PAH, PCB and OCP concentrations in the sediments, local mussels, transplanted mussels and passive samplers in the İstanbul Strait and Marmara Sea, Turkey O. S. Okay1, B.Karacık1, B. Henkelman2, K-W.Schramm2,3 1Istanbul Technical University, Faculty of Naval Architecture and Ocean Engineering, 34469, Maslak, İstanbul, Turkey 2Helmholtz Zentrum München, Research Center for Environmental Health, Institute of Ecological Chemistry, Ingolstädter Landstrasse 1, 85764 Neuherberg, Germany 3TUM, Wissenschaftszentrum Weihenstephan für Ernährung und Landnutzung, Department für Biowissenschaften, Weihenstephaner Steig 23, 85350 Freising, Germany E-mail contact: [email protected] 1. Introduction Polycyclic aromatic hydrocarbons (PAHs) and persistent organic pollutants (POPs) are accumulated in several matrices of the aquatic environments and have several negative effects on the organisms [1] Most lipophilic anthropogenic organics tend to be associated to the suspended particles in the water column due to their low solubility and accumulate in the sediments [2]. They also accumulate in fish and shell fish especially in mussels and may lead to serious human health hazards [3]. In this study, the surface sediments and mussels were collected from and transplanted mussels and passive samplers (SPMDs and butyl rubber sorbents; BRs) were deployed to the five sites in the İstanbul Strait and Marmara Sea. The samples were then analyzed for PAHs, polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs). The results of the analysis for several matrices were compared. The previous monitoring studies carried out in the İstanbul Strait ecosystem showed that it was contaminated by those pollutants [4,5]. The Strait is a part of the Turkish Strait system connecting the Black Sea to the Medditerranean and one of the busiest waterways in the world. Passive samplers have been developed to monitor organic pollutants and frequently used in several monitoring studies. Lipid-containing semipermeable membrane devices (SPMDs) have been most commonly utilized as passive samplers. Butyl rubber sorbents synthesized to remove the organic pollutants and oil spills from the aquatic environments were used in this study as a passive sampler and the efficiency of the sorbents were compared with the SPMDs [6]. 2. Materials and methods Surface sediments (0-10 cm) and mussels (Mytilus galloprovincialis; 4-5 cm) were collected from five coastal stations in the Istanbul strait and Marmara Sea and transferred to the laboratory in foam boxes filled with ice. Mussels were dissected in the laboratory, and transferred into the vials. Samples were frozen at - 20oC until analysis. SPMDs were prepared from 29 cm x 2.5 cm low-density polyethylene lay- flat (LDPE) tubing (VWR Ismaning, Germany) with a membrane thickness of approximately 65 µm. The triolein- containing part of the sampler - excluding the mounting loops- has a surface area of 115 cm2. 700 µL of triolein (Sigma, Munich, Germany, 99 %) was spiked with performance reference compounds The prepared SPMDs were stored in closely aluminum sealed heat cleaned 10 mL glass vials, further stored at -20 oC and kept cooled during transportation until deployment. SPMDs, butyl rubber sorbents and mussels were deployed with specially designed stainles steel cages and in nets respectively. The samplers and mussels were retrieved from the sites after 7 and 21 days of deployment, carried to the laboratory and stored at - 20oC until analysis. After extraction and clean-up processes, the samples were analyzed with a high resolution mass spectrometer Finnigan MAT 95S (Thermo Electron GmbH, Bremen, Germany) coupled with an Agilent GC 6890 (Agilent Technologies, Palo Alto, CA, USA). 3. Results and discussion Maximum sediment T-PAH concentration was measured at site 24 (6431 ng/g). This site is situated at the coast of the main shipyard area of Turkey. Local mussels at sites 12 and 24 do not exist. Among the other sampling sites, the highest mussel T-PAH concentration (201 ng/g) was determined at site 6a which is the mouth of a creek entering site 6. The local and transplanted mussels have nearly the same T-PAH concentrations both after 7 and 21 days of deployment. However, passive samplers have higher T-PAH concentrations. The lower amounts of T-PAH concentrations in mussels compared to the passive samplers show that T-PAHs could be metabolized by the mussels. The T-PAH values of the passive samplers after 21 days of deployment were higher compared to the values measured after 21 days of deployment. The maximum sediment (25602 ng/g) and local mussel (881 ng/g) T-PCB concentrations were measured at site 6. In general, the differences in the concentrations of the local mussel, transplanted mussels and passive samplers were not significant. This shows that the PCB compounds could not be metabolized as the PAH compounds by the mussels. The accumulation of PCBs by the BR sorbents were not efficient as in case of PAHs. When SPMDs and BR sorbents were compared, the accumulation of PCB congeners in SPMDs were found much higher compared to the BR sorbents. Among the PCBs, the indicator PCBs were the dominant congeners in all matrices. The percentage of indicator PCBs were different in sediments and mussels. For example at site 6, the percentage of indicator PCBs were 80%, whereas that value was 90% in sediments. None of the non-ortho and mono-ortho PCB congeners were measured at site 12 which is one of the pristine sites in the Strait situated at the Black Sea entrance. OCP concentrations were only measured in sediments (113974 ng/g) and transplanted mussels (7 days: 14370 ng/g and 21 days: 38261 ng/g). The highest concentrations were measured at site 24. The most dominant OCP compounds were HCH and DDT derivatives. DDT concentrations in sediments were higher compared to the concentrations in mussels. 4. Conclusions The results of the study show that some of the sites in the Strait are highly polluted by the analyzed pollutants and especially the levels in the mussels may be hazordous for the human health. The necessary precautions should be taken for mussel consumption from those contaminated areas. The compared efficiencies of passive samplers indicate that BR sorbents may also be used as passive samplers for PAHs. 5. References [1] Kolonkaya D. 2006. Organochlorine pesticide reidues and their toxic effects on the environment and organisms in Turkey, Intern. J. Environ. Anal. Chem 86:147-160. [2] Hong SH, Yim UH, Shim WJ, Li DH, Oh JR. 2006. Nationwide monitoring of polychlorinated biphenyls and organochlorine pesticides in sediments from coastal environment of Korea, Chemosphere 64:1479- 1488. [3] Yang N, Matsuda M, Kawano M, Wakimoto T. 2006. PCBs and organochlorine pesticides (OCPs) in edible fish and shellfish from China, Chemosphere 63:1342-1352. [4] Karacık B, Okay OS, Henkelmann B, Bernhöft S, Schramm K-W. 2009. Polycyclic aromatic hydrocarbons and effects on marine organisms in the Istanbul strait. Environ Int 35:599-606. [5] Okay OS, Karacık B, Henkelmann B, Bernhöft S, Schramm K-W. 2009. PCB and PCDD/F in sediments and mussels of the Istanbul Strait (Turkey). Chemosphere 76:159-166. [6]Ceylan D, Doğu S, Karacık B, Yakan S, Okay OS, Okay O. 2009. Evaluation of butyl rubber as sorbent material for the removal of oil and polycyclic aromatic hydrocarbons from seawater. Environ Sci Technol 43:3846-3852. Acknowledgement - This research has been supported by The Scientific and Technological Research Council of Turkey (TÜBİTAK) and International Bureau of the Federal Ministry of Education and Research, Germany through a Joint Research Project (Project nos: 106Y302 in Turkey and TUR 06/007 in Germany) Equilibrium Sampling of Environmental Pollutants in Baltic Sea Sediment along a Transect in the Stockholm Archipelago Annika Jahnke1, Philipp Mayer2 and Michael S. McLachlan1 1 Department of Applied Environmental Science (ITM), Stockholm University, SE-10691 Stockholm, Sweden 2 Department of Environmental Science, Aarhus University, DK-4000 Roskilde, Denmark E-mail contact: [email protected] 1. Introduction The determination of the fugacity, freely dissolved concentration (Cfree) or chemical activity of environmental pollutants in sediment is important since sediment is the dominant exposure medium for bottom-dwelling organisms and therefore is particularly relevant in a bioaccumulation context. Further, sediment represents a reservoir for numerous hydrophobic organic chemicals (HOCs) in the aquatic environment, and the chemical activity in the sediment can govern the chemical activity in the water column. Especially the small-grained material often has a high storage capacity for HOCs due to its large fraction of organic carbon (OC). We differentiate between accumulation (A) sediment with >75% water content and high fractions of OC and thus pollutants and erosion/transport (E/T) sediment with lower water content that often is relatively coarse with lower percentages of OC and pollutants. To measure Cfree of HOCs such as polychlorinated biphenyls (PCBs), a polymer is brought into contact with the sediment and removed after equilibrium between the two phases has been established. The silicone rubber polydimethylsiloxane (PDMS) is an all-round sampling phase that can be applied in complex matrices [1]. Here we used a coated glass jar method [2,3]. The aim of this study was to investigate Cfree of PCBs in paired A and E/T sediment samples from the Baltic Sea, collected along a gradient from central Stockholm towards the middle of