Some Chemical Contaminant of Surface Sediments at the Baltic Sea ...

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Journal of Environmental Science and Health Part A, 41:2127–2162, 2006 C Taylor & Francis Group, LLC Copyright  ISSN: 1093-4529 (Print); 1532-4117 (Online) DOI: 10.1080/10934520600872433

Some Chemical Contaminant of Surface Sediments at the Baltic Sea Coastal Region with Special Emphasis on Androgenic and Anti-Androgenic Compounds J. Falandysz,1 T. Albanis,2 J. Bachmann,3 R. Bettinetti,4 I. Bochentin,1 V. Boti,2 S. Bristeau,5 B. Daehne,6 T. Dagnac,5 S. Galassi,7 R. Jeannot,5 J. Oehlmann,3 A. Orlikowska,1 V. Sakkas,2 R. Szczerski,1 V. Valsamaki,2 and U. Schulte-Oehlmann2 1

´ Department of Environmental Chemistry & Ecotoxicology, University of Gdansk, ´ Gdansk, Poland 2 Department of Chemistry, University of Ioannina, Ioannina, Greece 3 Department of Ecology and Evolution, J.W. Goethe University, Frankfurt, Germany 4 Department of Chemistry and Environmental Sciences, University of Insubria, Como, Italy 5 Bureau de Recherches Geologiques et Minieres, Orleans, France 6 Limnomar, Laboratory for Aquatic Research and Comparative Pathology, Hamburg/Norderney, Germany 7 Department of Biology, University of Milan, Milano, Italy Androgenic and anti-androgenic compounds including p,p -DDE, Diuron, Linuron, Fenarimol, Vinclozolin, 1-(3,4-dichlorophenyl) urea (DCPU), 1-(3,4-dichlorophenyl)-3methylurea, (DCPMU), tributyltin (TBT) and triphenyltin (TPT) and their metabolites (DBT, MBT, DPT, MPT) as well as metallic elements (Ni, Cu, Zn, As, Cd, Pb, Co, Tl, Cr, Fe, Mn, Al, K, Mg, Na, Ca, Ba, Ti, Sn), PAHs (16 indicator compounds), DDTs and PCBs have been quantified in top layer (0–10 cm) of up to 37 surface sediment samples ´ collected from several sites in costal zone of the Gulf of Gdansk, an inland freshwater

Received January 18, 2006. Address correspondence to Jerzy Falandysz, Department of Environmental Chemistry ´ ´ and Ecotoxicology, University of Gdansk, 18 Sobieskiego Str., PL 80-952, Gdansk, Poland; E-mail: [email protected]

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area of Brdyuj´scie in Poland and the tidal flats of the Norderney Island, Wadden Sea in 2002–2003. These sites differed in the degree of anthropogenic activities, including chemical pollution and related impact on biota. Especially in sediments near shipyards, ship repair facilities, harbours, other industrial activities or close to municipal sewage treatment plant outlets butyltins, PAHs and some metallic elements were found at high concentrations. Diuron, Linuron and DCPMU were detected at a few sites, Fenarimol only once, while Vinclozolin and DCPU were not detected. DDT concentrations in the ´ sediments from the Gdansk and Gdynia region of the Gulf show a stepwise decrease following the ban for production and use, while diffusion of PCBs at some industrial sites seems to continue. Elevated PAH concentrations in sediments seem to be mainly due to pyrogenic and less to mixed pyrogenic and petrogenic sources, while for a few sites rather petrogenic sources dominated. The reference sites in the Norderney Island, Wadden Sea showed similar or slightly higher loads of DDTs, BTs, PAHs, PCBs and metallic elements when compared to sediments from the least contaminated sites in ´ the coastal Gulf of Gdansk area, while phenyltins were not detected at both spatially distant European areas. Key Words: Diuron; Endocrine disrupters, Fenarimol; Heavy metals; Linuron; Organotins; PAHs; PCBs; Pesticides; Vinclozolin.

INTRODUCTION Since decades, the Baltic Sea and especially the surrounding–its coastal regions are impacted by many anthropogenic factors, including discharged chemicals, which disturb the quality of water and sediments, influence the composition of the aquatic biocenosis, the survival of biota and may eventually bio-accumulate in the food-chain.[1,2] Because of these unsolved environmental problems the Baltic Sea is considered as an area of high scientific interest. Nevertheless, scientific data concerning its pollution by some noxious organic or organo-metallic compounds such as phenylurea herbicides, Fenarimol, Vinclozolin or triphenyltin (TPT), which exhibit androgenic or anti-androgenic activity, are scare or even non-existing. The aim of this study was to assess the environmental exposure to androgenic and anti-androgenic compounds (AACs) in two European areas with different environmental pollution history. Surface sediment samples were collected in autumn 2002 and winter 2002–2003 to assess their androgenic and anti-androgenic potential both analytically and biologically. The selected ´ sampling points included the near shore region of the Gulf of Gdansk located ´ in the neighbourhood of the cities of Gdansk and Gdynia, inland sites of the Brdyuj´scie area in the vicinity of the city of Bydgoszcz as well as two reference sites in Northern Germany (Norderney Island). The collected sediment samples were analyzed for the occurrence of AACs and a range of further environmental contaminants. The target analytes included pesticides and their metabolites (p,p-DDT, p,p-DDD, p,p-DDE, Diuron, Linuron, DCPU, DCPMU, Fenarimol, Vinclozolin, tributyltin, dibutyltin, monobutyltin,

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Figure 1: Location of the sediment sampling sites in the Gulf of Gdansk. ´

triphenyltin, diphenyltin and monophenyltin), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs: naphthalene, acenaphthylene, acenaphthalene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, dibenzo(ah)anthracene, benzo(ghi)perylene and indeno(123cd)-pyrene), and metallic elements (As, Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sn, Ti, Tl and Zn).

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Figure 2: Location of the sediment sampling sites in inland Poland.

MATERIALS AND METHODS Study Areas ´ is the main area of this study. Few The coastal zone of the Gulf of Gdansk sediment samples were also collected from the Brdyuj´scie site of inland Poland as well as two reference sites from Northern Germany (Norderney island), ´ is part of the Gdansk ´ Basin which respectively (Figs. 1–3). The Gulf of Gdansk is a southward extension of the Eastern Gotland Basin. This area—frequently treated as a separate natural region because of its maximum depth of 118 m—acts as a sink for suspended matter carried by the Vistula River, the largest river draining into the Baltic proper.[1] ´ The Gulf of Gdansk is known to be also under the direct impact of an intensively urbanized and industrialized region due to the Tr´ojmiasto agglom´ eration with two large cities, Gdansk and Gdynia, as well as numerous small towns, villages and settlements. Some local industrial activities are situated along its southern, western and north-western (Hel Peninsula) coastline. The ´ is considered as southwestern region of the coastal zone of the Gulf of Gdansk a region of high anthropogenic activity. This is due to a long history of port activity, shipyard and ship repair industry, navy, chemical industry (fertilizer production, petroleum refinery), fishery industry, agriculture, residential and communal heating as well as transport and city run-offs.

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Figure 3: Location of the reference sediment sampling sites in the tidal flats of the island Norderney (Lower Saxonian Wadden Sea, Germany).

The Brdyuj´scie area in the vicinity of the city of Bydgoszcz is situated about ´ in inland Poland (Fig. 2). At the Brdyuj´scie 180 km south of the Gulf of Gdansk sites (nos. 50 and 51/52) sewage was dumped, in recent years largely purified, coming from the city of Bydgoszcz with its large chemical industries. The Brda River in the Brdyuj´scie site flows into the Vistula River which enters finally ´ the Gulf of Gdansk. The two reference sites in Germany (nos. R1 and R2) are situated in the tidal flats of Norderney, an island in the Lower Saxonian Wadden Sea. These two selected sites were routinely tested within the German Federal Environmental Monitoring programme and represent the lower level of contamination with xenobiotics in this area (Fig. 3).

Sediment Collection and Processing Thirty seven surface (0–10 cm) sediment samples with a mass of ´ region using an Eckman grab ∼15 kg each were collected in the Gulf of Gdansk sampler. Sampling sites were selected to obtain a good coverage of different kinds of pollution sources both from fresh and brackish waters in the coastal zone in the Gulf as well as to establish transects from point sources whenever it was relevant and possible in autumn 2002 and winter 2002/03 (Fig. 1). At the same time sediments were collected also in inland Poland (Fig. 2) and at the

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two reference samples in the tidal flats of the East Frisian island Norderney (Germany) at low tide (Fig. 3). Each wet sediment sample from a particular site was well mixed, divided into aliquots of ∼2 kg and packed into polyethylene bags. The bags were wrapped with aluminium foil and kept deep-frozen until chemical analysis was completed. A ∼2 kg sediment sub-sample from each site was further lyophilized under dark condition. After being dried at 40◦ C sediment subsamples were initially sieved at 2 mm, followed by crushing and sieving at 250 µm, and further divided into several portions and packed into precleaned high or low density sealed polyethylene containers, depending on further chemical analysis. Dry sediment subjected to butyltins and phenyltins analyses were cold stored in brown-coloured containers. The organic matter content of the sediments was determined by weight-loss-on-ignition at 550 ◦ C.

FENARIMOL, VINCLOZOLIN, DIURON, LINURON, DCPU AND DCPMU QUANTIFICATION Chemicals Analytical grade standards of Diuron (1-(3, 4-dichlorophenyl)-3, 3-dimethylurea), Linuron (3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea), Fenari¨ mol and Vinclozolin were obtained from Riedel-de-Haen, (Seelze-Hannover, Germany), respectively. The common metabolites of phenylurea pesticides, 1-(3,4-dichlorophenyl) urea (DCPU) and 1-(3,4-dichlorophenyl)-3-methylurea (DCPMU) were purchased from Dr. Ehrenstorfer GmbH (Augsburg, Germany) and were used without further purification (minimum percent purity greater than 98%). Stock standard solutions were prepared at 2 g/L in methanol for Fenarimol and Vinclozolin and in acetonitrile HPLC grade for the rest analytes. Secondary and working calibration standards were prepared at various concentrations by serial dilution in methanol and acetonitrile, respectively. Empore extraction disks of 47 mm diameter containing SDB (styrenedivinylbenzene) copolymer were purchased from 3M (Saint Paul, MN, USA). The SDB disks comprised 10% fibrillated PTFE and 90% 15 µm (particle diameter) SDB adsorbent material. Particles in the SDB disks had an average pore size of 80 A˚ and a 350 m2 /g surface area. Filter Aid FA 400 was purchased from 3M (Saint Paul, MN, USA) and copper powder (150 mesh, 99.5%) was supplied by Aldrich (Milwaukee, WI, USA). Methanol, dichloromethane, acetone, ethyl acetate, hexane, isooctane and toluene, were trace analysis grade from Pestiscan (Labscan Ltd., Dublin, Ireland). HPLC-grade solvents acetonitrile, dichloromethane, acetone, methanol and water as well as hydrochloric acid and anhydrous sodium sulphate were purchased from Merck (Darmstadt, Germany).

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Extraction and Quantification A different extraction methodology was developed for the extraction of the target analytes. A 5 g aliquot of sediment material (freeze-dried) was consequently extracted 3 times using 7 mL each time of the following solvents: acetone, dichloromethane and hexane for Fenarimol and Vinclozolin, while acetone, methanol and dichloromethane were used as the extraction solvents of phenylurea herbicides as well as their metabolites, respectively. Both extracts were combined separately and centrifuged at 5000 rpm for 5 min. Afterwards the supernatants were collected and evaporated to dryness under a gentle stream of nitrogen. The residue for the analysis of Diuron, Linuron and their metabolites was then reconstituted in acetonitrile:water (50:50) up to a final volume of 0.05 mL prior to HPLC-UV/DAD analysis. Further centrifugation or filtration through PTFE membranes was carried out when particulate matter interfered the analysis. Regarding Fenarimol and Vinclozolin analysis, the residue was redissolved in 0.5 mL of methanol, and diluted with distilled water to a final volume of 100 mL. Then the pH was adjusted to 3 and subjected to SPE procedure (clean up step). Isolation of the AACs was performed off-line using a standard SPE-system from Supelco (Bellefonte, PA, USA) connected to a vacuum pump. SDB disks were first activated by wetting with 5 mL acetone. Then, they were washed with 2 × 5 mL ethyl acetate: dichloromethane (50:50 v/v) and were vacuum dried. Methanol (5 mL) was then percolated through the disks and without letting the disk become dry, the diluted extract (100 mL) was applied to a speed of 10 mL/min. Next the disks were dried under vacuum for 10 min. The analytes were eluted in the opposite way to the sample application (back flush desorption) with 2 × 5 mL of a ethyl acetate-dichloromethane mixture (50:50 v/v). The extract was dried over anhydrous sodium sulphate and concentrated under a gentle nitrogen stream to 0.2 mL. Additional clean-up with activated copper powder was mandatory for the elimination of elemental sulphur that causes problems in the chromatographic analysis. The activation of copper powder was performed by washing under sonication (3 minutes) three times each with 20% HCl, water, acetone and toluene. After this procedure, copper remains active for at least 3 months when stored immersed in toluene or cyclohexane. The elimination of sulphur was done in situ by adding into the vials containing the concentrated sediment extract (0.2 mL) about 200 mg of activated copper powder. The mixture (extract and activated copper) was subjected to sonication for 20 minutes, and it was allowed to stand overnight in the refrigerator to let copper complex with free sulphur in the sediment extract. The HPLC system consisted of a Shimadzu (Kyoto, Japan) Model LC10ADVp pump associated with a valve with a 20 µL loop and a Shimadzu Model SPD-10AVp UV-vis diode-array detector connected to a Shimadzu Model

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Class VP 5 integrator. The analytes were separated by means of a Discovery C18 (250 × 4.6 mm ID: 5 µm) analytical column from Supelco (Bellefonte, PA, USA) that was fitted with a guard column cartridge of the same composition. The detector was set at 252 and 250 nm. Gradient elution was performed by increasing the percentage of acetonitrile in water from 10 to 70% over the first 20 minutes and then to 100% over a 2-minute period. This composition was maintained for 2 minutes, after which time the initial solvent conditions were restored using a linear ramp over a 3-minute period. The column was equilibrated for an additional 5 min before the next sample injection. Flow rate was 1 mL min−1 and the volume injected was 20 µL. The oven temperature was set to 40◦ C. Chromatographic analysis of Fenarimol and Vinclozolin was performed using a Shimadzu 14A capillary gas chromatograph equipped with a 63 Ni electron capture detector (ECD) at 300◦ C. Analytes were separated with a DB1 column (J & W. Scientific, Folsom, CA, USA), 30 m × 0.32 mm I.D., containing dimethylpolysiloxane with a phase thickness of 0.25 µm. The temperature program used for the analysis was: from 55◦ C (2 minutes) to 210◦ C (15 minutes) at 5◦ C/min and to 270◦ C at 10◦ C/min. The injector was set to 240◦ C in the splitless mode. Helium was used as the carrier at 1.5 mL/min. and nitrogen was used as the make-up gas at 35 ml/min according to the optimization results of the instrument given by the manufacturer. Identification of peaks was based on the comparison of the retention times of compounds in the standard solutions. Quantification of the analyzed compounds was performed using the method of the internal standard. Confirmation of the presence of Fenarimol and Vinclozolin was carried out using a QP 5000 Shimadzu instrument, equipped with a capillary column DB-5-MS, 30 × 0.25 mm, 0.25 µm, containing 5% phenyl-methylpolysiloxane (J & W Scientific) at the following chromatographic conditions: from 50◦ C (1 min) to 140◦ C (2 min) at 30◦ C/min and to 280◦ C at 5◦ C/min (12 min). Helium was used as the carrier gas at a flow-rate of 1 mL/min. The ion source and transfer were kept at 290◦ C and 240◦ C, respectively. Electron impact ionization mode, with 70 eV electron energy, was selected. The splitless mode was used for injection with the valve opened for 30 s. The screening analysis was performed in the SIM mode, monitoring at least two characteristic ions for each compound. In some experiments and for confirmation purposes, scan acquisition mode (m/z 50–450) was used. The ion traces were divided into four groups that were recorded sequentially during the injection, on the basis of the retention times of the single substances. In this way we avoid false positives due to the occurrence of other compounds which give common fragment ions but belong to a different retention time group.

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Phenylurea Herbicides and Metabolites Sediment samples were spiked at a concentration range of 5–100 µg/kg of the target AACs and extracted using sonication bath coupled to HPLC/UVDAD to check recoveries, method linearity and detection limits in natural matrices. Linearity was evaluated by the calculation of linear plot based on linear regression and the correlation coefficient R2 . All analytes exhibited a linear range from 5–100 µg/kg and an average correlation coefficient above or equal to 0.994 was observed. Replicate analysis of spiked sediments (n = 5) revealed satisfactory recovery values ranged from 66% to 92% for the two herbicides and their metabolites. The limit of detection varied between 0.6 and 0.9 µg/kg for all analytes.

Fenarimol and Vinclozolin Replicate analysis of spiked sediments with Fenarimol and Vinclozolin at 25 µg/kg (n = 5) revealed sufficient recovery values of 75% for Fenarimol and 74% for Vinclozolin. Relative standard deviation values were 14% and 11% for Fenarimol and Vinclozolin, respectively. Both compounds had a linear range from 25–400 µg/kg and an average correlation coefficient R2 ≥ 0.995. The limit of detection was 5 µg/kg, to both analytes. Intra-day (repeatability) and inter-day (reproducibility) precision experiments by analyzing three samples spiked at 25 µg/kg of each compound showed excellent results with RSDs less than 12% in all cases.

DDTs AND PCBs QUANTIFICATION Extraction and Cleanup Soxhlet extraction of dried sediment (2–3 g) was performed for 8 hours with n-hexane (100 mL). After solvent evaporation under reduced pressure, extractable organic matter (EOM) content was determined gravimetrically. Organic matter was then destroyed with H2 SO4 (98%) and chlorinated hydrocarbons were recovered by shaking with several portions of n-hexane. Next, combined n-hexane extracts were further concentrated down to about 2 mL and passed through a Florisil column (4 × 0.7 cm I.D.) with Cu powder (0.1 g) on the top. Cu powder was previously activated by HCl (18.5%) and washed with water, acetone and n-hexane. The Florisil column was eluted with 25 mL of n-hexane and the eluate was concentrated to exactly 0.5 mL.

Quantification and AQ/AC The purified extracts were introduced by on-column injection into a gas chromatograph Termo-Finnigan TOP 8000 equipped with a fused silica column

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(CP-Sil 8 CB, Chrompack, 50 m × 0.25 mm × 0.25 mm I.D., film thickness 0.25 µm). A Carlo Erba ECD 80 was used as electron capture detector heated at 320◦ C. p,p -DDE, p,p -DDD (Dr. Ehrenstorfer, Germany) and p,p -DDT Pestanal (Riedel-de Haen, Germany) were reference standards used at the final concentration of 10 µg/L in iso-octane. The technical polychlorinated biphenyls (PCBs) formulation of Aroclor 1260 (10 mg/L in iso-octane, Dr. Ehrenstorfer, Germany) was used as reference standard for PCBs quantification. Single PCB congeners were identified and quantified both by reference-pure PCBs (BCR, Brussels, Belgium) and published data.[3] Recovery efficiency was tested on reference sediment previously used in an intercalibration exercise.[4,5] Recoveries for p,p -DDE and PCBs were within 60–80% and for p,p -DDT and p,p -DDE around 50%.

PAHs Quantification Sediments were analysed for their contents of PAH (naphtaline, acenaphthylene, acenaphtene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, dibenz(ah)anthracene, benzo(ghi)perylene and indenol(1,2,3-cd)pyrene) according to DIN 38414 S 21 (DIN 1996) by means of HPLC (high performance liquid chromatography).[6] Samples were freeze dried and milled, followed by an accelerated solvent extraction (ASE). Cyclohexane served as extractant. Analysis parameters for the extraction were as follows: extractin pressure was 10 MPa; extraction temperature was 100◦ C; heating time was 5 min; static extraction was 3 × 5 minutes; rinsing with solvent (60% of cell volume) and rinsing with nitrogen (1 MPa for 150 seconds). The sample volume was reduced to 1.0 ml and cleaned over 2.8 ml cartridges with 0.5 g silica gel filling (SPE column). The cleaned extract was transferred into an acetonitrile phase and prepared for HPLC analysis. In deviation from the guideline, the separation was achieved by means of a gradient elution, with parameters as follows: injection volume was 20 µL; column temperature was 20◦ C; flow rate was 0.9 ml/min: at elution time 0–20 minutes acetonitryle in deionized water (50:50; eluent A) was used; at elution time 20–35 minutes acetonitryle (eluent B) was used; at elution time 35–40 minutes, again eluent A was used. For the detection of organic hydrocarbons, both fluorescence detectors and photodiode-array detectors may be used. In order to obtain optimal results, both detector types were used for this study. For quality assurance and control, a standard reference material was analysed (harbour sediment CRM 104, Resource Technology Corporation, USA). The obtained results for these analyses showed concentrations in the certified range. The reported PAH concentrations are mean values of three measurements, each of three digestions of a sediment sample.

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ORGANOTINS QUANTIFICATION Chemicals The standards of tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT), triphenyltin (TPT), diphenyltin (DPT) and monophenyltin (MPT) were purchased from STREAM Chemicals (Bischheim, France). 2,2,4-trimethylpentane (VWR, France), methanol (HPLC) (JT Baker, France), tropolone (99%), acetic acid glacial (99%), ammonium acetate (98%; Lancaster, Bischheim, France), and sodium tetrahydroborate (min. 98%; STREM Chemicals, Bischheim, France) all were of analytical grade.

Extraction, Quantification and AQ/AC Organotins were extracted from dried sediment samples by using Pressurized Liquid Extraction (PLE). The following conditions were used for the PFE: temperature 80◦ C, pressure at 100 bars, extraction time 5 minutes and number of cycles was 5. Then, 1 to 10 mg of each sample was extracted with 30 mL of acetic acid 0.5 M in methanol (3/97 v/v) containing 0.2% of tropolone. After extraction, 5 mL of extract were mixed with 2 to 5 mL of 2,2,4-trimethylpentane, internal standard mixture and 2 mL of NaBEt4 (2%) at pH 4.8 (100 mL of acetate buffer 0.6 to 1 M). The 2,2,4-trimethylpentane, which contained the organotin compounds, was recovered and concentrated down to 1 mL under gentle stream of nitrogen. The extract was analyzed by gas chromatography tandem mass spectrometry (GC-MS/MS). GC/MS/MS analyses were performed using a Thermoquest (Les Ulis, France) system consisting of a Trace GC 2000 GC equipped with a PTV split-splitless temperature injector, an AS 2000 autosampler and a POLARIS Q ion-trap mass spectrometer (Thermofinnigan, Les Ulis, France). For data processing, Excalibur software from Thermofinnigan was used. The injector was equipped with a 12 cm × 2 mm I.D. Silcoseeve liner (Thermofinnigan). They 2 µL of extract was injected onto the PTV injector in constant flow mode set at 1 mL/min and with an injection rate of 1 µL/s. The split flow was set at 50 mL/min. The temperature of the injector was initially set at 85◦ C then increased to 300◦ C at a rate of 10◦ C/s where it was maintained for 12 minutes. The PTV split/splitless valve was operating in splitless mode until the temperature of 300◦ C was achieved. Once the temperature stabilized, it was maintained for a period of 1.5 minutes, then changed to split mode. Compounds were separated on a 30 m × 0.25 mm I.D. column, coated with 0.25 µm of 65% dimethyl-35% phenyl polysiloxane phase (BPX-35, SGE, Courtaboeuf, France). The temperature of the column was initially set at 85◦ C for a period of 1 minute, and then increased at different rates to 280◦ C. Helium was the carrier gas at a constant flow of

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Table 1: Interlaboratory round robin for organotin compounds in sediments. Butyltin species concentration (ng/g) MBT DBT TBT SED 1 (mean value) Measured value SED 2 (mean value) Measured value

111.2 (34%) 126.6 124.7 (50.5%) 93.7

165.3 (19.6%) 168.3 205.3 (19.8%) 247.2

319.2 (13%) 310.3 28.5 (24%) 24.4

1 mL/min. The transfer line was set at 300◦ C with the external ion source at 280◦ C. The ions in EI for the target species were selected and fragmented with helium gas CID in the ion trap. The second-order mass spectra resulting from the most intense fragment were scanned from m/z ion 50 to the mass of the selected ions. The concentrations were calculated using the calibration curves established for each compound in internal standardisation mode with tripropyltin and diheptyltin as internal standards. Organotin compound recoveries for certified reference material (sediment CRM 462 and CRM 646) were in the range of 120–130% for TBT, 90–112% for DBT, 70–89% for MBT, 54–125% for TPT, 77–119% for DPT and 75–100% for MPT. The results of an intercalibration exercise are presented in Table 1.

Metallic Elements Quantification and AQ/AC Sediments were analysed for their contents of the elements Ag, Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sn, Tl and Zn according to guideline DIN 38406 E 29 (DIN 1996) by means of ICP-MS (inductively coupled plasma mass spectrometry, Perkin Elmer Elan 6000 or Finnigan PQ3 for tin) and ICP-OES (inductively coupled plasma optical emission spectroscopy, Perkin Elmer Optima 3000).[7] Therefore, 250 mg of the sediment sample were freeze dried (Alpha 1–4, Christ, Osterode/Harz, Germany), and 6 mL HNO3 (65% subboiled), 2 mL H2 O2 and 1 mL HF (suprapure) were added. Sediments were digested in teflon tubes in a High Performance Microwave Digestion Unit MLS 1200 mega (Microwave Lab Systems GmbH, Leutkirch, Germany), combined with a EM-45/A unit for used air. A rhodium solution (50 µL of a 10 mg/L stock solution each) served as internal standard for ICP-MS analysis. Analytical performance of element quantification was checked by analysis of two standard reference material (SRM)—river sediment 1407–1 and sediment GBW 08301. The obtained results for these analyses showed concentrations in the certified range (Table 2). Instruments were optimised by means of a manganese standard (Kraft, Duisburg, Germany) and subsequent calibration was achieved by ICP multielement standard VI (Merck, Darmstadt, Germany).

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Table 2: Metallic element data of sediment GBW 08301(µg/g dry matter). Element Ni Cu Zn As Cd Pb Co Mn Cr

Certified value

Measured value

32 53 ± 6 251 56 ± 10 2.4 ± 0.3 79 ± 12 16.5 ± 1.5 975 ± 34 90 ± 8

32 51 235 53 2.4 88 14 958 86

Instruments were rinsed with 3% HNO3 (subboiled). Analysis parameters for ICP-MS were as follows: CEM voltage, 3.72 V; plasma 1000 W; argon pressure, 4.4 bar; nebulizer gas flow, 0.93 L/min; plasma gas flow, 0.8 L/min. Analysis parameters for ICP-OES were as follows: plasma, 1200 W; argon pressure, 4–5 bar; argon flow 15 L/min; nebulizer gas flow, 0.7–0.9 L/min; plasma gas flow, 0.8 L/min. Al, Fe and Mn concentrations were determined by ICP-OES. The reported metal concentrations are mean values of four measurements, each of two digestions of a sediment sample.

RESULTS AND DISCUSSION Overview The sediment collected from the sampling sites in the region of the Gulf ´ had various texture. The sediments ranged from sandy material at of Gdansk sites 8, 9, 12, 20–22, 30–33, 40–44, 60, 61, 70, 80, and 81 to muddy sediments relatively rich in organic matter (> 2%) at sites 1–7, 11, 13–15, 50, 51/52, 82, 83, R1 and R2 (Figs. 1–3, Table 3). Some bulk data on concentrations of butyltins (BTs), DDTs (p,p -DDE;  p,p -DDT and p,p -DDD), PCBs and PAHs but also some individual compounds such as tin (Sn), Diuron, Linuron, (DCPU), (DCPMU), Fenarimol and Vinclozolin in sediment from the sites investigated are summarized in Table 3. Generally, amongst organic contaminants PAH concentrations were greater than those of PCBs, DDTs or phenylurea herbicides. As expected, sediments from shipyard and other industrial sites are characterized by high concentrations of tributyltin and its metabolites. In addition, PCBs, some parent PAHs as well as heavy metals were quantified at elevated concentration at some of the sites sampled (Tables 3, 5, 7 and 8). No live benthic fauna

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1 2 3 4 5 6 7 8 9 11 12 13 14 15 20 21 22

Site no.

3.8 10 7.5 8.5 4.9 5.1 2.7 0.4 0.5 11.5 0.5 2.2 7.5 3.9 1.8 1.5 1.7

OM (%)

30 7.2 4.1 2.8 0.64 0.53 0.18 ND ND ND ND ND 0.063 ND ND ND ND

BTs µg/g d.m.∗

38 5.8 5.3 4.2 3.1 2.7 3.2 3.6 0.9 0.3 0.2 0.5 0.9 0.3 0.3 0.4 0.2

Sn µg/g d.m. 34 27 5.4 7.1 6.8 30 0.87 0.16 0.08 0.41 0.17 0.11 0.12 0.09 0.14 0.16 0.26

DDTs ng/g d.m. 420 230 21 52