Lehoczki, Róbert

Tuba, Z.

Ötvös, E.

English

Ötvös E.

Lehoczki Róbert

Tuba Z.

University of Szeged

3.9 . ATMOSPHERIC HEAVY METAL DEPOSITION ALONG FOUR MAJOR HUNGARIAN RIVER VALLEYS Ötvös, E., Lehoczki, R. and Tuba, Z. 3 .9 .1 . INTRODUCTION River valleys are the most populated areas of Hungary and the industrial centres are also located here. On the other hand these regions mean biotops for many plant and animal associations included protected species. Environmental pollution accidents and damages, as e.g. recent cyanide pollution in the north-eastern rivers (Febr. 2000), Szamos and Tisza may prove the importance of biomonitoring studies over large areas. Bryophytes have been widely used as bioindicators of air contaminants for the past few decades, especially to estimate heavy metal, organic and radioactive pollution (Berg et al., 1996; Markert ed., 1993; Knulst et al, 1995). Numerous studies (Gydesen et al., 1983; Herpin et al., 1996; Markért et al., 1996; Meenks et al., 1991; Rühling et al., 1987; Rühling ed., 1994; Steinnes et al., 1994; Tuba et al., 1994) have shown that surveys of the heavy metals by cryptogams are valuable, easy and cheap method to identify the possible emission sources and long range transport of pollutants. Mosses have no root system, so they can take up nutrients and chemical substances mainly from dust-fall and precipitation. They are good bioaccumulators because of their high capacity to retain many trace elements. An international moss monitoring programme (Rühling et al., 1987; Rühling ed., 1994) was initiated and conducted by Nordic Countries under the Nordic Council of Ministers in 1985 to characterize quantitatively and qualitatively the regional and atmospheric deposition pattern of heavy metals. In 1995-1996, about 30 European countries joint this project, considering methods of Scandinavian guidelines to map and to compare results among different areas. In the Nordic countries there is a long-term survey, data from 1985 to 1995 show a general decline in concentrations of most metals, e.g. in the cadmium deposition with a reduction in 35 % in Denmark or in the lead deposition with a decrease about 30% in Sweden, and present that the deposition is dominated by long-range transport (Rühling et al., 1987; Rühling ed., 1994; Gydesen et al., 1983; Berg et al., 1996; Steinnes et al., 1994. The decrease in concentrations of metals is mainly due to stricter emission legislation, filter technique, closure of old polluting industrial plants and use of petrol without lead. Our present study is the first attempt to provide data on pollution with heavy metals by moss analysis at a larger scale, along main river valleys (see Fig.l.) including the Danube which is 417 km long, Tisza with length of 597 km, Kőrös with 219 km and Rába with 192 km in Hungary. 3.9.2. MATERIALS A N D METHODS Samples of the moss species Hypnum cupressiforme were collected from 47 sites up to a distance of 15 km from rivers, from September to November, during a relatively dry 162 Ecology of river valleys autumn in 1997. This carpet-forming moss growing on stumps, barks, rocks, walls and soils is widespread in Hungary, and very useful for bioindication because heavy metal content analysis can be done months or later after the collection. Procedure of sampling was performed according to the Scandinavian guidelines; the samples were taken mainly from forests, not exposed directly to precipitation. The sampling sites were at least 300 m far from main roads and built-up areas, and at least 100 m far from any roads and buildings. 5-10 subsamples were collected and mixed from each sample point (50 x 50 m). Each sample was analysed in three repetitions. The green parts of mosses were cleaned carefully without washing and then dried at 70 °C. Samples of 0,2 g were digested with 2 cm3 of cc. HNO, and 2 cm' of cc. H 20 2 at 130°C under pressure in Teflon bombs for 45 min. Then it was filtered through Whatman No. 42 filter paper and brought to a volume of 10 ml with bi-distilled water. Cd, Cr, Cu, Ni, Pb, V and Zn concentrations were determined with ICP-AES measurement technique. Fig. I. Map of Hungary with sampling sites 3 . 9 . 3 . RESULTS A N D DISCUSSION The heavy metal concentrations data (Tables 1, 2 and Fig. 2) show that the highest values were measured at the rivers Danube and Tisza, close to industrial towns. The maximum concentrations were found at the sampling sites surrounding Budapest, Százhalombatta, Dunaújváros, Szolnok and Tiszaújváros. Effect of traffic compared to influence of industry is much milder as the sampling points were not close to the roads and contamination is rapidly reduced with distance (Tuba et al., 1994). Cadmium Background average level for cadmium is 0.86 pg g ' that is higher than the mean European values (0,2-0,7 pg g'1) and similar to Russia (Rühling 1994). Main emission sources may be metal industry, mining and use of phosphate fertilizers in agriculture. The highest values are found along Danube around Budapest, Százhalombatta and Dunaújváros, and near the river Tisza (Tiszaújváros) due to industrial activities. There is also a high Chapter 3. Water quality 163 concentration of Cd in the village of Ásványráró (2,08 pg g"') that suggests that the cadmium may be transported to Hungary from the neighbouring regions (Slovakia and Austria) (Rühling ed., 1994). Table 1 Concentrations of heavy metals in mosses taken near four river valleys (ig g'1 d.w.) Cd Cr Ni V Cu Pb Zn DUNA median 0,9 2,3 4,5 3,9 11.0 15,4 60,1 mean 1,0 3,4 6,0 6,9 11,4 18,7 62,5 min 0,3 0,9 2,1 1,5 6,7 5,4 32,1 max 2,1 7,3 19,9 46,7 17,2 43,4 115,7 RABA median 0,7 1,4 4,3 1,9 11,9 9,7 38,1 mean 0,6 1,6 4,1 2,7 10,0 15,7 43,1 min 0,3 0,9 3,1 1,0 6,6 5,4 32,7 max 0,7 2,5 4,9 4,6 12,8 31,0 60,6 TISZA median 0,8 1,7 3,0 1,9 10,4 14,1 45,7 mean 1,0 3,2 5,6 11,8 10,1 15,8 56,5 min 0,3 0,3 1,0 1,7 7,3 7,9 32,2 max 2.1 14,0 30,4 86,0 15,2 35.6 128,2 KOROS median 0,6 2,7 4.1 2,7 11.0 14,7 48,9 mean 0.6 2,4 4,6 2.9 11,2 16,7 55,0 min 0,3 0,7 2,5 1,7 7.2 9,7 37,6 max 0,7 4,3 7,8 4,8 16,0 25,6 82,9 AVERAGE median 0,7 2,4 4,4 2,8 11,0 15,5 51,9 mean 0,8 3,1 6,7 11,4 11,0 17,8 58,2 min 0,3 0,3 1,0 1,0 6,6 5,4 32,1 max 2,1 14,0 30,4 86,0 17,2 43,4 128,2 Chromium The European baseline level for chromium in rural areas is around 1 pg g~'(Rühling ed., 1994). Among investigated sites, environs of river Rába is the less polluted with range 0,93-2,07 pg g"1. Higher concentrations are found around Budapest and in Dunaújváros (7.33 pg g'1) by the rivers Danube because the local industry, especially iron and steel mills cause contamination. The river Kőrös and Tisza are more polluted than Rába, due to effects of industry of bordering country. The values were measured above 21 pg g"' close to the frontier in Romania. A peak value was noted near industrial chemical centre of Tiszaújváros 13,98 pg g"1. Nickel The main emission sources of Ni are steel industry, oil and coal burning. In most of European countries the concentration varies between 2-4 pg g-1 in mosses, higher concentrations (10-20 pg g-1) are measured near to smelters and chemical company (Rühling ed., 1994). The Hungarian average level is about 4-6pg g-1, but there are some local emittors. Elevated concentrations were found at Esztergom (10,28 pg g-l) , Bugyi (15,02 pg g-l) , DunafÖldvár (9,34 pg g-l), Mezőberény (7,76 pg g-l) , Gyoma (11,03 pg g-l) Százhalombatta (19,86 pg g-1) and Tiszaújváros (30,39 pg g-1). Only background contamination (~ 4pg g-1) could be detected at the river Rába. Pollution of Ni is also relatively low at the river Tisza apart from values of Tiszaújváros and Tiszafüred. 164 Ecology of river valleys Vanadium Vanadium is mainly originated from coil and oil burning. Deposition of V in Hungary does not reach a considerable amount and it is similar to values of West-European countries (4-6 pg g"') (Riihling ed., 1994). The concentrations of V show strong relationship with Ni levels, the most polluted areas are the same as we have already mentioned at Ni. There are only three industrial establishments representing potential pollution sources: an oil refinary and an oil-fuelled heat power station located in Százhalombatta (46,69 pg g ') (Tuba et al., 1994) and a chemical company in Tiszaújváros 30,39 pg g'1). ,4 - • RÁBA .KÖRÖS «TISZA • DUNA 70 - q r A b a q k ö r ö s h t i s z a q d u n a 12 - _ 60 -10 - I 50 -I » - L z 4 0 - R I ? 6 - 1 1 S 3 0 -- - r i l M l U " T W I r f l I • -Cd Cr Ni V Cu Pb Zn Fig. 2. Mean concentrations of heavy metals in mosses in the regions of four rivers (ig g'1 d.w.) Copper Copper can be originated from metal industry and from copper-containing fungicides used by agriculture. The background concentration of copper is about 10 pg g-1 in Hungary that is similar to European values (Riihling ed., 1994). Local effects could be not detected, however the input from bordering countries is remarkable. Eastern part of the country (at river Körös) is notably more contaminated than the others. (Timi°oara, Romania 126 pgg'1). Lead The main sources of lead the combustion of leaded fuel, waste incineration and industry. As we measured background contamination of the country, our values are relatively low (10-20 pg g"1) to compared with other countries (Riihling ed., 1994). Background levels near rivers Rába and Kőrös are the lowest. Higher concentration can be observed near towns, in the region Budapest (10-43 pg g'1) due to a long-range transport of lead from extensive traffic. Zinc Zinc contamination is related with metal industries and use of pesticides in the agriculture. Zn level in European countries usually is less than 40 pg g'1 (Riihling ed., 1994), the average values in Hungary are between 30-50 pg g~'. The background contamination of Zn is the highest by Danube, input from Austria and Slovakia could be well detected at the Upper Danube (60-116 pg g'1). Locally increased Zn levels were also found near to central part of river, but a purification can be definitely observed at the Lower Danube (32-47 pg g"'). Peak concentrations were found close to the capital (Érd 116 pg g 1 ) and at Tiszaújváros (128 pg g"1). Chapter 3. Water quality 165 Table 2 Sampling sites and concentrations of heavy metals measured in collected mosses (pg g"1 dry weight) Duna Cd Cr Ni V Cu Pb Zn 1 Ásványráró 2,1 2,3 5,7 9,0 9.S 13,9 50,0 2 Mosonszentmiklós 0,4 1.8 3,2 2,0 11,0 7,5 81,2 3 Gönyü 0,6 1,4 4,9 1,9 12,8 5,4 60,6 4 Nagyszentjános 0,5 2,1 3,0 2.5 6,7 13,0 36,4 5 Esztergom 1.6 5,9 10,3 9,8 10,2 11,7 87,9 6 Visegrád 1,7 7,0 7,1 12,3 13,6 27,0 75,9 7 Leányfalu 1,1 3,4 4,1 4,9 11,0 21,7 65,0 8 Pusztazámor 0,8 4.8 8,7 12,8 15,3 43,4 61,5 9 Érd 0,9 5,7 9,9 11,7 17,2 17.4 115,7 10 Alsónemedi 0,9 3,4 4,9 5,2 11.9 22,9 59,6 11 Bugyi 1,5 6,1 15,0 6,8 15,8 28,5 105,0 12 Szalkszentmárton 1,2 2,3 2,4 2,5 9,0 7,9 54,3 13 Százhalombatta 1.9 6,0 19,9 46,7 13,9 37,9 73,2 14 Adony 1,0 3,9 5,1 4.8 14,8 42,3 49,3 15 Mezőfalva 1,4 1,9 2,5 3,0 9,5 21,0 40,7 16 Dunaújváros 1,8 7,3 8,6 7,4 13,4 27,9 94,0 17 Baracs 0,9 2,3 3,8 2,3 10,3 11,2 57,1 18 Dunaföldvár 1,3 6,8 9,3 6,1 14,0 14,1 63,6 19 Bölcske 0,7 1,4 2,1 2,2 8,1 9,0 61,0 20 Paks 0,9 0,9 2,6 3,1 11,3 22,4 37,0 21 Kalocsa 0,6 1,0 2,2 1,5 6,7 6,7 47,2 22 Dombon 0,5 1,0 2,5 2,9 8,7 7,4 46,2 23 Baja 0,3 1,8 2,9 2,5 10,5 13,1 32,1 24 Pócsa 0,5 1,9 3,3 2,4 8,3 16,8 45,2 Tisza Cd Cr Ni V Cu Pb Zn 1 Vásárosnamény 0,5 2,4 3,7 2,0 7,6 14,8 43,1 2 Kisvárda 0,6 3,0 4,3 3,3 10,6 21,6 80,3 3 Nyirbogdány 0,3 1,2 1,8 1,8 11,0 35,6 46,1 4 Tiszaújváros 1,9 14,0 30,4 86,0 15,2 18,9 128,2 5 Poroszló 1,2 3,0 4,3 14,2 12,2 13,3 74,3 6 Tiszafüred 1,9 7,5 8,6 23,2 10,3 13,2 67,5 7 Jászkísér 0,9 1.6 4,0 1.8 8.6 14,2 45,4 8 Kunhegyes 0,3 1,5 2,4 2,0 11,7 14,0 34,5 9 Szolnok 2,1 0,4 1,9 1,8 8,2 15,1 55,4 10 Szentes 0,7 0,3 1,0 1,7 7.4 8,3 36,8 11 Derekegyháza 0,8 1,0 2,3 1,8 7,3 12,5 33,8 12 Kistelek 0,7 1,8 2.4 1,7 11,3 7,9 32,2 Kába Cd Cr Ni V Cu Pb Zn 1 Körmend 0,7 1,2 3,4 1,9 6.6 9,7 32,7 2 Vasvár 0,7 2,5 4,3 4,6 11,9 31,0 50,3 3 Sárvár 0,3 0,9 3,1 1,0 6,6 7,9 33,7 4 Vág 0,7 2,1 4,6 4,2 12,1 24,5 38,1 5 Gönyü 0,6 1,4 4,9 1.9 12,8 5,4 60,6 Kőrös Cd Cr Ni V Cu Pb Zn 1 Gyula 0,6 3,0 4,2 3,2 14,3 15,7 82,9 2 Doboz 0,3 2,6 4,0 2.3 7,6 13,6 37,6 3 Mezöberény 0,6 4,3 7,8 4,8 13,2 23,4 52,5 4 Gyoma 0,6 0,7 3,0 1.7 7,2 9,7 72,6 5 Szarvas 0,7 1,1 2,5 1,8 8,8 12,2 45,3 6 Öcsöd 0,5 2,7 5.8 4,0 16,0 25,6 39,2 166 Ecology of river valleys 3 . 9 . 4 . C O N C L U S I O N Effects of the major pollution sources located in river valleys and influence of the long-distance transport from bordering countries could be well detected on base of moss analysis. The local emittors are steel, metal and chemical industry, oil refinery and heat power plants, the burning of coil and oil, cement production and transport. Peak concentrations along four major river valleys were measured in the region of Budapest, near Százhalombatta, Dunaújváros, Tiszaújváros, Tiszafüred and Gyoma. The Hungarian background concentrations of Cd, Cr, Cu and Zn are mildly elevated on an international scale (Rühling 1994). The level of Ni is increased compared to other countries, but it is mainly due to input from industry of neighbouring countries (Rühling 1994). The values of Pb and V were found similar to European average (Rühling 1994). Among the investigated river valleys, the most polluted one is the Danube, especially higher values of Cr, Ni and Zn were measured by upper and central region. The valley of the Rába is less contamined by Cr and Pb, but levels of Ni and Cu are elevated. Cd and Pb concentration are mildly increased at surroundings of river Tisza, local sources and Romanian input seems to be significant in cases of Ni and V. The area of river Körös is less polluted by Cd, but average values of Cr, Ni and V are elevated. The present survey of heavy metal deposition reflects a mildly increased pollution in Hungary in 1997 compared to European values of 1995 (Rühling 1994). Our presented data serve a reference data base for the future to follow-up any changes and trends of the background heavy metal pollution due to atmospheric deposition. 3 . 9 . 5 . S U M M A R Y The atmosphere is an important pathway for transport and deposition of the pollutants to both aquatic and terrestrial ecosystems. Hungary, due to its geographical situation in the Carpathian Basin can be regarded as a deposit area of the contaminants. There is a significant anthropogenic impact from neighbouring countries, adding to it an important internal emission, especially from the industrial centers located mainly near rivers. As a great part of population lives in the rivers valleys, and these regions are biotops for many rare species, there is a demand to estimate the state of their surroundings. The aim of this paper is to characterize the atmospheric deposition of Cd, Cr. Cu, Ni. Pb, V and Zn in largest Hungarian river valleys (Duna = Danube, Tisza, Körös, Rába) to present days. Our studies join an international mapping project (Atmospheric Heavy Metal Deposition in Europe) (Rühling et al., 1987; Rühling ed., 1994) following their standardized methods. Samples of moss Hypnum cupressiforme were collected at a total of 47 sampling points near the rivers during the autumn of 1997 and were analysed by atomic emission spectrometry with inductively coupled plasma (ICP-AES). Results prove that major pollution sources are the industrial towns (Százhalombatta, Dunaújváros. Tiszaújváros), and mean concentrations of heavy metals are higher than in most European countries, particularly in cases of cadmium and chromium. There also is significant input of nickel by atmospheric transport from bordering countries. The values of Cu, Pb, V and Zn were measured similar to European levels. Chapter 3. Water quality 167 3 . 9 . 6 . A C K N O W L E D G E M E N T S This work was supported by ECOCRAFT and MEGARICH EU R&D projects, Hungarian Scientific Research Foundation (OTKA 10009), Research Development in Higher Education (FKP 0472/97) and by Hungarian Academy of Sciences, Research Group. 3 . 9 . 7 . REFERENCES Berg, T., Pedersen, U., Steinnes, E. (1996): Environmental indicators for long-range atmospheric transported heavy metals based on national moss surveys. Environ. Monitoring and Assess. 43, 11-17. Gydesen, H., Pilegaard, K., Rasmussen, L., Riihling., A. (1983): Moss analyses used as a means of surveying the atmospheric heavy-metal deposition in Sweden, Denmark and Greenland in 1980. Bulletin SNV PM 1670. pp. 1-44. Herpin, U., Berlekamp, J., Markert, B. et al. (1996): The distribution of heavy metals in a transect of the three states the Netherlands, Germany and Poland, determined with the aid of moss monitoring. The Science of the Total Environ. 187,185-198. Knulst, J.C., Westling, H.O., Brorstrom-Lunden, E. (1995): Airborne organic micropollutant concentrations in mosses and humus as indicators for local versus long-range sources. Environ. Monitoring and Assessment. 36, 75-91. Markert, B., Herpin, U., Siewers, U., Berlekamp, J., Lieth, H. (1996): The German heavy metal survey by means of mosses. The Science of the Total Environ. 182,159-168 Markert, B., (ed.) (1993): Plants as biomonitors for heavy metal pollution of terrestrial environment. VHC - Publisher Inc., Weinheim - New York. Meenks, J. L. D., Tuba Z., Csintalan Zs. (1991): Eco-physiological responses of Tortula ruralis upon transplantation around a power plant in West Hungary. Journ. Hattori Bot. Lab. 69,21-35. Riihling, A., Rasmussen, L., Pilegaard, K., Makinen, A., Steinnes, E. (1987): Survey of atmospheric heavy metal deposition in the Nordic countries in 1985 - monitored by moss analyses. NORD. 21, 1-44. Riihling, A., (ed) (1994): Atmospheric heavy metal deposition in Europe - estimations based on moss analyses. NORD. 9 Steinnes, E. (1994): Atmospheric deposition of trace elements in Norway: Temporal and spatial trends studied by moss analysis. Water, Air and Soil Pollution. 74, 121-140. Tuba, Z., Csintalan, Zs., Nagy, Z., Szente, K., Takacs, Z. (1994): Sampling of terricolous lichen and moss species for trace element analysis with special reference to bioindication of air pollution. In: B. Markert (ed.): Sampling of environmental materials for trace analysis, pp. 415-434 VHC Publisher, Weinheim, New York, Tokyo. 

Atmospheric heavy metal deposition along four major Hungarian river valleys

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Atmospheric heavy metal deposition along four major Hungarian river valleys

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