Marine Pollution Bulletin 48 (2004) 10761083 www.elsevier.

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A survey to determine levels of chlorinated pesticides and PCBs in mussels and seawater from the Mid-Black Sea Coast of Turkey
Perihan Binnur Kurt
a b

a,*

, Hulya Boke Ozkoc

Department of Environmental Engineering, Faculty of Engineering, Akdeniz University, 07200 Topcular, Antalya, Turkey Department of Environmental Engineering, Faculty of Engineering, Ondokuz Mayis University, 55139 Kurupelit, Samsun, Turkey

Abstract A mussel and seawater monitoring survey was conducted at six sampling points between Yalikoy (Ordu) and Sinop in 19992000 along the Mid-Black Sea Coast of Turkey in order to assess concentrations of organochlorine pesticides (OCs) and polychlorinated biphenyls (PCBs). Chlorinated pesticides and PCBs were measured in the mussel Mytilus Galloprovincialis and in seawater. In the mussel samples, the most common pollutants in terms of average concentration per g of wet weight (ww), were DDT (max. 1800 pg/ g ww, min. 240 pg/g ww) and its metabolites DDD (max. 5400 pg/g ww, min. 240 pg/g ww) and DDE (max. 2800 pg/g ww, min. 70 pg/g ww). Also, dieldrin, heptachlor and HCB were notable contaminants in the mussel samples. PCBs were determined in none of the biota or seawater samples. The concentrations of the OCs and PCBs in mussels were higher in coastal areas receiving river discharges and close to the largest city of the region, Samsun (especially in sampling points in the harbour area). The well-known long persistence of DDTs and other chlorinated compounds was conrmed by residues of these pollutants measured in mussels. On the other hand, even though the usage of such kind of persistent compounds in Turkey was banned, there may still be illegal usage and it is not certain whether the application of these compounds did end in the region. 2003 Elsevier Ltd. All rights reserved.
Keywords: Black Sea; Turkey; Mytilus Galloprovincialis; Monitoring; OCs; PCBs

1. Introduction There is widespread concern about chemical pollution reecting increasing population, agricultural activities and industrial development (Travis and Hester, 1991), and the coastal environment is particularly at risk from the eects of these contaminants (Wade et al., 1998). Organisms that live in aquatic environments are suitable representative samples for assessing pollution and mussels are used in many pollution monitoring and assessment studies because: they have world-wide geographical distributions; they are relatively stationary reecting contamination better than mobile species; they can concentrate the chemicals 102 105 times higher than the water they live in (Farrington et al., 1983; Villeneuve
* Corresponding author. Tel.: +44-1524-592578; fax: +44-1524593985 (till July 2005), tel.: +90-242-323-23-64; fax: +90-242-323-2362 (after July 2005). E-mail addresses: p.kurt@lancaster.ac.uk, perihankurt@akdeniz. edu.tr (P.B. Kurt).

et al., 1999) by uptake as they can lter large volumes of water (Kryger and Riisgard, 1998) and remove all seston (suspended particles) between 1 and 250 l (Jorgensen et al., 1984); they have little ability to degrade most chemicals due to lack of necessary enzymes; and they are important for public health due to being prefered food for many people (Farrington et al., 1983; Villeneuve et al., 1999). The mussel Mytilus galloprovincialis, is common along the Black Sea Coast of Turkey due to the low sea water temperature and salinity which are the optimum conditions for life and productivity of M. galloprovincialis (Uysal, 1970). The marine environment of the Black Sea Coast of Turkey has degraded recently due to increased usage of the region, and it has been impossible to estimate the pollution loading in this agricultural and industrial coastal area (Tufekci, 1996). In the past two decades, the Black Sea has been threatened with problems from chlorinated compounds as well as other chemical pollutants (Bakan and Buyukgungor, 2000; Tuncer et al., 1998).

0025-326X/$ - see front matter 2003 Elsevier Ltd. All rights reserved. doi:10.1016/j.marpolbul.2003.12.013

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Transport of various pollutants by many rivers and streams passing from the main agricultural and urban areas of Turkey and other neighbouring countries is the main source of pollution in the Black Sea. From Turkeys side, Kizilirmak and Yesilirmak are probably the main rivers in this pollutant transport, and both of these rivers reach the Black Sea in this study area (Pinarli et al., 1991; Bakan et al., 1996; Bakan and Buyukgungor, 2000; Tuncer et al., 1998). Carsamba and Bafra Basins are the two main agricultural basins of Turkey in the region and these rivers receive many pollutants including pesticides from these basins as well as from the cities which they pass through (Bakan et al., 1996; Tufekci, 1996; Ozkoc et al., 1999; Tuncer et al., 1998). Additionally, due to lack of proper sewage and wastewater treatment systems in most cities in the region, wastewater from these cities has been discharged directly either to these two main rivers or to smaller other rivers or directly to the Black Sea (Pinarli et al., 1991; Bakan et al., 1996; Tufekci, 1996; Tuncer et al., 1998). Due to high annual rainfall in the region, oods result in transport of contaminants from agricultural areas to the sea. Also, due to a high population increase in the region, land-lling along the coast is common, and thus another pollution transport pathway is being created. Important also are atmospheric deposition, global distribution and transportation of chlorinated compounds as well as their persistence and long life cycles, which increase the occurrence of these pollutants in the region (Ozkoc et al., 1999). Because of their environmental persistence, accumulation capacity and toxicity, there is increasing global concerns for chlorinated compounds in the environment and these concerns have led to the gradual reduction of

these compounds all over the world. Production of DDT was reduced in 1960s and after recognition of its environmental hazards, its use was banned in the 1970s in economically developed countries (e.g. it was banned in France in 1975) but it is still being used in many developing countries (especially in African countries). PCB production was reduced slowly in the 1970s in most European countries but PCBs still remain a potential threat (Phillips, 1986; Kruus, 1991; Villeneuve et al., 1999). Although production and usage of many chlorinated compounds such as Dieldrin, Aldrin, Endrin, Chlordane, DDT, BHC, Lindane and Heptachlor were completely banned in Turkey in the 1990s, total pesticide usage in Turkey in 1995 was 37,000 tons, and this usage shows a steady increase year by year (TCV, 1998). Although there are some studies related to organochlorine compounds in the region, data from these studies either concerned mussels from a dierent part of the region (Telli, 1991) or from main rivers as annual uxes (Tuncer et al., 1998). Therefore, this study is important as the beginning of a series of surveys based on the mussel watch concept, and will serve as a guide for future surveys to monitor trends of pollution risk from chlorinated compounds in the Mid-Black Sea Coast of Turkey (Ozkoc et al., 1999).

2. Materials and methods 2.1. Sampling Fig. 1 shows the the sampling points which were located along the Mid-Black Sea Coast of Turkey, from Yalikoy (Ordu) to Sinop. Mussel and sea water samples

Fig. 1. Study area and location of sampling points.

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were collected three times from six sampling points in 1999 and 2000. Composite samples were collected from Sinop and Yalikoy (Ordu) due to an estimated low pollution risk for these contaminants; therefore only one sampling point was conducted in these places. The major study area was the Samsun coast where four sampling points were chosen. Sampling point selections were based on proximity of industrial facilities, sewage discharge and distance from river deltas. One sampling point selected was very close to the Mert River in Samsun, which is the most polluted river passing through the city. Two sampling points were in the harbor area and the last one was very close to a landll site. Sea water sampling was carried out at the same sampling points. Due to fast urban/ industrial development along the coastal area, mussel populations no longer exists at several points on the coast of the region, and the occurrence of mussel populations was of course an important factor in determining sampling points and sampling times. A large number of mussels of similar size (48 cm shell length) were collected from each sampling point. These mussel samples were stored in pre-cleaned aluminium coated containers and transported to the laboratory as soon as possible after collection. In the laboratory, after measuring the width, length and weight (with shell) of each mussel, the mussels were opened with pre-cleaned stainless steel knives; the soft parts were removed and frozen for analysis. The sampling procedure could only be repeated three times in the year because suitably sized mussel samples could not be found. The samples were homogenized and 20 g of samples were analysed for OCs and PCBs following well-established standard techniques of UNEP, IAEA and FAO (UNEP/IOC/IAEA, 1988, 1995, 1996; UNEP/ FAO/IAEA/IOC, 1991; IOC, 1993).

3. Determination of chlorinated pesticides and PCBs in mussel and water samples 3.1. Mussel samples After homogenization of the mussel samples, precleaned anhydrous sodium sulphate was used to remove the water content of the samples. Before the extraction of samples, a pre-extraction procedure was applied to glassware, cellulose extraction thimbles and sodium sulphate using a Soxhlet apparatus. Twenty grams of homogenized mussel samples were mixed with anhydrous sodium sulphate, and then extracted in a Soxhlet apparatus for 8 h using 250 ml of glass distilled 1:1 DCM:hexane mixture. In order to calculate recoveries, all samples were spiked with 25 ng/ml of 2,4,5 TCB (trichlorobiphenyl) and e-HCH as internal standards. An extracted aliquot of 10 ml was also removed for lipid

content analysis. DCM:hexane extracts were concentrated to about 15 ml using a rotary evaporator and they were evaporated to a few milliliters in a water bath (about 70 C). An aliquot of this extract was taken for treatment with concentrated sulphuric acid to destroy lipids. Both aliquots were through the orisil clean-up. Analytes were back extracted with 60 ml of hexane. This extract was evaporated to 1 ml in a water bath and then cleaned-up using orisil chromatography column to separate classes of compounds in dierent fractions as described below. Activated orisil (at 130 C for 12 h) was used to pack a clean-up column. From the orisil column, the rst fraction was obtained by eluting the sample with 70 ml of hexane, this fraction contained mainly PCBs, HCB, DDE and Aldrin. The second fraction was obtained with 50 ml of a freshly prepared mixture of 70:30 hexane:DCM and it contained toxaphene, DDD, DDT, HCH. The third fraction containing Endrin and Dieldrin was eluted with 40 ml of DCM and this fraction was recovered only from the aliquot of the sample extract not treated with concentrated sulphuric acid, since H2 SO4 destroys Dieldrin and Endrin. Forty milliliter of hexane was added to the evaporation ask of the third fraction directly for solvent exchange. A blank sample was prepared using 30 g of pre-cleaned sodium sulphate to determine any contamination during analyses and the same procedures were applied to the blank sample as to mussel samples. All fractions were further concentrated to about 1 ml and analyzed by gas chromatography (Fisons HRGC Mega 2 Series) equipped with an electron capture detector (ECD 800) and a capillary column (DB-5, 30 m long, 0.32 mm id, coated with 0.245 lm lm). The injector temperature was 250 C, the detector at 300 C and the oven programmed from 70 C for 2 min up to 260 C with a range of 3 C per min. The carrier gas was nitrogen with a ow of 2 ml/min and the make-up gas was helium with a ow of 20 ml/min. Added standards included a-, b-, c- and d-BHC, Heptachlor, Aldrin, Heptachlor Epoxide, Endosulphane-I, EndosulphaneII, Endosulphane Sulphate, Endrin, Endrin Aldehite, Dieldrin, Lindane, HCB, pp0 -DDE, pp0 -DDD, pp0 -DDT, Arochlor 1260 and Arochlor 1254. 3.2. Water samples In order to recover compounds of interest, a liquid liquid extraction process was applied to 1 l of water sample with a total of 240 ml of hexane in three steps. Before starting the extraction process, samples were spiked with 25 ng/ml of internal and recovery standards. A blank sample was prepared with 240 ml of hexane. After extraction process, the same clean-up processes as for mussel samples were applied to water sample extracts, except H2 SO4 treatment.

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3.3. Quality control Blanks were included at a rate of one for every ve samples and were treated in exactly the same manner as the samples. Average recoveries of internal standards ranged from 30% to 99% for mussel samples, while it ranged from 40% to 85% for seawater samples. All results are blank and recovery corrected. Detection limit was based on mean blank plus three times the standard deviation of replicate blank analyses. Detection limits were 24 pg/g and 0.2 pg/ml for mussel and seawater samples respectively.

4. Results and discussion Average concentrations of chlorinated pesticides and PCBs in mussel and sea water samples during the study period are shown in Tables 1 and 2 respectively. Many chlorinated pesticides were determined in both types of sample but no PCBs were detected in any sample. Lipid content of mussel samples ranged from 11 to 30 mg/g. In mussel samples, DDT concentration was quite high, ranging from 240 to 1800 pg/g ww and these concentrations depended on the location of sampling. The concentrations of DDE and DDD ranged from 70 to 2800 pg/g ww and from 240 to 5400 pg/g ww respectively. At the end of the analysis, it was observed that DDD and DDE were in higher concentrations than DDT. This result is similar to results in ICES (1974).

DDE especially occurs in higher organisms as a metabolic product. Mussels are in the second step of the food chain in aquatic environment (Alloway and Ayres, 1994), and they obtain their food, mainly plankton, by ltering large amount of water (Uysal, 1970). Thus this result is not very surprising and it also suggests the bioaccumulation of DDT and its conversion to DDD and DDE in metabolism (Roger and Lea, 1972; Villeneuve et al., 1999). The persistent half-life of DDT in aquatic environments has been suggested to be approximately 5 years (Villeneuve et al., 1999) and 1020 years (estimated from studies) on bivalves (Sericano et al., 1990). DDT can be transformed to DDE and DDD slowly in this process (Klumpp et al., 2002). The prohibition of use of DDT in Turkey is considered to be the late 1980s, so it is not surprising to nd very high concentrations of DDT in biota samples. On the other hand, it is thought that there is still continuous input of this compound into marine environment from atmospheric deposition of DDT (Villeneuve and Cattini, 1986) and DDT probably leaches from highly DDT contaminated areas and agricultural soils as well as illegal usage in the region and other countries. Additionally, there may be input from illegal usage of these compounds in the region. DDE, which is the most often recognized metabolite of the DDT is a very slowly degradable compound. Although DDD production is completely banned in the world, it was produced and sold under the name Rothane for several years (Washington State Pest. Mon.

Table 1 Average concentrations of chlorinated pesticides and PCBs in mussels from the Mid-Black Sea Coast of Turkey in 1999 and 2000 Compound a-BHC b-BHC c-BHC d-BHC p; p0 -DDT p; p0 -DDE p; p0 -DDD Dieldrin Endosulfan-I Endosulfan sulphate Endrin Endrin aldehide Heptachlor Heptachlor epoxide HCB Lindane Aldrin Endosulfan-II PCBs Baruthane (1), pg/g wwa 5 12 3 2 290 2800 950 780 4000 5700 180 1300 110 nd 270 130 590 270 nd Yesil Fener (2), pg/g wwa nd 13 18 1 400 300 850 180 nd nd 310 140 20 nd 170 160 nd 2100 nd Kirmizi Fener (3), pg/g wwa 8 70 8 200 240 70 2200 130 600 790 180 420 14 nd nd nd 70 nd nd Belediye Evleri (4), pg/g wwa 600 3900 nd nd 1800 2400 1000 600 16,000 3400 1500 1200 1600 nd nd nd nd 11,000 nd Sinop (5), pg/g wwa 190 22 nd nd 1100 230 240 380 80 nd 190 nd 40 nd 180 120 nd 12 nd Yalikoy (6), pg/g wwa 50 140 nd 30 nd 120 5400 360 20 7 20 3 8 nd nd nd nd 2 nd

Yesil Fener (2) and Kirmizi Fener (3) sampling points are in harbor along Samsun Coast, Baruthane (1) is on west part of Samsun Coast and Belediye Evleri (4) is on east part of Samsun Coast. nd Not detected. a Bolded numbers are below detection limit.

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Table 2 Average concentration of chlorinated pesticides and PCBs in seawater from the Mid-Black Sea Coast of Turkey in 1999 and 2000 Compound a-BHC b-BHC c-BHC d-BHC p; p0 -DDT p; p0 -DDE p; p0 -DDD Endosulfan-I Endosulfan sulphate Endrin Endrin aldehide Heptachlor Heptachlor epoxide HCB Lindane Aldrin Endosulfan-II PCBs Baruthane (1), pg/mla 0.6 7 nd 3 nd nd nd nd nd nd nd 0.7 nd nd nd nd 6 nd Yesil Fener (2), pg/mla nd nd 0.3 nd nd nd nd 0.1 nd nd 0.5 0.2 nd nd nd nd nd nd Kirmizi Fener (3), pg/mla 1 nd nd nd nd nd nd 1 nd nd nd 30 nd 8 nd nd nd nd Belediye Evleri (4), pg/mla nd nd nd nd nd nd nd 15 nd nd nd 1 nd 2 nd nd 2 nd Sinop (5), pg/mla nd nd nd nd nd 1 105 nd nd nd 15 1 nd nd nd nd nd nd Yalikoy (6), pg/mla nd nd nd nd nd nd nd nd nd nd nd 1 nd nd nd nd nd nd

Yesil Fener (2) and Kirmizi Fener (3) sampling points are in harbor along Samsun Coast, Baruthane (1) is on west part of Samsun Coast and Belediye Evleri (4) is on east part of Samsun Coast. nd Not detected. a Bolded numbers are below detection limit.

Prog, 1996). Another reason for high concentrations of DDD and DDE compared to DDT in mussel samples is the metabolism and discharge of DDT from the body of mussels rather than DDD and DDEs (Roger and Lea, 1972; ICES, 1974). Other compounds determined in mussel samples were Dieldrin (max. 780 pg/g ww, min. 180 pg/g ww), Heptachlor (max. 1600 pg/g ww, min. 40 pg/g ww) and HCB (max. 270 pg/g ww, min. 170 pg/g ww). In spite of banning and ending of usage of these compounds in the early 1980s, some compounds such as Heptachlor and Chlordane are still being used to ght termites and ants. Heptachlor is the main constituent of chlordane and it occurs as a result of the degradation of chlordane. HCB occurs as a result of degradation of some compounds such as Lindane and therefore it is not surprising to nd HCB in an environment where Lindane is present. HCB has also been produced as a by-product and in its own right (Washington State Pest. Mon. Prog, 1996). In Table 3, a comparison is given of results with other similar survey results for mussels. According to the results of this study, the concentrations of chlorinated pesticides in mussels in the Mid-Black Sea Coast of Turkey are much higher than concentrations in mussels obtained from similar studies in other parts of the world. Also, as it is seen from Fig. 2, Human Health Criteria and Wild Life Criteria of EPA are exceeded in most of the sampling points for dierent chlorinated compounds. Especially, DDT and its metabolites DDE P and DDD and BHCs concentrations are noticeably high compared to other similar surveys (Table 3) and

EPA criteria (Fig. 2AD respectively) and this conrms the long life and persistence of these compounds in the environment and also the observed high concentration of DDTs can be assigned as a sign of the continuing illegal usage of DDT in the region as reported by Tuncer et al. (1998). Although concentrations of Dieldrin and HCB (Fig. 2E and F respectively) are not as high as the concentrations of DDT and its metabolites, values are still higher than EPA criteria. PCB pollution was not observed in any of the sampling points. Unfortunately, the kind of survey reported here for chlorinated compounds has not been carried out previously in the Mid-Black Sea region for the same sampling area. Therefore, there is no data to compare these results with in order to assess the trend of pollution in the region. Although there are similar surveys reported for chlorinated compounds, one of these surveys (Telli, 1991) was carried out in mussel and sea water in a different area in the Black Sea and the other study (Tuncer et al., 1998) was carried out in rivers in the region giving the annual pollutants uxes. There is no doubt that it would be better if the same sampling points were used in both surveys to get a time trend of these pollutants. But, the same sampling points as those of Telli (1991) could not be included in this study due to long distance and limited budget of the study. Due to lack of a previous dataset from a survey for the same sampling area, results could not be compared with each other to determine past contamination or to estimate a trend. In water samples, heptachlor was the chlorinated compound with the highest concentration of max. 30

P.B. Kurt, H.B. Ozkoc / Marine Pollution Bulletin 48 (2004) 10761083 Table 3 Comparison of study results with similar study results from dierent geographical locations Study area Baruthane (1) Yes il Fener (2) Kirmizi Fener (3) Belediye Evleri (4) Sinop (5) Yalikoy (6) Owen Anchorageb Rawsonc Punto Loyolac Punto Banderasc Deer Islandc Staten Islandc Boston Horbourd North Seae Western Scheldte P p; p0 -DDT, pg/g wwa 290 400 240 1800 1100 nd 2 p; p0 -DDE, pg/g wwa 2800 300 70 2400 230 120 p; p0 -DDD, pg/g wwa 950 850 2200 1000 240 5400

1081

P DDTs, pg/g wwa 4040 1550 2510 5200 1570 5520 2.02 2.91 59.58 73.32 119.41 78

BHC, pg/g wwa 22 32 290 4500 4712 220 6.99 2.65 6.59 2.7 3.16

116

68 240

P BHC a-BHC b-BHC d-BHC c-BHC. DDTs p; p0 -DDT p; p0 -DDD p; p0 -DDE; nd Not detected. a Bolded numbers are below detection limit. b Burt and Ebell (1995). c Report of Woods Hole Oceanographic Institution Coastal Research Center (1995). d Lauenstein (1995). e Cited in Cleemann et al. (2000).

pg/ml and min. 0.2 pg/ml. Other compounds were not found because these compounds are hydrophobic and tend to accumulate in fatty tissue of organisms and in sediments. Therefore, concentrations of chlorinated compounds in water are lower than the concentrations in organisms and sediments (Alloway and Ayres, 1994). No PCBs were found in both seawater and mussel samples. These high concentrations of chlorinated compounds can be considered to be evidence of heavy contamination of chlorinated compounds for the region in both past and present times. Chlorinated pesticides as a certain class of persistent organic pollutants have long biochemical half-lives in the environment. For instance, the biochemical half-life of DDT in the environment is at least 15 years (Carvalho et al., 1996; EEA, 2002). The results of the study are not surprising when long halflives of these compounds in the environment are considered. On the other hand, due to continued atmospheric depositions from remote sources to the Mediterranean and Black Sea as well as other regions of the world, leaching from heavily chlorinated compounds used and contaminated agricultural areas, concentrations of these compounds are very high and it can be concluded from the results that these concentrations will remain at measurable levels for several years. In water samples, concentrations of the pollutants were very low compared to the mussel samples. This result conrms that these compounds are hydrophobic and tend to accumulate in fatty tissue of organisms and also in sediments (Chau and Afghan, 1982; Alloway and Ayres, 1994; Bioaccumulation, 1997).

The whole Black Sea region receives a very heavy pollution load and this is increasing over time. While people are polluting the sea and coastal area in the region, they also consume sh, mussels and other sea organisms as food. When the increasing accumulation potential of these compounds in the food chain is considered, it is clear that humans are the most aected organisms in the food chain. Although mussels are not preferred seafood for Turkish people, the detected level of contamination can still be a threat for public health since sh is the most common preferred seafood in the region. In 1999, the amount of annual mussel (Mediterranean mussel) production in the Black Sea region was 1600 t/a and annual export of mussel of Mytilus spp. and Perna spp. from the whole country was 0.15 and 10 t/a respectively. As seen from the statistics, total mussel catch in the region is not as much as other European countries. However, catch of sh is nearly 300 times of catch of mussel in the region. (Fisheries Statistics, 1999). When the place of sh in aquatic food chain is taken into account, it is obvious that this kind of pollution in the region is very important for public health. Since there was no data on catch of M. galloprovincialis in the region, it did not seem very meaningful to calculate the tolerable daily intake (TDI) value using these statistics and to correlate the results with public health. Because of important environmental and human health based reasons, more coastal water and marine organisms watch programs (i.e. mussel watch programs) must be carried out comprising the whole Black Sea Coast of Turkey as well as other countries of the Black

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pp'-DDT 2000 1800 2500 1500 C (pg/g-ww) 1100 1000 EPA Wild Life EPA Human Criteria Health Criteria 200 pg/g-ww 32 pg/g-ww 400 290 240 C (pg/g-ww) 2000 1500 1000 500 0
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Fig. 2. Average concentrations of OCs (pg/g ww) in mussels and comparison with EPA criteria.

Sea. We hope that this study will be a starting point for such kind of assessment and monitoring studies to determine the level of pollution from chlorinated compounds in the region.

their feedback. We are grateful to Dr. Feryal Ozturk Akbal (Ondokuz Mayis University) for her endless help and patience, and also thanks to all other people at the Department of Environmental Engineering of Akdeniz University and Ondokuz Mayis University for their support. References
Alloway, B.J., Ayres, D.C., 1994. Chemical Principles of Environmental Pollution. University of Reading and University of London. Bakan, G., Buyukgungor, H., 2000. The Black Sea. Marine Pollution Bulletin 41 (16), 2443.

Acknowledgements The authors are indebted to Dr. Jean Pierre Villeneuve (training ocer in IAEA-MEL) and IAEA for their help in supplying related papers, pesticide standards and experimental apparatus. We also would like to thank to Prof. Kevin C. Jones (Lancaster University), and Dr. Gareth O. Thomas (Lancaster University) for

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