Toxicol. and Environ. Chem., 2003, Vol. 85, Nos. 4–6, pp. 51–60 POLYCHLORINATED BIPHENYLS, POLYCYCLIC AROMATIC HYDROCARBONS AND ALKYLPHENOLS IN SEDIMENTS FROM THE ODRA RIVER AND ITS TRIBUTARIES, POLAND K. KANNANa,*, J.L. KOBERc, J.S. KHIMc, K. SZYMCZYKb,y, J. FALANDYSZb and J.P. GIESYc a Wadsworth Center, New York State Department of Health, Empire State Plaza, Albany, NY 12201-0509, USA; bDepartment of Environmental Chemistry and Ecotoxicology, University of Gdańsk, PL80-952, Gdańsk, Poland; cDepartment of Zoology, 213 National Food Safety and Toxicology Center, Institute for Environmental Toxicology, Michigan State University, East Lansing, Michigan 48824, USA (Received 6 November 2000; Revised 15 March 2001; In final form 16 March 2001) Concentrations of polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), nonylphenol (NP) and octylphenol (OP) were measured in sediments collected during June–August 1998 along the Odra River and its tributaries (Warta, Obrzyca, Barycz, Kaczawa and Bóbr Rivers) in Poland. In addition, raw and treated sewage sludge collected from Gdańsk, Poland, were analyzed for the target compounds. Concentrations of PCBs in sediments varied widely, ranging from 2.7 to 412 ng/g, on a dry weight basis (dry wt). PAHs were the predominant compounds in sediments with concentrations ranging from 150 to 19 000 ng/g, dry wt. The distribution of concentrations of PAHs was more homogenous than that of PCBs. NP concentrations in sediments ranged from <1 to 762 ng/g, while that of OP from <1 to 9.8 ng/g, dry wt. Measured concentrations of target analytes in sediments of the Odra River and its tributaries were comparable to or greater than those reported for riverine sediments in other eastern European countries. Concentrations of total PCBs, PAHs and NP in raw and treated sewage sludge collected from a sewage treatment plant in Gdańsk, Poland, were in the ranges of 203–284, 11 720–13 880 and 6760–99 600 ng/g, dry wt, respectively. Primary treatment of sewage did not appear to reduce PCB or PAH concentrations, although NP and OP concentrations were much less in treated sludge than in raw sludge. This is one of a few studies that document concentrations of PCBs, PAHs and NP in sediments of the Odra River and its tributaries in Poland. Keywords: PAHs; PCBs; Alkylphenols; Sediment; Sewage sludge INTRODUCTION The Baltic Sea is polluted by the discharge from various rivers, atmospheric deposition, spills and dumping of dredged materials from the surrounding countries. The long hydraulic residence time and cold waters of the Baltic Sea make it vulnerable as a *Corresponding author. Tel.: þ1 518-474-0015. Fax: þ1 518-473-2895. E-mail: kkannan@wadsworth.org y Present address: University of Warmia and Mazury, Olsztyn, Poland ISSN 0277-2248 print: ISSN 1087-2620 online/03/01-20001-06 ß 2003 Taylor & Francis Ltd DOI: 10.1080/0277221042000 52 K. KANNAN et al. sink for persistent and semi-volatile organic contaminants [1]. Organochlorine compounds such as polychlorinated biphenyls (PCBs) are among the most widespread contaminants in the Baltic Sea. The hydrophobic nature of these compounds favors them to sorb onto suspended particulate matter, which are finally deposited in sediments. While several studies have reported the occurrence of organochlorines in biota from the Baltic Sea and its coastal areas [2–9], reports of organochlorines in sediments are fragmentary [10,11]. In particular, on a regional scale, organochlorine concentrations in sediments of rivers that drain into the southern part of the Baltic Sea are limited. Monitoring of trace organic pollutants in sediments of rivers that discharge into the Baltic Sea would provide information regarding local sources. In this study, PCBs, polycyclic aromatic hydrocarbons (PAHs) and alkylphenols such as nonylphenol (NP) and octylphenol (OP) were measured in sediments from the Odra River and its tributaries in Poland, that drains into the southern Baltic Sea. The Odra River is one of the largest rivers that empties into the Baltic Sea and drains through urbanized, industrialized and agricultural areas of Poland, Czech Republic and Germany. The Odra River is polluted by the discharges of wastewater from several industries and municipal wastewater treatment plants [1]. A few studies have reported the occurrence of trace organic contaminants in estuarine regions of the Odra River [12–16]. In this study, sediment samples were collected from various locations along the Odra and Warta Rivers and their tributaries in Poland to study the distribution of PCBs, PAHs, NP and OP. Few studies have reported the occurrence of PAHs, NP and OP in sediments from Baltic countries [13–16] and, therefore, this is one of a few reports that document the concentrations of PAHs, NP and OP in sediments. The target analytes were also measured in raw and treated sewage sludge from a municipal sewage treatment plant in Gdańsk, Poland. Since effluents from municipal wastewater treatment plants are a major source of NP, OP and other organic contaminants to riverine systems, analysis of sewage sludge provided information regarding the magnitude and sources of contamination to rivers. MATERIALS AND METHODS Sample Collection and Analysis Seventeen sediment samples were collected during June–August 1998 along the Odra River and its tributaries (Warta, Obrzyca, Barycz, Kaczawa and Bóbr Rivers), and the Odra River estuary (Roztoka Odrzańska) in Poland (Fig. 1). Several samples (10) from each location were pooled to obtain a representative sample. Surface sediments (0–5 cm) were collected using a Van Veen grab sampler. After collection, pebbles and twigs were removed, then samples were freeze dried and ground with a mortar and pestle. Samples were stored in HDPE (high density polyethylene) bottles at 20 C until extraction. Sewage sludge samples were collected from the Gdańsk–Wschód sewage treatment plant (Oczyszczalnia Gdańsk-Wschód) in the city of Gdańsk (Fig. 1). Sludge samples were collected before and after primary treatment. In the Gdańsk– Wschód sewage treatment plant, open fermentation tanks were used for primary sewage treatment. The period of sludge fermentation was between three and four months. POLYCHLORINATED SEDIMENTS OF ODRA RIVER BALTIC SEA RIVER ODRA Gdansk Gryfino Gorzow Szczecin Odra R. Szczecin GERMANY Estuary Kostrzyn 53 POLAND Poznan Warsaw Wroclaw Poznan Frankfurt Krosno Bytom Odrz. Odrzanskie Bob R Wroclaw CZECH REPUBLIC Krakow Zawiercie Roztoka FIGURE 1 Map of Poland and the Odra and Warta Rivers showing sampling locations of sediments. PCBs, PAHs, NP and OP were analyzed following the methods described elsewhere [17,18]. Sediment and sludge samples were Soxhlet extracted for 20 h using high purity dichloromethane (DCM). Extracts were then treated with acid-activated copper granules to remove sulfur. Aliquots of extracts were concentrated to approximately 5 mL by rotary evaporation (40 C), and then to 1 mL under a gentle stream of nitrogen. Extracts were passed through 10 g of activated Florisil (60–100 mesh size) packed in a glass column (10 mm i.d.) for clean up and fractionation. The first fraction (F1) eluted with 100 mL of hexane contained PCBs. PAHs were eluted in the second fraction (F2) using 100 mL of 20% DCM in hexane. NP and OP were eluted in the third fraction (F3) with 100 mL of 50% DCM in methanol. Florisil separation was confirmed using a spike recovery test (n ¼ 3) and standard reference material (SRM), 1974a sediment, obtained from the National Institute of Standards and Technology (Gaithersburg, Maryland, USA). Recoveries of the analytes were examined by spiking known amount of PCBs (100 ng), PAHs (1000 ng) and NP (500 ng) to sodium sulfate, which was extracted and processed through the whole analytical procedure. Recoveries of these analytes were between 90 and 105%. Procedural blanks were run with every five samples to check for interferences. Further details regarding the fractionation procedure are presented elsewhere [17,18]. PAHs were quantified using a Hewlett Packard 5890 series II gas chromatograph equipped with a 5972 series mass spectrometer detector. A fused silica capillary column (30 m 0.25 mm i.d.) coated with DB-17 [(50% phenyl)-methyl polysiloxane; J&W Scientific, Folsom, CA, USA] at 0.25 mm film thickness was used. The column oven temperature was programmed from 80 C (1 min hold) to 100 C at a rate of 25 C/min, and then ramped at a rate of 5 C/min to 100 C with a final holding time 54 K. KANNAN et al. of 6 min. The injector and detector temperatures were maintained at 250 and 300 C, respectively. The PAH standard (AccuStandard, New Haven, CT, USA) consisted of 16 priority pollutant PAHs identified by the U.S. Environmental Protection Agency (U.S. EPA Method 8310). The mass spectrometer was operated under selected ion monitoring (SIM) mode using the molecular ions selective for individual PAHs. Concentrations based on individually resolved peaks were summed to obtain the total PAH concentrations. The detection limits of individual PAHs in sediment samples were 10 ng/g, dry wt. PCBs were quantified using a gas chromatograph (Perkin Elmer series 600) equipped with 63Ni electron capture detector (GC-ECD). A fused silica capillary column coated with DB-SMS [(5%-phenyl)-methylpolysiloxane, 30 m 0.25 mm i.d.] having a film thickness of 0.25 mm was used. The column oven temperature was programmed from 120 C (1 min hold) to 180 C at a rate of 10 C/min (1 min hold) and then to 260 C at a rate of 2 C/min with a final hold time of 12 min. Injector and detector temperatures were kept at 250 and 300 C, respectively. Helium and nitrogen were used as carrier and make up gases, respectively. A solution containing 98 individual PCB congeners (AccuStandard, New Haven, CT, USA) with known composition and content was used as a standard and concentrations of 98 individually resolved peaks were summed to obtain total PCB concentrations [19]. Detection limits of individual PCB congeners were 0.01 ng/g, dry wt. Reverse phase high performance liquid chromatography (HPLC) with fluorescence detection was used to quantify NP and OP. High-purity p-nonylphenol and p-tert-octylphenol standards (Schenectady International, Freeport, TX, USA) were used as standards. Samples and standards were injected (10 mL) by a Perkin Elmer Series 200 autosampler (Perkin Elmer, Norwalk, CT, USA) onto an analytical column, ProdigyTM ODS (3), 250 4.6 mm column (Phenomenex, Torrance, CA, USA), which was connected to a guard column (ProdigyTM ODS (3), 30 4.6 mm), and eluted with a flow of acetonitrile (ACN) and water at a gradient from 50% ACN in water to 98% ACN in water delivered by Perkin Elmer Series 200 pump for 20 min. Detection was accomplished using a Hewlett Packard 1046A fluorescence detector (Hewlett-Packard, Wilmington, DE, USA) with an excitation wavelength of 229 nm and an emission wavelength of 310 nm. NP and OP detection limits for the analytical method were 1 ng/g, dry wt. RESULTS AND DISCUSSION Sediments PCBs were found in all sediment and sewage sludge samples analyzed. Concentrations of PCBs in sediments varied widely, and ranged from 2.7 to 412 ng/g, dry wt (Table I). Sediment collected from the Obrzyca River contained the highest concentration of PCBs, which was approximately 7-fold greater than the average PCB concentration calculated for the Odra River basin (60.5 ng/g dry wt). Sediment from Police and Gorzów Wielkopolski contained PCB concentrations greater than 100 ng/g, dry wt. This suggests the presence of local sources in these locations. Several large chemical industries (fertilizer manufacturers) are located in Police. The measured concentrations of PCBs in sediments collected along the Odra River and its tributaries were greater POLYCHLORINATED SEDIMENTS OF ODRA RIVER 55 TABLE I Concentrations of total PCBs, PAHs and alkylphenols (ng/g, dry wt) in sediment collected along the Odra River and its tributaries, Poland Location Total PCBs Total PAHs OP NP Kaczawa River Barycz River Bytom Odrzański (Odra River) Obrzyca River Bóbr River Police Krosno Odrzańskie (Odra River) Zawiercie (Warta River) Poznań (Warta River) Gorzów Wlpk. (Warta River) Kostrzyn (Warta River) Frankfurt (Odra River) Mescherin Gryfino (Odra River) Podjuchy (Odra River) Szczecin (Odra River) Roztoka Odrzanska 15.3 41.4 12.0 412 7.2 131 18.1 65.8 9.7 125 2.7 18.5 4.0 25.4 44.7 11.2 85.1 5710 6150 10 400 1520 4280 19 000 6010 18 400 1480 4600 150 4230 1000 6560 1720 9690 9590 1.9 3.6 3.3 5.9 <1 2.5 <1 1.9 1.1 3.1 <1 3.5 <1 4.1 3.2 9.8 <1 47 161 762 91 48 224 48.7 498 185 71.7 11 65.8 18 682 35.2 757 <1 Max Min Mean 412 2.7 60.5 19 000 150 6500 9.75 <1 2.89 762 <1 232 than those reported for the Odra River Estuary, which ranged from 0.13 to 16 ng/g, dry wt [12,13]. Roztoka Odrzańska is a part of the Odra River Estuary, which contained a PCB concentration in sediment of 85.1 ng/g, dry wt (Table I). Sediments collected along the western and eastern Odra River near Szczecin and Gryfina contained total PCB concentrations in the range of 12–86 ng/g, dry wt [20]. The results suggest that the Odra River and its tributaries are a source of PCBs in the southern Baltic Sea. Sediment quality guidelines (SQG) have been proposed for PCBs in sediments using theoretical and empirical approaches [21]. Based on the review of available SQGs, consensus threshold- (TEC) and moderate-effect concentrations (MEC) of 40 and 400 ng/g, dry wt, respectively, have been proposed for total PCBs [21]. Sediment collected in the Obrzyca River exceeded the MEC whereas 7 of the 17 sediments contained total PCB concentrations greater than TEC but less than MEC. Concentrations of PCBs in 53% of the sediments analyzed were less than the TEC. PAHs were the predominant compounds in sediments of the Odra River and its tributaries in Poland. Concentrations of PAHs were approximately two orders of magnitude greater than those of PCBs (Table I). Concentrations of PAHs were uniformly high in all the locations and were relatively less variable. PAH concentrations greater than 10 000 ng/g, dry wt, were measured in sediments from Police, Zawiercie, Bytom Odrzański. This suggests the presence of point sources of PAHs in these local areas. Zawiercie and Bytom Odrzański are located in lower Silesia region in the southwestern Poland; Several industrial activities in lower Silesia including coal burning and processing could have contributed for the great PAH concentrations. A recent study has reported the occurrence of PAHs in sediments of the Odra River Estuary. A median PAH concentration of 395 ng/g, dry wt, was found in sediments from the Odra River Lagoon [16]. Mean PAH concentration of 6500 ng/g, dry wt, measured in the sediments of the Odra River and its tributaries was 16 times greater than that reported for the Odra River Lagoon. A study on the spatial distribution of K. KANNAN et al. 2.0 1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 ena Ac Na ph tha le pht ne hyl Ac ene ena pht hen Flu e or Ph ena ene nth ren An e thr ace Flu ne ora nth ene Be nzo P yre [a] n ant hra e cen Be e Ch nzo Be [b]fl rysen nzo u e [k] orant flu he n ora nth e Be e ne n z o[a Ind ]py e Dib no[1 r e ne enz 23c d [a, h]a ]pyre Be n nth nzo rac e [gh ene i]p er y len e Mean concentration (µg/g, dry wt) 56 FIGURE 2 Mean concentrations (mg/g) of individual PAHs in sediments collected from the Odra and Warta Rivers. Bars indicate SD. PAHs in the Baltic Sea suggested that sediments from the Odra Trough had the highest PAH concentration of 1070 ng/g, dry wt, and suggested that the Odra River has been a major source of PAHs in the southern Baltic Sea [22]. Concentrations of PAHs in sediments from the Morava and Drevnice Rivers in the Czech Republic were from 1160 to 40 000 ng/g, dry wt [23]. The mean concentrations of PAHs in sediments from the Odra River were similar to those found in the Morava River in the Czech Republic. Mean concentration of 16 PAH compounds analyzed in the study is shown in Fig. 2. Three and four-ringed aromatic compounds such as chrysene, fluoranthene, phenanthrene and pyrene were the major PAHs accounting for, on average, 58% of the total PAH concentrations in sediments. Some molecular ratios of specific PAH compounds are used to distinguish between PAHs of various origin [24]. These criteria are based on the characteristics of composition and distribution pattern as a function of the emission source. Phenanthrene (Phe) is a thermodynamically more stable tricyclic aromatic isomer than anthracene (Ant). Hence petroleum contains more phenanthrene relative to anthracene (Phc/Ant >5). On the contrary, high-temperature processes such as incomplete combustion of fossil fuel (e.g., coal) can result in low Phe/Ant ratios (Phe/Ant <15) [25]. Similarly, fluoranthene (Flu) to pyrene (Py) ratios greater than one are attributed to pyrolytic sources, whereas less than 1 are related to petrogenic sources. However, exceptions exist in some cases [25] and, therefore, caution should be exercised to use the above ratios. In this study, all sediments exhibited Flu/Py ratios of greater than 1, which suggests pyrolytic inputs (Table II). Further, the ratios of Phe/Ant were less than 15 in all locations except locations on the Barycz River (Poznań and Kostrzyn), further suggesting that the major source of PAHs in sediments is combustion of fossil fuel such as coal. The values of Flu/Py and Phe/Ant in sediments from Barycz River as well as of the Warta River at the sites Poznań and Kostrzyn suggested that they receive inputs both from petrogenic acid pyrolytic sources of PAHs. A variety of approaches to the development of biological effects-based SQG have been proposed and compared (see [26] for review). A consensus threshold concentration of total PAHs of 290 mg/g OC has been proposed [26]. Assuming an organic carbon content of 1% in sediments, the organic carbon normalized PAH POLYCHLORINATED SEDIMENTS OF ODRA RIVER 57 TABLE II Ratios of Phenanthrene to Anthracene (Phe/Ant) and Fluoranthene to Pyrene (Flu/Py) in sediments collected along the Odra River and its tributaries in Poland Location Kaczawa River Barycz River Bytom Odrzański (Odra River) Obrzyca River Bóbr River Police Krosno Odrzańskie (Odra River) Zawiercie (Warta River) Poznań (Warta River) Gorzów Wielkopolski (Warta River) Kostrzyń (Warta River) Frankfurt (Odra River) Mescherin Gryfino (Odra River) Podjuchy (Odra River) Szczecin (Odra River) Roztoka Odrzańska (Odra River estuary) Phe/Ant Flu/Py 4.2 87.3 4.1 0.2 3.5 5.0 3.8 4.9 116 7.7 23.3 2.8 2.7 4.7 4.4 5.1 4.9 1.1 1.2 1.3 2.5 1.2 1.2 1.3 1.2 1.2 1.1 1.1 1.3 1.2 1.2 1.3 1.2 1.2 concentrations in Odra and Warta River sediments were estimated to be between 15 and 1900 mg/g OC. Twelve of the 17 sediments exceeded the consensus SQG for PAHs of 290 mg/g OC. Nonylphenol was detected in sediments from all the locations except that from Roztoka Odrzańska. The highest NP concentration was 762 ng/g, dry wt, found for the sediment from Bytom Odrzański. Very few studies have reported the occurrence of alkylphenols in riverine sediments in Europe. The concentrations of NP in sediments were comparable or greater than those found in sediments from the Morava River (6–150 ng/g, dry wt) in the Czech Republic [27]. Sediments from rivers in the UK contained NP concentrations in the order of a few mg/g dry wt [28]. NP concentrations in sediments from the Rhine, Glatt and Sitter Rivers in Switzerland ranged from 190 to 13 000 ng/g, dry wt [29]. Concentrations of OP were one to two orders of magnitude less than those of NP. Greater concentrations of NP and OP suggest sources originating from municipal wastewater treatment plants. Sewage Sludge PCBs, PAHs, NP and OP were found in raw and treated sewage sludge collected from Gdańsk, Poland (Table III). Concentrations of PCBs in sludge ranged from 130 to 371 ng/g, dry wt. There was no significant reduction in PCB concentrations after primary treatment (fermentation). Similarly, concentrations of PAHs in sewage sludge ranged from 7980 to 18 400 ng/g, dry wt. In general, 4-ring aromatic hydrocarbons accounted for 58% of the total PAH concentrations in sludge (Fig. 3). Fluoranthene, pyrene, chrysene and phenanthrene accounted for 62% of the total PAH concentrations in sludge. Similar to that found for sediments, the ratios of Phe/Ant and Flu/Py were <15 and >1, respectively, for all sewage sludge samples. This suggests that the major source of PAHs in sewage sludge is combustion related. Primary treatment of the sewage did not reduce PAH concentrations in sludge. Concentrations of PCBs and PAHs were greater than those found in sediments from several locations. These results suggest that the discharge of wastewater and sewage 58 K. KANNAN et al. TABLE III Concentrations of PCBs, PAHs and alkylphenols (ng/g, dry wt) in raw and treated sewage sludge from a treatment plant in Gdańsk, Poland Location Raw sewage sludge Tank #1 Raw sewage sludge Tank #2 Raw sewage sludge Tank #3 Raw sewage sludge Tank #4 Mean (raw) Sewage sludge after clarification #1 Sewage sludge after clarification #2 Mean (treated) Total PCBs Total PAHs OP NP 186 253 130 242 203 371 198 284 12 100 7980 10 900 15 900 11 720 18 400 9360 13 880 4320 411 495 622 1460 365 361 363 17 800 154 000 111 000 116 000 99 600 6670 6840 6760 % of total PAH concentrations 120 100 80 60 40 20 0 2 3 4 5 6 Number of rings FIGURE 3 Profile of PAHs in sewage sludge collected from a treatment plant in Gdańsk, Poland. Values are presented as (average) % of total PAH concentrations for individual PAH groups selected based on the number of rings. Bars indicate SD. sludge from treatment plants can contribute to a major source of PCBs and PAHs in rivers. Concentrations of NP in sewage sludge ranged from 6670 to 154 000 ng/g, dry wt. This is within the range of values reported for sewage sludge from various countries (see [30] for review). NP concentrations in raw sludge were, on average, 68fold (range 4–370) greater than those of OP concentrations. In contrast to that observed for PCBs and PAHs, NP and OP concentrations in treated sewage sludge were 7 and 25% of that found in raw sewage sludge. The reduction in NP and OP concentrations in treated sewage sludge suggests degradation of these compounds during treatment. Several studies have examined the degradation of NP in wastewater treatment processes [31–33]. Although the rate of removal of NP can vary depending upon the type of treatment applied, the results of this study suggest considerable reduction in NP concentrations following treatment. However, the treated sludge still contained NP concentrations of 6760 ng/g, dry wt. References [1] I. Holoubek, A. Kočan, I. Holoubková, K. Hilscherová, J. Kohoutek, J. Falandysz and O. Roots (2000). Persistent, coaccumulative and toxic chemicals in central and eastern European countries – state-of-the-art Report. Tocoen Report No. 150a. RECETOX-TOCOEN & Associates, Brno, Czech Republic. [2] K. Kannan, J. Falandysz, N. Yamashita, S. Tanabe and R. Tatsukawa (1992). Temporal trends of organochlorine concentrations in cod-liver oil from the southern Baltic proper, 1971–1989. Mar. Pollut. Bull., 24, 358–363. POLYCHLORINATED SEDIMENTS OF ODRA RIVER 59 [3] K. Kannan, J. Falandysz, S. Tanabe and R. Tatsukawa (1993). Persistent organochlorines in harbour porpoises from Puck Bay, Poland. Mar. Pollut. Bull., 26, 162–165. [4] J. Falandysz, K. Kannan, S. Tanabe and R. Tatsukawa (1993). Persistent organochlorine residues in canned cod-livers of the southern Baltic origin. Bull. Environ. Contam. Toxicol., 50, 929–934. [5] J. Falandysz, K. Kannan, S. Tanabe and R. Tatsukawa (1994a). Concentrations, clearance rate and toxic potential of non-ortho-coplanar PCBs in cod liver oil from the southern Baltic Sea from 1971 to 1987. Mar. Pollut. Bull., 28, 259–262. [6] J. Falandysz, K. Kannan, S. Tanabe and R. Tatsukawa (1994b). Organochlorine pesticides and polychlorinated biphenyls in cod-liver oils: North Atlantic, Norwegian Sea, North Sea and Baltic Sea. Ambio, 23, 288–293. [7] O. Roots (1995). Organochlorine pesticides and polychlorinated biphenyls in the ecosystem of the Baltic Sea. Chemosphere, 31, 4085–4097. [8] J. Koistinen, C. Stenman, H. Haahti, M. Suonpera and J. Paasivirta (1997). Polychlorinated diphenyl ethers, dibenzo-p-dioxins, dibenzofurans and diphenyls in seals and sediment from the Gulf of Finland. Chemosphere, 35, 1249–1269. [9] A. Olsson, M. Vilinsh, M. Plikshs and Å. Bergman (1999). Halogenated environmental contaminants in perch (Perca pluviatilis) from Latvian coastal areas. Sci. Total Environ., 239, 19–30. [10] D. Dannenberger (1996). Chlorinated microcontaminants in surface sediments of the Baltic Sea – Investigations in the Belt Sea, the Arkona Sea and the Pomeranian Bight. Mar. Pollut. Bull., 32, 772–781. [11] B. Strandberg, B. van Bavel, P.-A. Bergqvist, D. Broman, R. Ishaq, C. Näf, H. Pettersen and C. Rappe (1998). Occurrence, sedimentation, and spatial variations in organochlorine contaminants in settling particulate matter and sediments in the northern part of the Baltic Sea. Environ, Sci. Technol., 32, 1754–1759. [12] D. Dannenberger, R. Andersson and C. Rappe (1997). Levels and patterns of polychlorinated dibenzo-pdioxins, dibenzofurans and biphenyls in surface sediments from the western Baltic Sea (Arkona Basin) and the Odra River estuarine system. Mar. Pollut. Bull., 34, 1016–1024. [13] D. Dannenberger and A. Lerz (!999). Occurrence and transport of organic micro-contaminants in sediments of the Odra River estuarine system. Acta Hydrochim. Hydrobiol., 27, 303–307. [14] B. Bierawska, D. Glod, J. Blaźejowski, B. Lammek, J. Szafranek and E. Niemirycz (1999). Polycyclic aromatic hydrocarbons and polysaccharides in river sediments from the Odra basin after the 1997 flood. Acta Hydrochim. Hydrobiol., 27, 350–356. [15] L. Wolska, V. Wardencki, M. Wiergowski, B. Zygmunt, B. Zabiegala, P. Konieczka, L. Poprawski, J.F. Biernat and J. Namieśnik (1999). Evaluation of pollution degree of the Odra River basin with organic compounds after the 1997 summer flood – general comments. Acta Hydrochim. Hydrobiol., 27, 343–349. [16] G. Witt and E. Trost (1999). Distribution and fate of polycyclic aromatic hydrocarbons (PAHs) in sediments and fluffy layer material from the Odra River Estuary. Acta Hydrochim. Hydrobiol., 5, 308–315. [17] J.S. Khim, K. Kannan, D.L. Villeneuve, C.H. Koh and J.P. Giesy (1999). Characterization and distribution of trace organic contaminants in sediment from Masan Bay, Korea: 1. Instrumental analysis. Environ. Sci. Technol., 33, 4199–4205. [18] N. Yamashita, K. Kannan, T. Imagawa, D.L. Villeneuve, S. Hashimoto, A. Miyazaki and J.F. Giesy (2000). Vertical profile of polychlorinated dibenzo-p-dioxins, dibenzofurans, naphthalenes, biphenyls, polycyclic aromatic hydrocarbons, and alkylphenols in a sediment core from Tokyo Bay, Japan. Environ. Sci. Technol., 34, 3560–3567. [19] J.S. Khim, D.L. Villeneuve, K. Kannan, W.Y. Hu, J.P. Giesy, S.-G. Kang, K.-J. Song and C.H. Koh (2000). Instrumental and bioanalytical measures of persistent organochlorines in blue mussels (Mytilus edulis) from Korean coastal waters. Arch. Environ. Contam. Toxicol., 39, 360–368. [20] M. Protasowicki, E. Nicdźwiscki, W. Ciereszko, A. Perkowska and E. Meller (1999). The comparison of sediment contamination in the area of estuary and the lower course of the Odra before and after the flood of summer 1997. Acta Hydrochim. Hydrobiol., 27, 338–342. [21] D.D. MacDonald, L.M. Dipinto, J.F. Christopher, C.G. Ingersoll, E.R. Long and R. Swartz (2000). Development and evaluation of consensus-based sediment effect concentration for polychlorinated biphenyls. Environ. Toxicol. Chem., 19, 1403–1413. [22] G. Witt (1995). Polycyclic aromatic hydrocarbons in water and sediment of the Baltic Sea. Mar. Pollut. Bull., 31, 237–248. [23] K. Hilschereva, K. Kannan, Y.-S. Kang, I. Holoubek, M. Machala, S. Masunaga, J. Nakanishi and J.P. Giesy (2001). Characterization of dioxin-like activity of riverine sediments from the Czech Republic. Environ. Toxicol. Chem., 20, 2768–2777. [24] P. Baumard, H. Budzinski and P. Garrigues (1998). Polycyclic aromatic hydrocarbons in sediments and mussels of the western Mediterranean Sea. Environ. Toxicol. Chem., 17, 765–776. [25] B.A. Benner, G.E. Gordon and S.A. Wise (1989). Mobile sources of atmospheric polycyclic aromatic hydrocarbons: a roadway tunnel study. Environ. Sci. Technol., 23, 1269–1278. [26] R.C. Swartz (1999). Consensus sediment quality guidelines for polycyclic aromatic hydrocarbon mixtures. Environ. Toxicol. Chem., 18, 780–787. [27] K. Hilscherova, K. Kannan, J. Holoubek and J.P. Giesy (2002). Characterization of estrogenic activity of riverine sediments from the Czech Republic. Arch. Environ. Contam. Toxicol., 43, 175–180. 60 K. KANNAN et al. [28] M.A. Blackburn, S.J. Kirby and M.J. Waldock (1999). Concentrations of alkyphenol polyethoxylates entering UK estuaries. Mar. Pollut. Bull., 38, 109–118. [29] M. Ahel, W. Giger and M. Koch (1994). Behavior of alkylphenol polyethoxylate surfactants in the aquatic environment – I. Occurrence and transformation in sewage treatment. Wat. Res., 28, 1131–1142. [30] D.T. Bennie (1999). Review of the environmental occurrence of alkylphenols and alkylphenol ethoxylates. Water Qual. Res. J. Canada., 34, 79–122. [31] T. Tanghe, G. Devriese and W. Versuaete (1998). Nonylphenol degradation in lab scale activated sludge units is temperature dependent. Wat. Res., 32, 2889–2896. [32] F.A. Banat, S.B. Prechtl and F. Bischof (2000). Aerobic thermophilic treatment of sewage sludge contaminated with 4-nonylphenol. Chemosphere, 41, 297–302. [33] K. Fujii, N. Urano, Kimura, Y. Nomura and I. Karube (2000). Microbial degradation of nonylphenol in some aquatic environments. Fish. Sci., 66, 44–48.