Polish Journal of Environmental Studies Vol. 13, No. 5 (2004), 495-502 Original Research Distribution of Mercury and Other Heavy Metals in Bottom Sediments of the Middle Odra River (Germany/Poland) L. Boszke1*, T. Sobczyński2, G. Głosińska1, A. Kowalski2, J. Siepak2 1Department of Environmental Protection, Collegium Polonicum, Adam Mickiewicz University, Kościuszki 1, 69-100 Słubice, Poland 2Department of Water and Soil Analysis, Faculty of Chemistry, Adam Mickiewicz University, Drzymaly 24, 60-613 Poznań, Poland Received: 3 December 2003 Accepted: 14 February 2004 Abstract The Odra is the second largest river in Poland, running from the Czech Republic through a large part of Poland before entering the Baltic Sea. Its catchment area has been heavily polluted by anthropogenic emis- sions. Our data document an intensive anthropogenic impact on the abundance of heavy metals in bottom sediments of the middle part of the Odra. Normalized heavy metal concentrations in sediments and indices of geoaccumulation (Igeo) indicate that this area is polluted by various metals, especially mercury, cadmium and zinc. The ranges of their concentrations vary as follows: Hg 0.12-2.99 mg/kg, Cd 2.93-7.87 mg/kg, Pb 21.2-163 mg/kg, Cu 11.5-88.3 mg/kg, Zn 28.0-471 mg/kg, Cr 1.57-47.5 mg/kg, Ni 5.10-19.1 mg/kg, Fe 1493-37972 mg/kg and Mn 47.6-1242 mg/kg. Keywords: mercury, heavy metals, bottom sediments, Odra River Introduction The Odra River basin is divided into the upper course (source - Wroclaw, 21.4% of total area), the The Odra, as one of the five longest rivers in Europe, is mid-altitude course (Wroclaw-Warta, 54.6% of to- a system transporting and collecting a large number of sub- tal area), and the lower course (Warta-Szczecinski stances from natural and anthropogenic sources. The Odra Lagoon, 24% of the total area). In the upper part of River Basin has a catchment area of 118.861 km2. The basin the Odra catchment, pollution comes from mining is situated in the industrialized and highly populated centre of coal, copper, lead and zinc and sulphur as well as of Europe, shared by Poland (89 %), the Czech Republic (6 heavy industry. In the middle part and the underflow %) and Germany (5 %). The Odra has its sources in the Odra the sources of pollution are agriculture, oil indus- Mountains (the Czech Republic, 632m above sea level), and try and communal waste. In the middle part of the after 854.3 km the river flows into the Szczeciński Lagoon river urban and industrial agglomerations localized and through Pomeranian Bay into the Baltic Sea. The Odra directly on the river impact the quality of its water: is one of the largest rivers entering Baltic. Over a distance of Wrocław, Brzeg Dolny, Malczyce, Głogów, Nowa Sól 176 km the Odra forms the state border between Poland and and Krosno Odrzańskie. In the border part the river Germany. At present, 15.4 million people live in the catch- also collects wastes from Germany, and via the Nysa ment area: 13 million in Poland, 1.4 million in the Czech Łużycka river also from the Czech Republic. On the Republic and 1 million in Germany [1, 2]. Polish side the main sources of pollution are Kostrzyń and Słubice, while on the German side Eisenhutten- *Corresponding author; e-mail: [email protected] stadt and Frankfurt/Oder [1, 3-5]. 496 Boszke L. et al. The objective of this study was to estimate the con- Analytical Procedure tamination of the Odra river bottom sediments by mer- cury and other heavy metals in the middle of its course Total mercury concentration was determined by cold- and to identify potential sources of heavy metal pollution vapour atomic fluorescence spectroscopy (CV-AFS) us- in this part of the Odra river and its drainage area. ing a Millenium Merlin Analyzer (PS Analytical) after sample digestion with aqua regia. The total content of Materials and Methods heavy metals was determined after sample digestion with concentrated HNO and 30% H O . Heavy metals were Sediment Sampling 3 2 2 determined by flame atomic absorption spectrometry Bottom sediments were collected from 7 sites in the (AAS) on a Varian spectrometer Spectr AA 20 plus. Cad- middle part of the Odra in 2002 (Figure 1). The samples mium was determined by the graphite furnace technique. from German (A) and/or Polish (C) banks, and/or from Organic matter was determined as a loss on ignition at the middle part of the river-bed (B) were collected at each 5500C in 12 hours to obtain constant weight. site. Generally, the sediment samples were taken with a hand corer made of stainless steel. They were placed in Analytical Methods plastic boxes of 1000 cm3 volume and transported to the laboratory where they were dried at room temperature to Standard Reference Materials were analysed routinely constant weight. as laboratory reference materials: SRM 2711 (Montana Soil - agricultural soil) for mercury and LKSD-2 (Canadi- Sediment Fractionation an Lake Sediment) for other heavy metals. Recoveries of heavy metals were: Hg-97%, Cu-88%, Pb-86%, Ni-82%, The sediment samples, homogenized in an agate mor- Cr-79%, Mn-85%, Zn-88%, Fe-79%. tar, were dry sieved to separate the required fractions from ~250 g bulk sediment. In order to avoid sample contami- Indicator of Sediment Contamination nation, nylon sieves were used. Geochemical analyses (Geoaccumulation Index) of mercury were performed for the grain-size fraction of < 0.2 mm. The other heavy metals were analyzed from In order to classify local anthropogenic sources of the fraction of < 0.8 mm. heavy metal pollution, the Igeo index (geoaccumulation Fig. 1. Map of study area. Distribution of Mercury and Other Heavy Metals in... 497 Table 1. Concentrations of heavy metals (mg/kg dry weight) in bottom sediments of the Odra. Sampling River LOI Fe I Mn I Hg I Cd I Pb I Cu I Zn I Cr I Ni I site bank (%) (%) geo geo geo geo geo geo geo geo geo A 4.9 1.5 1 418 1 1.78 3 4.7 3 91.1 1 51.7 1 323 1 47.6 1 19.2 1 1 B 0.2 2.0 1 284 1 - - 4.48 3 60.3 1 11.5 1 59.2 1 2.37 1 13.6 1 C 0.5 2.0 1 47.6 1 0.28 0 3.69 3 28.8 1 14.2 1 47.4 1 2.98 1 13.3 1 2 A 6.3 17.3 1 711 1 1.36 2 7.87 4 163.3 1 88.3 1 471 1 44.2 1 31.0 1 A 1.1 2.9 1 95.7 1 0.35 0 3.36 3 33.5 1 14.8 1 70.0 1 3.39 1 17.6 1 3 B 0.3 1.9 1 263 1 - - 3.36 3 38.4 1 13.4 1 56.5 1 2.03 1 19.0 1 C 0.8 2.8 1 100 1 1.32 2 3.27 3 31.0 1 15.2 1 61.9 1 3.04 1 14.1 1 A 0.7 2.6 1 138 1 0.51 0 3.44 3 30.8 1 16.2 1 92.0 1 4.33 1 11.5 1 4 B 0.4 2.0 1 257 1 - - 3.34 3 31.8 1 14.8 1 71.0 1 1.57 1 8.23 1 C 2.8 8.9 1 324 1 2.99 6 4.18 3 83.3 1 64.5 1 225.3 1 20.6 1 14.0 1 A 4.1 37.9 1 1242 1 0.12 0 3.86 3 42.8 1 25.1 1 71.0 1 13.5 1 18.0 1 5 B 0.6 2.1 1 248 1 - - 2.93 3 23.9 1 13.3 1 68.8 1 2.33 1 12.0 1 C 0.7 3.4 1 110 1 0.21 0 3.90 3 38.5 1 16.4 1 57.5 1 7.51 1 7.57 1 A 2.4 5.5 1 205 1 1.49 2 4.35 3 42.8 1 30.6 1 303 1 12.6 1 14.1 1 6 B 0.5 1.8 1 222 1 0.25 0 4.62 3 33.6 1 13.9 1 72.2 1 2.32 1 11.7 1 C 0.4 1.9 1 109 1 0.28 0 3.73 3 21.2 1 12.5 1 55.6 1 2.00 1 5.11 1 A 1.0 2.1 1 79.4 1 0.42 0 3.88 3 27.3 1 16.2 1 62.0 1 4.15 1 9.59 1 7 B 0.5 1.6 1 284 1 0.89 0 4.33 3 30.0 1 13.5 1 47.1 1 2.64 1 12.12 1 C 0.6 1.5 1 51 1 0.18 0 4.37 3 28.7 1 11.7 1 28.1 1 2.03 1 10.49 1 1.3a 140a 0.2b <0.5c 10c 6c 48c 5c 5c 4.67d 850d 0.3d 20d 45d 95d 90d 68d e e e e e e Background 960 0.3 30 51 115 46 a Background values for Fe and Mn in Vistula river (Poland) (fraction < 0.060 mm) [vide 16], b For worldwide river sediments [21, 22], c Background for rivers sediments in Poland (fraction < 0.2 mm) [10], d For worldwide river sediments (fraction < 0.002 mm) [23], e Background for Rhine river sediments (Germany) [7] index) was calculated and classification in Igeo classes was the upper limit of maximum contamination.