 0.94 0.61 0.86 0.63 0.71 0.76 0.64 0.58 0.5 I 0.58 0.60 41.00 44.59 42.58 43.27 44.94 41.37 44.08 42.47 42.64 41.67 42.40 31.92 50. 19 43.49 42.32 40.56 40.35 40 75 42.04 42.53 42.74 40.03 93. I 8 62 I 82.57 409 61.71 537 69.79 348 55.5Y 434 76. I6 498 63.56 609 63.88 660 66.35 475 65.60 54 1 55.56 468 45. 10 882 49.87 55 I 58.36 982 69.03 639 59.60 463 53.36 549 63.04 339 70.2s 315 X2.13 301 73.32 468 71.23 449 I195 895 1018 312 1116 627 2348 I539 719 928 1039 251 I 2322 3781 I264 561 939 711 729 494 916 1258 480 453 480 235 507 331 1 I 8 0 602 323 333 396 697 810 843 480 888 840 456 438 290 496 - 589 313 570 354 518 398 612 820 41 1 614 490 1015 715 516 655 497 55 I 36 I 305 264 447 482 south and west-east transects are within the range of metallic dust depositions throughout the year. The concentration of heavy metals and sulphur i n the air and i n precipitation on the Kola Peninsula is high and is correlated with the distance from emission sources (Ayras et al. 1995; Glazov et al. 1995; Jaffe et al. 1995; Kelley et al. 1995: Reimann et al. 1995). This accounts for the varying concentrations found in the species studied since lichens obtain minerals as well as pollutants from precipitation and from dry deposi- tion (Tyler 1990). Levels of most of the chemicals i n the lichen studied. particularly the heavy metals, were related to the distribution of emission sources. The highest accumulation of metals i n C. stellrtris was found near smelters, iron ore mines and processing plants (Monchegorsk. Ole- negorsk, Nikel, Zapolyarni). Why concentrations of Cd, Pb and C o in lichen collected near the Barents Sea were higher than in samples from sites closer to the emission sources is difficult to explain. The large shipping port at Murmansk may be an additional source of these elements. References Alexeyev. V . A. 1995: Impacts of air pollution on far north forear vegetation. The Science of rhr Tom/ En\,irontnenr /60/ 161,605-617. Ayris, M.. de Caritat, P., Chekushin, V. A,, Niskavadra, H. & Reimann. C. 1995: Ecogeochemical investigation, Kola Peninsula: sulphur and trace element content in snow. Wafer, Air mid Soil Pollrction 8.5. 749-754. Baklanov. A. A,, Klyuchnikova. E. M.. Limkina. C. Yu.. Rigina, 0. Y u . & Rodyushkina, 1. A. 1995: Airborne sulphur pollution i n industrial districts of the Kola Peninsula (abstract). Arid Reigit '95:) Conferenre Absrruct Book. P. 452. Dordrecht, Netherlands: Kluwer Academic Publ. Folkeson, L., Ander~son-Bringinark, E. 1988: Impoverishment of vegetation i n a coniferous forest polluted by copper and zinc. Cunrniinn J. Bor. 66. 417428. Glazov, M. V . , Kdrdban, R. T.. Leontyeva, 0. A. & Gytarsky. M. L. 1995: The influence of air pollution on forest ecosystems i n Pechenganickel region of Kola Peninsula. Arrhiivritn 0cliron.v Srorlowiska 2, 53-62. Grodziliska, K . & Godzik. 8.1991: Heavy metal and sulphur in mosses from southern Spitsbergen. fokur Research 9(2J, I 33- 140. Grodziliska, K., Godzik, B. & Szarek, G . 1993: Heavy metals and sulphur in lichens from southern Spitabergen. Frrtgni. Flor. Grohor. Suppl. 2(21, 699-708. F i g 3 . North-south (sites 1-15) and west-east (sites 16-16) gradients of heavy metal (Ni. Cu, Mn, Fe, Co. Cd. Pb, Zn, Cr) and Al concentrutions (pg g- ' ) in lichen samples collected along trilnsects running southward from Zapolyarni. via Murniansk, to Monchegorsk and eastward from Murniansh to Dalnye Zeleiil\y. 1 10 K . Grodziiiska et al. Heino, S., Anttonen, S., Wulf, A. & Karenlanyi. L. 1992: Nickel and copper accumulation in the lichen Cerruria nivalis ( L . ) Ach. in Lapland. Symposium on the State of the Environ- mental Monitoring in Northern Fennoscandia and the Kola Peninsula, 6 8 October 1992, Rovaniemi. Finland (E. Tikkanen et al., eds.). Arctic Centre Publications 4 . p. 269. Jaffe, D., Cerundolo. B., Rickers, .I., Stolzberg, R. & Baklanov, A. 1995: Deposition of sulfate and heavy metals on the Kola Peninsula. The Science of the Tot01 Environment 160/16/, 127-1 34. Kelley, J . A,, Jaffe, D. A,. Baklanov. A. & Mahura, A. 1995: Heavy metals on the Kola Peninsula: aerosol size distribution. The Science of the T o t d Ein~ironntent 160/161. 135-138. Koptsik, G. & Koptsik. S. 1995: Critical loads of acid deposition for forest ecosystems in the Kola Peninsula. Water, Air und Soil Pollutiun 85, 2553-2558. Kortesharju, J., Savonen, K. & Saynatkari, T. 1990: Element contents of raw humus, forest moss and reindeer lichens around a cement works in northern Finland. Ann. But. Fennici 27, 221-230. Kozlov, M. V.. Hankioja, E. & Yarmishko, V. T. (eds.) 1992: Aeriul pollution in Kola Peninsula. Procredings of rhe irrrernutional workshop. 14-16 April 1992, St. Petersburg. Luzin, G. P., Pretes, M. & Vnsiliev. V. 1994: The Kola Peninsula: geography, history and resources. Arctic 4 7 ( 1 ) , I - 1 s. Markert, B. (ed.) 1992: Plant.\ a,\ bioinorritorsr irrdicarors f o r heiivy nietals iii the terreJtria1 environnrerrr. Weinheim: VCH Verlagsgesselschaft mbH. Mikinen, A. 1994: Biomonitoring of atmospheric deposition in the Kola Peninsula (Russia) and Finnish Lapland. based on the chemical analysis of mosses. 83 pp. Helginki: Ministry of the Environment. Yliopistopaino. Moiseenko, T. 1995: Critical loads of SO4 for surface waters in the Kola region of Russia. Wurer, Air on(/ Soil Po1/~tio11 85. 4 6 9 4 7 3 . Nuorteva. P. 1990: Metal distribution patterns and forest decline. Seeking Achilles' heels for metals in Finnish forest biocoenoses. Publications of the Depurtinetzt qf Environ- nwntnl Conservrition UI the Universih. of Helsinki 1 1 , 1-77. Nuorteva, P., Autio, S., Lehtonen, J.. Lepisto. A,, Ojala. S., Seppinen, A,. Tulisalo, E., Veide, P., Viipuri. J. & Willamo. R. 1986: Levels of iron, aluminium, zinc, cadmium and mercury in plants growing in the surroundings of an acidified and a non-acidified lake in Espoo. Finland. Ann. Bot. Fennici 23.333-340. Pakarinen, P.. Mikinen, A. & Rinne. R . J . K. 1978: Cltidoniu arlntsculu and Clu~lwiia tniris in eastern Fennoscandia. Ann. BOI. Fentiiri 15, 281-286. Reimann, C., Niskavaara. H., de Caritat, P.. AyrHs, M., Chekushin, V. A. & Finne. T. E. 1995: Snowpack sampling to fingerprint environmental contamination in the surround- ings of the nickel smelter at Nikel, Kola Peninsula. Russia. I n Wilken, R. D. et al. (eds.): Inrerr~ationd Conference - Heu1.y Metals in the Enciroimient. Vol. 1. Pp. 84-87. Hamburg: CEP Consultants Lid. Riihling, A. (ed.) 1993: Atmospheric heavy metal deposition in Europe -estimation based on moss analysis. NORD 9, 1-53. Riihling. A,, Rasmussen, L.. Pilegaard, K., Mikinen. A. & Steinnes. E. 1987: Nordic countries i n 1985 - monitored by moss analysis. NORD 21, 1-44. Skiba, S. 1994: Soils of the Dalnye Zelentsy tundra region in the northern part of the Kola Peninsula (Russia). Wyprait:,' G e o g r u f i c x r i i u Spifsbergerr (Geojiriiphicul Expedition on Spifsbergerr). Pp. 71-77. Lublin: Uniwersytet Marii Curie- Sklodowskiej (Maria Curie-Sklodowska University ). Steinnes, E.. Hanssen, J. E., Rambnk, .I. P. & Vogt, N. B. 1994: Atmospheric deposition of trace elements i n Norway: temporal and spatial trends studied by moss analysis. Ware,; Air- and Soil Pullrctiorr 74, 121-140. T i k a n e n , E.. Varmola, M. & Katermaa. T. (eds.) 1992: Symposium on the State of the Environmental Monitoring i n Northern Fennoscandin and the Kola Peninsula. 6-8 October 1992. Rovaniemi, Finland. 369 pp. A r d c Centre Publications 3. Tyler, G. 1990: Bryophytes and heavy metals: a literature review. Bor. Linnean. Soc. 104, 231-253.