- Email: [email protected]
Heavy metals in organisms and sediments from Turkish Coast of the Black Sea, 1997–1998
Environment International 27 (2002) 521 – 526 www.elsevier.com/locate/envint
Heavy metals in organisms and sediments from Turkish Coast of the Black Sea, 1997–1998 S. Topcuog˘lu*, C¸. Kırbas¸og˘lu, N. Gu¨ngo¨r C¸ekmece Nuclear Research and Training Center, P.O. Box 1, Atatu¨rk Airport, 34831 Istanbul, Turkey Received 10 December 2000; accepted 27 July 2001
Abstract During the period 1997 – 1998, macroalgae, sea snail, mussel, fish and sediment samples were collected at different stations of the Turkish Black Sea coast in order to establish the concentration of selected heavy metals. Heavy metals analyzed were Cd, Co, Cr, Ni, Zn, Fe, Mn, Pb and Cu. The results showed that the Turkish Black Sea coast is facing heavy metal pollution. The metal concentrations in macroalgae, sea snail, mussel and sediment samples are very high. However, Cd, Pb and Cu concentrations in anchovy fish decreased, while Co, Fe, Zn, Cr, Mn and Ni contents had changed when compared previous data. The metal levels in macroalgae did not follow the same pattern as concentrations in sediments at the same station. On the other hand, concentrations of Cd, Co, Cr, Zn, Fe, Mn and Cu in sea snail, mussel and fish samples were related to sediment data in the examined stations. D 2002 Elsevier Science Ltd. All rights reserved.
1. Introduction Contaminants such as metals are introduced into the Black Sea through rivers or direct discharge of industrial wastes and agricultural and municipal usage. Moreover, the metal levels in the Black Sea have increased due to oil pollution and airborne contaminants. About 60% of the petroleum hydrocarbons in the Turkish Black Sea coast during the period of 1980 and 1995 came from spill and discharges related to marine transportation and ballast wastes in hundreds barrels that had been dumped irresponsibly by foreign ships (Topcuog˘lu et al., 1990a). In one study, the concentrations of many elements in airborne particles were found to be a factor of two higher in the western part of the Black Sea compared to the corresponding concentrations in the eastern part (Hacisalihoglu et al., 1992). This study also showed that Europe is the dominant source of anthropogenic metals in the Black Sea atmosphere. In an earlier study, Polikarpov et al. (1994) indicated that the quality of river and sewage waters has been changed during the period of 1980 and 1990. As a result, the concentration of the metals has also increased in river and sewage waters delivered to the Black Sea. Heavy metals in aquatic envir-
onment can remain in solution or in suspension and precipitate on the bottom or be taken up by organisms. The analysis of metal concentrations in biota samples at the same locations can indicate the transfer of metals through food chains. Some papers have been published concerning heavy metal levels observed in macroalgae (Gu¨ven et al., 1992, 1998; Topcuog˘lu et al., 1998), sea snails (Topcuog˘lu et al., 1994), mussels (Topcuog˘lu et al., 1998), fish (Topcuog˘lu et al., 1990b, 1995a) and sediment samples (Topcuog˘lu et al., 1995b; Gu¨ven et al., 1998) at the Turkish Black Sea Coast. Moreover, the heavy metal contamination in Turkish Black Sea marine environment has been reviewed in another report (UNEP, 1998). The objectives of this paper are to examine the concentration selected heavy metals in marine organisms and sediments at different stations during 1997 and 1998, to compare heavy metal concentrations in any trophic level and to examine the relation of heavy metals in organism and sediment to land use in the Turkish Coast of the Black Sea. In addition, the present results are compared with the similar studies that have been carried out in the region.
2. Materials and methods * Correspoding author. Tel.: +90-212-548-4050; fax: +90-212-5482230. E-mail address: [email protected] (S. Topcuog˘lu).
The sampling stations of biota and sediment samples in Turkish Coast of the Black Sea are shown in Fig. 1. The
0160-4120/02/$ – see front matter D 2002 Elsevier Science Ltd. All rights reserved. PII: S 0 1 6 0 - 4 1 2 0 ( 0 1 ) 0 0 0 9 9 - X
522
S. Topcuog˘lu et al. / Environment International 27 (2002) 521–526
Fig. 1. The sampling stations and surface currents in the Black Sea.
macroalgae species were Ulva lactuca (green alga) and Cystoseria barbata (brown algae). About 200 g of fresh weigh were harvested at low tide. The algae samples were washed in seawater at the sampling station and transferred to the laboratory under refrigerated conditions. After their arrival at the laboratory, they were rinsed in seawater to remove sand and other contaminating materials. Lastly, samples were rinsed in distilled water. They then were dried at 85 C (to constant weight) and then homogenized. The samples were kept away from metallic materials to avoid contamination. Immediately after collection, sea snail, mussel and fish samples were stored on ice in an insulated box and transferred to the laboratory and then were frozen at 21 C until required for metal analysis. The species of the organisms and related specifications are given in Table 1. Prior to metal analysis, all the soft part and muscle tissue for each sea snail (10 – 12 cm shell length) and all the soft part of each mussel (7 – 8 cm shell length) was dissected. The muscle samples of the fish were prepared from the tail part of the fish. The samples were pooled and freeze-dried for 7– 10 days to a constant weight. About 4 cm of the top of sediment samples were collected within the same 20– 40 m reach at each station using a Lenz Bottom Sampler. The collected sediment was composed and sieved in the field and the < 63 m size fraction was kept for heavy metal analysis. They then were stored in plastic cups that were cleaned by 1:1 HCl and 1:1 HNO3 until analysis. About 100 g of sediment samples were dried at 85 C for 48 h, crushed and homogenized prior of the analysis. Five g of the biota sample were transferred into a 250-ml glass beaker. Firstly, 5 ml of concentrated H2SO4 were added
on the sample and the beaker placed the hot plate at 70 –80 C. After 15 min, a small amount of the concentrated HNO3 was added very slowly and continued heating at 120 C. When the sample solution became liquid, hydrogen peroxide was added and continued heating at the same temperature for 30 min. The hydrogen peroxide was added until the sample remained clear for 2 h at 150 C. After that, the sample was diluted to 100 ml with 2% HNO3 in a volumetric flask. One gram of the sediment sample was dissolved in concentrated nitric acid in a Teflon beaker and small amount of hydrofluoric acid was added. The other procedure was followed as biota sample. The accuracy of the analysis was verified by analyzing the IAEA’s certified reference materials, SL-1 and lake sediment, by the same procedure used for the samples. The heavy metal concentrations were determined by atomic Table 1 Sea snail, mussel and fish samples analyzed
Name Sea snail
Scientific name
Rapana venosa Mussel Mytilus galloprovincialis Anchovy fish Engraulis encrasiocolus Shad fish Alosa bulgarica Whiting fish Merlangius euxinus Bass fish Dicentrarchus labrax
Weight ratio Weight ratio dry/wet dry/wet Number of in muscle in soft part samples * 0.27 ± 0.02
0.29 ± 0.02
8
0.13 ± 0.02
40
0.33 ± 0.03
24
0.19 ± 0.02
8
0.22 ± 0.02
20
0.24 ± 0.01
3
* Minimum number for each result.
S. Topcuog˘lu et al. / Environment International 27 (2002) 521–526 Table 2 Heavy metal concentrations ( mg g ˙Ig˘neada Feb. 1998
1
523
dry wt) in macroalgae species Kilyos Mar. 1998
Sinop Dec. 1997
Pers¸embe Dec. 1997
Metal
C. barbata
U. lactuca
C. barbata
U. lactuca
C. barbata
U. lactuca
C. barbata
Cd Co Cr Ni Zn Fe Mn Pb Cu
6.41 ± 0.02 < 0.05 < 0.06 10.66 ± 0.84 94.9 ± 0.2 869 ± 9 46.79 ± 0.19 < 0.5 12.74 ± 0.06
< 0.02 < 0.05 < 0.06 7.85 ± 0.18 76.6 ± 0.2 1929 ± 9 45.96 ± 0.14 < 0.5 10.47 ± 0.09
< 0.02 2.08 ± 0.29 5.42 ± 0.49 8.20 ± 0.27 105.5 ± 0.2 511 ± 3 71.93 ± 0.28 < 0.5 8.94 ± 0.03
< 0.02 3.97 ± 1.76 < 0.06 8.76 ± 0.05 122.9 ± 0.2 494 ± 16 54.03 ± 0.05 < 0.5 8.93 ± 0.08
< 0.02 < 0.05 7.76 ± 0.55 10.35 ± 0.05 111.4 ± 0.1 427 ± 3 79.95 ± 0.32 < 0.5 8.62 ± 0.08
< 0.02 < 0.05 < 0.06 8.97 ± 0.42 72.75 ± 0.2 1127 ± 6 82.18 ± 0.57 < 0.5 9.93 ± 0.10
< 0.02 < 0.05 < 0.06 8.44 ± 0.25 44.26 ± 0.1 310 ± 1 19.37 ± 0.08 < 0.5 7.33 ± 0.04
absorption spectrophotometer (Varian, Model Spectra AA 100/200). Values are expressed as the mean of three analyses for each sample. Errors were calculated from standard deviations of the absorbencies.
3. Results The metal contents of algae are shown in Table 2. The Cd and Cr concentrations are higher in C. barbata species than U. lactuca species collected from the same stations. On the other hand, the Co level in U. lactuca at Kilyos station is higher than that the brown algae species. No comparison could be made regarding the other heavy metal concentrations of the algae species. The maximum concentrations of Cd, Ni, Fe, Cu and Co, Zn and Cr, Mn in algae samples were found at I˙g˘neada, Kilyos and Sinop, respectively. The result also showed that the Pers¸embe algae was less polluted than those at ˙Ig˘neada, Kilyos and Sinop. The heavy metal concentrations in the sea snail and mussel samples are presented in Tables 3 and 4. The patterns of heavy metals occurrences in muscle tissues of sea snail and mussel samples in order of decreasing contents were Pb > Cr > Cd > Mn > Ni > Co > Cu > Fe > Zn > for R. venosa and Pb > Co > Cd > Cr > Cu > Mn > Ni > Zn > Fe > for M. galloprovincialis. The heavy metal occurrences were in the order Pb > Co > Cr > Ni > Mn > Cd > Cu > Zn > Fe > for soft part of sea snail samples. These results showed that the orders of the metal levels changed between these two organisms and the soft part and muscle of the sea snail samples. The heavy metal concentrations in soft parts of sea Table 3 Heavy metal concentrations (mg g
1
snail were generally higher than muscle tissues of the same organism. However, Co and Cu concentrations were found significantly higher in muscle tissue than the soft part of sea snail collected from the Rize station. The Ni concentration was also high in muscle tissue of the sea snail in Rize station. At the same time, Cu, Co and Ni concentrations were higher in mussel species collected from the Rize station than other stations. On the other hand, the Zn, Cd and Pb were detected higher levels in Amasra mussel samples. The data for heavy metals in fish species are presented in Table 5. With the exceptional Ni difference was observed in the concentration of the metals in anchovy fish samples collected from western and eastern Black Sea stations. The Ni concentration of anchovy fish sample collected from Pers¸embe station during 1997 was much higher than other fish samples. But, the heavy metal concentrations in anchovy fish were not significantly changed from 1997 to 1998 at the same station. The Cd, Co, Cr, Ni and Pb concentrations in other fish samples, except bass, were found below the detection limit. The Zn, Fe and Mn concentrations in all fish samples were similar. However, Cu levels were much higher in shad fish and whiting fish collected from the I˙g˘neada and Rize stations. Lead was detected only in the Pers¸embe anchovy fish sample. The heavy metal concentrations in sediments are shown in Table 6. The Co, Fe, Mn and Cu concentrations decreased from I˙g˘neada to Kilyos and increased from Amasra to Rize. No correlation could be made regarding Cd, Cr, Ni, Zn and Pb in sediment samples collected from the stations. However, the maximum concentrations of Co, Zn, Fe, Mn, Cu and Cr, Ni in sediment samples were found in Rize and
dry wt) in sea snail samples
Stations
Samples
Cd
Co
Cr
Ni
Zn
Fe
Mn
Pb
Cu
R. Feneri Mar. 1998
Soft part Muscle Soft part Muscle Soft part Muscle Soft part Muscle
41.13 ± 0.08 1.78 ± 0.04 15.59 ± 0.07 2.19 ± 0.02 2.01 ± 0.03 0.37 ± 0.03 30.69 ± 0.15 < 0.02
< 0.05 < 0.05 0.5 ± 0.19 0.2 ± 0.10 0.7 ± 0.19 0.3 ± 0.05 < 0.05 6.9 ± 4.4
< 0.06 < 0.06 0.73 ± 0.40 0.62 ± 0.04 1.45 ± 0.04 0.47 ± 0.01 < 0.06 < 0.06
3.74 ± 0.08 < 0.01 < 0.01 < 0.01 1.17 ± 0.29 < 0.01 3.74 ± 0.59 5.83 ± 0.92
230.4 ± 0.9 202.2 ± 0.4 255.9 ± 0.8 40.6 ± 0.2 73.3 ± 0.9 44.6 ± 0.1 200.9 ± 0.6 68.3 ± 0.3
550 ± 3 138 ± 1 134 ± 1 27 ± 1 87 ± 4 98 ± 1 170 ± 1 99 ± 2
10.01 ± 0.05 5.53 ± 0.03 3.90 ± 0.04 1.94 ± 0.01 6.80 ± 0.06 3.48 ± 0.03 4.45 ± 0.04 3.61 ± 0.09
< 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5
41.02 ± 0.01 8.34 ± 0.01 36.19 ± 0.03 17.01 ± 0.03 72.20 ± 0.28 35.02 ± 0.14 47.44 ± 0.21 57.83 ± 0.19
Amasra Dec. 1997 Pers¸embe Dec. 1997 Rize Jun. 1998
524
S. Topcuog˘lu et al. / Environment International 27 (2002) 521–526
Table 4 Heavy metal concentrations (mg g Metal I˙g˘neada Feb. 1998 Cd Co Cr Ni Zn Fe Mn Pb Cu
1
3.25 ± 0.06 < 0.05 < 0.06 6.66 ± 0.44 233.4 ± 0.7 151 ± 1 6.21 ± 0.02 < 0.05 9.07 ± 0.01
dry wt) in mussel samples Kilyos Mar. 1998
R.Feneri Mar. 1998
Amasra Dec. 1997
2.76 ± 0.01 4.89 ± 1.83 < 0.06 11.08 ± 0.64 134.8 ± 0.8 574 ± 1 11.84 ± 0.04 < 0.05 7.21 ± 0.01
2.60 ± 0.06 < 0.05 < 0.06 4.97 ± 0.34 174.5 ± 0.7 256 ± 2 8.12 ± 0.02 < 0.05 8.12 ± 0.02
6.44 ± 0.01 2.68 ± 0.11 7.58 ± 0.28 4.17 ± 0.25 512.5 ± 2.6 355 ± 1 10.11 ± 0.05 2.60 ± 1.1 7.26 ± 0.02
Sinop stations, respectively. The Pb concentration was high in Pers¸embe station. These results indicate that Rize and ˙Ig˘neada sediments are more polluted than those at Kilyos, Amasra, Sinop and Pers¸embe.
4. Discussion Concentrations of some heavy metals in macroalgae species have been reported for the Black Sea (Gu¨ven et al., 1992, 1998; Topcuog˘lu et al., 1998) and Bosphorus (Kut et al., 2000) for C. barbata and U. lactuca. In present study, Cd in C. barbata at I˙g˘neada, Co in C. barbata and U. lactuca at Kilyos and Cr in C. barbata at Kilyos and Sinop stations are higher than were found in the same species and same locations in the previous studies. The concentrations of the metals are also higher than Bosphorus region. Moreover, Cu contents in the algae species in the present study are dramatically increased relative previous results for samples collected before 1994. On the other hand, Pb concentrations decreased during the past 5 years after preventative measures were enforced by the Turkish Coast Guard for discharging ballast and bilge water from ships. It is not possible to compare concentrations reported from other marine environments with those reported here. The wide variations of metal concentrations observed due to seasonal changes and to the chemical – physical characteristic of the sampling sites (Favero et al., 1996). Moreover, the influence of the systematic position and chemical composition of algae species on the uptake of metals have been investigated by many authors (Sivalingam, 1978; Topcuog˘lu and Fowler, 1984). Table 5 Heavy metal concentrations (mg g
1
Sinop Dec. 1997 1.79 ± 0.01 1.79 ± 0.01 2.20 ± 0.06 4.02 ± 0.19 256.4 ± 1.3 598 ± 7 22.8 ± 0.11 0.31 ± 0.19 8.01 ± 0.02
Rize Jun. 1998 < 0.02 5.36 ± 0.33 < 0.06 24.07 ± 0.26 78.12 ± 0.15 511 ± 3 5.66 ± 0.07 < 0.05 11.52 ± 0.02
In a previous study, the heavy metal concentrations were investigated in muscle tissue of sea snail collected from the Bosphorus and eastern Black Sea region during 1987 and 1988 (Topcuog˘lu et al., 1994). Their results indicated that the metal concentrations were higher in the Bosphorus than the Black Sea (except Ni). Contrary to the early findings, the Co, Cr and Cu concentrations are higher in the Black Sea stations than Bosphorus station (R. Feneri). When comparing the previous results with the presented in the Black Sea the Cd, Co, Cr, Ni, Zn and Mn concentrations increased, Pb decreased and Cu concentrations not changed during past 10 years. Comparison of the data in Table 4 shows that heavy metal levels in mussel samples at R. Feneri are lower than other stations. This result also showed that the Bosphorus region was less polluted than Turkish Black Sea coast. On the other hand, Zn, Fe and Cr concentrations in mussel at Kilyos station in the present study significantly decreased than the concentrations for the mussel collected from the Kilyos in 1993 (Topcuog˘lu et al., 1998). However, Co concentration not changed during past 5 years. In general, the concentrations of Mn, Cu and Cd in mussels collected from the Romanian Black Sea coast agree well with the present result (Bologa et al., 1988). Only in the case of our Cu data was the opposite trend noted. The present data for all stations indicates that Cu concentration tended to increase in all organisms during 1997 and 1998. The Cu concentrations of the mussel samples at the different stations of the Black Sea are similar to those reported for coastal area of Saronikos Gulf in Aegean Sea and other Mediterranean areas (Bei et al., 1998; UNEP, 1996). The fish production of Turkey from the Black Sea in 1995 was 442,000 tones annually (TSI, 1997). More than 80% of the fish caught is anchovy. The heavy metal levels in
dry wt) in fish samples
Stations
Samples
Cd
Co
Cr
Ni
Zn
Fe
Mn
Pb
Cu
I˙g˘neada Amasra Pers¸embe
Shad Feb. 1998 Anchovy Dec. 1997 Anchovy Dec. 1997 Bass Dec. 1997 Anchovy Dec. 1998 Whiting Dec. 1998 Whiting Jun. 1998
< 0.02 0.10 ± 0.01 0.16 ± 0.04 0.24 ± 0.02 0.15 ± 0.03 < 0.02 < 0.02
< 0.05 0.40 ± 0.18 0.24 ± 0.02 0.24 ± 0.13 0.30 ± 0.08 < 0.05 < 0.05
< 0.06 0.33 ± 0.02 0.84 ± 0.59 0.18 ± 0.01 0.76 ± 0.44 < 0.06 < 0.06
< 0.01 < 0.01 2.04 ± 0.25 0.06 ± 0.03 < 0.01 < 0.01 < 0.01
26.4 ± 0.2 35.7 ± 0.4 40.3 ± 0.1 25.7 ± 0.1 44.2 ± 0.2 43.1 ± 0.1 30.2 ± 0.1
48 ± 1 44 ± 1 37 ± 1 30 ± 1 61 ± 1 57 ± 1 46 ± 1
1.47 ± 0.02 2.23 ± 0.03 1.81 ± 0.03 0.69 ± 0.01 2.99 ± 0.05 3.56 ± 0.09 2.22 ± 0.04
< 0.05 < 0.05 0.6 ± 0.1 < 0.05 < 0.05 < 0.05 < 0.05
4.23 ± 0.10 2.21 ± 0.11 2.81 ± 0.02 1.01 ± 0.02 3.09 ± 0.05 1.86 ± 0.04 4.54 ± 0.11
Rize
S. Topcuog˘lu et al. / Environment International 27 (2002) 521–526 Table 6 Heavy metal concentrations (mg g
1
525
dry wt) in sediment samples
Stations
Cd
Co
Cr
Ni
Zn
Fe %
Mn
Pb
Cu
I˙g˘neada Feb. 1998 Kilyos Mar. 1998 Amasra Dec. 1997 Sinop Dec. 1997 Pers¸embe Dec. 1997 Rize Jun. 1998
< 0.02 < 0.02 0.73 ± 0.08 0.89 ± 0.11 0.93 ± 0.04 < 0.02
21.45 ± 4.44 < 0.05 8.28 ± 0.51 13.40 ± 0.71 16.8 ± 0.97 36.44 ± 10.5
74.7 ± 1.4 10.8 ± 0.2 58.5 ± 0.4 115.5 ± 0.5 21.8 ± 0.1 38.88 ± 0.34
31.57 ± 0.51 13.55 ± 0.38 33.50 ± 0.77 65.20 ± 0.71 18.50 ± 0.22 37.26 ± 0.38
119.3 ± 0.7 33.9 ± 0.1 92.6 ± 0.37 91.5 ± 0.45 82.9 ± 0.16 267.4 ± 0.26
2.9 0.5 2.7 3.5 4.4 5.4
519.1 ± 4.5 206.6 ± 1.0 338.2 ± 0.3 424.3 ± 1.3 514.1 ± 1.1 870.3 ± 3.5
< 0.05 < 0.05 21.4 ± 5.6 15.1 ± 2.9 31.1 ± 2.0 < 0.05
13.57 ± 0.08 4.00 ± 0.02 27.60 ± 0.24 37.3 ± 0.14 69.9 ± 0.20 95.5 ± 0.19
anchovy and some fish species in the Black Sea have been investigated during the period of 1987 –1989 (Topcuog˘lu et al., 1990b, 1995a). The results presented above clearly indicated that Cd, Pb and Cu concentrations in anchovy fish are slightly decreased, but Co, Fe, Zn, Cr, Mn and Ni concentrations have not changed when compared with the previous data. At the same time, the heavy metal concentrations in shad, bass and whiting fish samples are generally lower than goatfish, red mullet and turbot fish collected from the Igneada, Sinop and Trabzon regions during 1987. The heavy metal concentrations in several fish species from the Mamaia Bay of the Romanian Black Sea sector were determined by Bologa et al. (1988). The range of metal concentrations were as follows: Mn, 4.47 – 5.85; Fe, 52– 86– 66.18; Cu, 12.24 – 17.86; Cd, 13.62– 16.77 and Pb, 4.01– 5.56 mg g 1 (dry wt). This ranges in the present data are: Mn, 0.69 – 3.56; Fe, 37 – 61; Cu, 1.01 – 4.54; Cd, < 0.02– 0.24 and Pb, < 0.05– 0.6 mg g 1. Much lower concentrations of Mn, Cu, Cd and Pb were found at the stations of the Turkish Black Sea region. Recently, no similar published data in scientific literature from the Black Sea. For this reason, it is impossible to write any conclusion about metal levels in the Black Sea fish. At the same time, the comparison of heavy metal concentrations in fish with other studies carried out in different marine environments are also difficult because of differences in fish species, types of tissue analyzed, methodologies and other factors. The concentrations of Co, Cr, Zn and Fe in sediment samples at the Kilyos, Riva, S¸ile and Sinop stations were investigated after collected in 1993 (Topcuog˘lu et al., 1995b; Gu¨ven et al., 1998). When compared the results at the Kilyos and Sinop stations of the previous studies with the presented findings Cr and Zn and Co, Zn and Fe levels seemed increased, respectively. On the other hand, Co and Cr concentrations in Kilyos and S¸ile stations are decreased. The heavy metal levels in the Bosphorus and Marmara Sea sediments were also investigated during the period of 1990– 1994 (Gu¨ven et al., 1992; Esen et al., 1999; Kut et al., 2000). The Cd and Pb concentrations in the sediment samples of the present study were lower than the Bosphorus sediments. The Mn concentration is high than Bosphorus sediment. In general, the Co, Cr, Ni, Zn, Fe and Cu in our results are higher in Igneada, Sinop, Persembe and Rize stations than Bosphorus and Marmara Sea sediments. The Cr concentration in Sinop station sediment indicated that this area was heavily polluted and approaching the
‘‘severe effect level’’ when compared with the Sediment Quality Guidelines of the Ontario Ministry (Persaud et al., 1992). The concentrations of Mn, Pb and Cu in the sediment samples in this study are generally higher than the concentrations found in the northern sector of the Romanian marine environment (Bologa et al., 1988), while Cd, Pb and Cu concentrations are lower than in the sediment collected from the southern sector. The macroalgae and mussel species are most extensively used for monitoring heavy metal contamination in estuarine and seashore areas. There are no published data for use of sea snail as indicator in metal pollution. The previous study indicated that the use of the sea snail species for monitoring of heavy metals on the shoreline of the Black sea marine environment would be valuable tool (Onat and Topcuog˘lu, 1999). The regional variations in heavy metal concentrations among the Black Sea stations were evident in all species examined beside of the sediment results. At the same time, we found significant differences in heavy metal concentrations in different organisms at the same stations. On the other hand, some authors have noted no differences between the metal concentrations in similar organisms in the same area (Fowler, 1986). Heavy metals in the near shore sediments in the eastern Black Sea that might be related to agricultural and industrial activities of the region specially from mining practices. At the same time, elevated concentrations of some heavy metals can be related to geology of the sediment source. On the other hand, the heavy metal concentrations in the western Black Sea region influenced by the rivers and atmospheric precipitation. Furthermore, Heiny and Tate (1997) indicated that the concentrations of trace elements in fish tissue are also related to concentrations of elements in sediment. Heavy metal levels in macroalgae did not follow the same patterns as concentrations in sediment at the same station. On the other hand, concentrations of Cd, Co, Cr, Zn, Fe, Mn and Cu in sea snail, mussel and fish samples related to sediment results in the examined stations.
5. Conclusion The results presented above clearly demonstrated that the Turkish Black Sea coast is facing heavy metal pollution. The metal concentrations in macroalgae, sea snail, mussel and sediment samples are very high. On the other hand,
526
S. Topcuog˘lu et al. / Environment International 27 (2002) 521–526
some heavy metal levels decreased in fish species specially anchovy fish. Moreover, lead concentrations in biota samples found below detection limit after preventive measures were enforced by the Turkish Coastal Guard for discharging ballast and bilge waters from ship. Acknowledgments Thanks are due to IAEA projects (Research Contract No. 9712/RO and Technical Co-operation Contract No. TUR/2/012) for supporting samples collection and instrumental assistance. We also thank to I˙. Akkurt for this valuable assistance. References Bei F, Catsiki VA, Strongyloudi E. Seasonal and spatial variation of Cu, Cr, Ni and Pb concentrations in Mytillus galloprovincialis of Saronikos Gulf, Greece. Rapp Comm Int Mer Me´dit 1998;35:230 – 1. Bologa AS, Apas M, Cociasu A, Cuingioglu E, Patrascu V, Piescu I, Popa L. Present level of contaminants in Romanian Black Sea Sector Marine pollution. Proceeding of a symposium held in Monaco, 5 – 9 Oct. 1998. IAEA SM-354/26: 58 – 63; 1988. Esen N, Topcuog˘lu S, Eg˘illi E, Kut D. Comparison of trace metal concentrations in sediments and algae samples from the Ku¨c¸u¨kc¸ekmece Lagoon and Marmara Sea. 1999;240(2):673 – 676. Favero N, Cattalini F, Bertaggia D, Albergoni V. Metal accumulation in a biological indicator (Ulva rigida) from the lagoon of Venice (Italy). Arch Environ Contam Toxicol 1996;31:9 – 18. Fowler SW. Trace metal monitoring of pelagic organisms from the open Mediterranean sea. Environ Monit Assess 1986;7:59 – 78. Gu¨ven KC, Topcuog˘lu S, Kut D, Esen N, Erentu¨rk N, Saygı N, Cevher E, ¨ ztu¨rk B. Metal uptake by Black Sea algae. Bot Mar Gu¨vener B, O 1992;35:337 – 40. Gu¨ven KC, Okus¸ E, Topcuog˘lu S, Esen N, Ku¨c¸kcezzar R, Seddigh E, Kut D. Heavy metal accumulation in algae and sediments of the Black Sea Coast of Turkey. Toxicol Environ Chem 1998;67:435 – 40. ¨ lmez I˙, Balkas TI, Tuncel G. Chemical Hacisalihog˘lu G, Eliyakut F, O composition of particles in the Black Sea atmosphere. Atmos Environ 1992;264:3207 – 18.
Heiny JS, Tate CM. Concentration, distribution, and comparison of selected trace elements in bed sediment and fish tissue in the South Platte River basin, USA, 1992 – 1993. Arch Environ Contam Toxicol 1997;32: 246 – 59. Kut D, Topcuog˘lu S, Esen N, Ku¨c¸u¨kcezzar R, Gu¨ven KC. Trace metals in marine algae and sediment samples from the Bosphorus. Water, Air, Soil Pollut 2000;118:27 – 33. Onat B, Topcuog˘lu S. A laboratory study of Zn and 134 Cs depuration by the sea snail (Rapana venosa). J Environ Radioact 1999;46:201 – 6. Persaud D, Jaagumagi R, Hayton A. Guidelines for the protection and management of aquatic sediment quality in Ontario. Log 92-2309067, PIBS 1962, Queen’s Printer for Ontario, 1992. Polikarpov GG, Zaitsev YP, Zats VI, Radchenko LA. Pollution of the Black Sea (levels and sources). In: Gu¨ven KC, editor. Proceedings of the Black Sea Symposium, 16 – 18 Sep. 1991, I˙stanbul. 1994;15 – 42. Sivalingam PM. Biodeposited trace metals and mineral content studies of some tropical marine algae. Bot Mar 1978;21:327 – 30. Topcuog˘lu S, Fowler SW. Factors affecting the biokinetics of technetium (95mTc) in marine macroalgae. Mar Environ Res 1984;12:25 – 43. Topcuog˘lu S, Saygı N, Erentu¨rk N, Bulut AM. The toxicity study in barrel wastes thrown into the Black Sea Report of C¸ekmece Nuclear Research and Training Center, AR-276, 1990a (in Turkish). Topcuog˘lu S, Erentu¨rk N, Saygı N, Kut D, Esen N, Ba˛sari A, Seddigh E. Trace metal levels of fish from the Marmara and Black Sea. Toxicol Environ Chem 1990b;29:95 – 9. Topcuog˘lu S, Erentu¨rk N, Esen N, Saygı N, Kut D, Seddigh E, Bas˛sari A. The toxic element levels in oyster and sea snail. J Sci Fac Ege Univ, Ser B 1994;16(1):239 – 41 (in Turkish). Topcuog˘lu S, Kut D, Erentu¨rk N, Esen N, Saygı N. Some element levels in anchovy, bluefish, Atlantic mackerel and dolphin. Tr J Eng Environ Sci 1995a;19:307 – 10 (in Turkish). Topcuog˘lu S, Kut D, Esen N, Ku¨c¸u¨kcezzar R. Radioactivity and trace element levels in sediments of the Black Sea. Rapp Comm Int Mer Me´dit 1995b;34:232. Topcuog˘lu S, Esen N, Eg˘illi E, Gu¨ngo¨r N, Kut, D. Trace elements and 1137 Cs in macroalgae and mussel from the Kilyos in Black Sea. In: International Symposium on Marine Pollution, Monaco, 5 – 9 Oct. 1998, IAEA-SM-354/30, 1998;283 – 284. TSI (Turkish Statistic Institute). Statistic of Water Products. ISBN 1003 – 6177, 1997 (in Turkish). UNEP. Assessment of the state of pollution of the Mediterranean Sea by zinc, copper and their compounds. MAP Tech Rep Ser 1996;105: 65 – 70. UNEP. Black Sea biological diversity Turkey. Black Sea Environ Ser 1998;9:56 – 62.
Heavy metals in organisms and sediments from Turkish Coast of the Black Sea, 1997–1998 S. Topcuog˘lu*, C¸. Kırbas¸og˘lu, N. Gu¨ngo¨r C¸ekmece Nuclear Research and Training Center, P.O. Box 1, Atatu¨rk Airport, 34831 Istanbul, Turkey Received 10 December 2000; accepted 27 July 2001
Abstract During the period 1997 – 1998, macroalgae, sea snail, mussel, fish and sediment samples were collected at different stations of the Turkish Black Sea coast in order to establish the concentration of selected heavy metals. Heavy metals analyzed were Cd, Co, Cr, Ni, Zn, Fe, Mn, Pb and Cu. The results showed that the Turkish Black Sea coast is facing heavy metal pollution. The metal concentrations in macroalgae, sea snail, mussel and sediment samples are very high. However, Cd, Pb and Cu concentrations in anchovy fish decreased, while Co, Fe, Zn, Cr, Mn and Ni contents had changed when compared previous data. The metal levels in macroalgae did not follow the same pattern as concentrations in sediments at the same station. On the other hand, concentrations of Cd, Co, Cr, Zn, Fe, Mn and Cu in sea snail, mussel and fish samples were related to sediment data in the examined stations. D 2002 Elsevier Science Ltd. All rights reserved.
1. Introduction Contaminants such as metals are introduced into the Black Sea through rivers or direct discharge of industrial wastes and agricultural and municipal usage. Moreover, the metal levels in the Black Sea have increased due to oil pollution and airborne contaminants. About 60% of the petroleum hydrocarbons in the Turkish Black Sea coast during the period of 1980 and 1995 came from spill and discharges related to marine transportation and ballast wastes in hundreds barrels that had been dumped irresponsibly by foreign ships (Topcuog˘lu et al., 1990a). In one study, the concentrations of many elements in airborne particles were found to be a factor of two higher in the western part of the Black Sea compared to the corresponding concentrations in the eastern part (Hacisalihoglu et al., 1992). This study also showed that Europe is the dominant source of anthropogenic metals in the Black Sea atmosphere. In an earlier study, Polikarpov et al. (1994) indicated that the quality of river and sewage waters has been changed during the period of 1980 and 1990. As a result, the concentration of the metals has also increased in river and sewage waters delivered to the Black Sea. Heavy metals in aquatic envir-
onment can remain in solution or in suspension and precipitate on the bottom or be taken up by organisms. The analysis of metal concentrations in biota samples at the same locations can indicate the transfer of metals through food chains. Some papers have been published concerning heavy metal levels observed in macroalgae (Gu¨ven et al., 1992, 1998; Topcuog˘lu et al., 1998), sea snails (Topcuog˘lu et al., 1994), mussels (Topcuog˘lu et al., 1998), fish (Topcuog˘lu et al., 1990b, 1995a) and sediment samples (Topcuog˘lu et al., 1995b; Gu¨ven et al., 1998) at the Turkish Black Sea Coast. Moreover, the heavy metal contamination in Turkish Black Sea marine environment has been reviewed in another report (UNEP, 1998). The objectives of this paper are to examine the concentration selected heavy metals in marine organisms and sediments at different stations during 1997 and 1998, to compare heavy metal concentrations in any trophic level and to examine the relation of heavy metals in organism and sediment to land use in the Turkish Coast of the Black Sea. In addition, the present results are compared with the similar studies that have been carried out in the region.
2. Materials and methods * Correspoding author. Tel.: +90-212-548-4050; fax: +90-212-5482230. E-mail address: [email protected] (S. Topcuog˘lu).
The sampling stations of biota and sediment samples in Turkish Coast of the Black Sea are shown in Fig. 1. The
0160-4120/02/$ – see front matter D 2002 Elsevier Science Ltd. All rights reserved. PII: S 0 1 6 0 - 4 1 2 0 ( 0 1 ) 0 0 0 9 9 - X
522
S. Topcuog˘lu et al. / Environment International 27 (2002) 521–526
Fig. 1. The sampling stations and surface currents in the Black Sea.
macroalgae species were Ulva lactuca (green alga) and Cystoseria barbata (brown algae). About 200 g of fresh weigh were harvested at low tide. The algae samples were washed in seawater at the sampling station and transferred to the laboratory under refrigerated conditions. After their arrival at the laboratory, they were rinsed in seawater to remove sand and other contaminating materials. Lastly, samples were rinsed in distilled water. They then were dried at 85 C (to constant weight) and then homogenized. The samples were kept away from metallic materials to avoid contamination. Immediately after collection, sea snail, mussel and fish samples were stored on ice in an insulated box and transferred to the laboratory and then were frozen at 21 C until required for metal analysis. The species of the organisms and related specifications are given in Table 1. Prior to metal analysis, all the soft part and muscle tissue for each sea snail (10 – 12 cm shell length) and all the soft part of each mussel (7 – 8 cm shell length) was dissected. The muscle samples of the fish were prepared from the tail part of the fish. The samples were pooled and freeze-dried for 7– 10 days to a constant weight. About 4 cm of the top of sediment samples were collected within the same 20– 40 m reach at each station using a Lenz Bottom Sampler. The collected sediment was composed and sieved in the field and the < 63 m size fraction was kept for heavy metal analysis. They then were stored in plastic cups that were cleaned by 1:1 HCl and 1:1 HNO3 until analysis. About 100 g of sediment samples were dried at 85 C for 48 h, crushed and homogenized prior of the analysis. Five g of the biota sample were transferred into a 250-ml glass beaker. Firstly, 5 ml of concentrated H2SO4 were added
on the sample and the beaker placed the hot plate at 70 –80 C. After 15 min, a small amount of the concentrated HNO3 was added very slowly and continued heating at 120 C. When the sample solution became liquid, hydrogen peroxide was added and continued heating at the same temperature for 30 min. The hydrogen peroxide was added until the sample remained clear for 2 h at 150 C. After that, the sample was diluted to 100 ml with 2% HNO3 in a volumetric flask. One gram of the sediment sample was dissolved in concentrated nitric acid in a Teflon beaker and small amount of hydrofluoric acid was added. The other procedure was followed as biota sample. The accuracy of the analysis was verified by analyzing the IAEA’s certified reference materials, SL-1 and lake sediment, by the same procedure used for the samples. The heavy metal concentrations were determined by atomic Table 1 Sea snail, mussel and fish samples analyzed
Name Sea snail
Scientific name
Rapana venosa Mussel Mytilus galloprovincialis Anchovy fish Engraulis encrasiocolus Shad fish Alosa bulgarica Whiting fish Merlangius euxinus Bass fish Dicentrarchus labrax
Weight ratio Weight ratio dry/wet dry/wet Number of in muscle in soft part samples * 0.27 ± 0.02
0.29 ± 0.02
8
0.13 ± 0.02
40
0.33 ± 0.03
24
0.19 ± 0.02
8
0.22 ± 0.02
20
0.24 ± 0.01
3
* Minimum number for each result.
S. Topcuog˘lu et al. / Environment International 27 (2002) 521–526 Table 2 Heavy metal concentrations ( mg g ˙Ig˘neada Feb. 1998
1
523
dry wt) in macroalgae species Kilyos Mar. 1998
Sinop Dec. 1997
Pers¸embe Dec. 1997
Metal
C. barbata
U. lactuca
C. barbata
U. lactuca
C. barbata
U. lactuca
C. barbata
Cd Co Cr Ni Zn Fe Mn Pb Cu
6.41 ± 0.02 < 0.05 < 0.06 10.66 ± 0.84 94.9 ± 0.2 869 ± 9 46.79 ± 0.19 < 0.5 12.74 ± 0.06
< 0.02 < 0.05 < 0.06 7.85 ± 0.18 76.6 ± 0.2 1929 ± 9 45.96 ± 0.14 < 0.5 10.47 ± 0.09
< 0.02 2.08 ± 0.29 5.42 ± 0.49 8.20 ± 0.27 105.5 ± 0.2 511 ± 3 71.93 ± 0.28 < 0.5 8.94 ± 0.03
< 0.02 3.97 ± 1.76 < 0.06 8.76 ± 0.05 122.9 ± 0.2 494 ± 16 54.03 ± 0.05 < 0.5 8.93 ± 0.08
< 0.02 < 0.05 7.76 ± 0.55 10.35 ± 0.05 111.4 ± 0.1 427 ± 3 79.95 ± 0.32 < 0.5 8.62 ± 0.08
< 0.02 < 0.05 < 0.06 8.97 ± 0.42 72.75 ± 0.2 1127 ± 6 82.18 ± 0.57 < 0.5 9.93 ± 0.10
< 0.02 < 0.05 < 0.06 8.44 ± 0.25 44.26 ± 0.1 310 ± 1 19.37 ± 0.08 < 0.5 7.33 ± 0.04
absorption spectrophotometer (Varian, Model Spectra AA 100/200). Values are expressed as the mean of three analyses for each sample. Errors were calculated from standard deviations of the absorbencies.
3. Results The metal contents of algae are shown in Table 2. The Cd and Cr concentrations are higher in C. barbata species than U. lactuca species collected from the same stations. On the other hand, the Co level in U. lactuca at Kilyos station is higher than that the brown algae species. No comparison could be made regarding the other heavy metal concentrations of the algae species. The maximum concentrations of Cd, Ni, Fe, Cu and Co, Zn and Cr, Mn in algae samples were found at I˙g˘neada, Kilyos and Sinop, respectively. The result also showed that the Pers¸embe algae was less polluted than those at ˙Ig˘neada, Kilyos and Sinop. The heavy metal concentrations in the sea snail and mussel samples are presented in Tables 3 and 4. The patterns of heavy metals occurrences in muscle tissues of sea snail and mussel samples in order of decreasing contents were Pb > Cr > Cd > Mn > Ni > Co > Cu > Fe > Zn > for R. venosa and Pb > Co > Cd > Cr > Cu > Mn > Ni > Zn > Fe > for M. galloprovincialis. The heavy metal occurrences were in the order Pb > Co > Cr > Ni > Mn > Cd > Cu > Zn > Fe > for soft part of sea snail samples. These results showed that the orders of the metal levels changed between these two organisms and the soft part and muscle of the sea snail samples. The heavy metal concentrations in soft parts of sea Table 3 Heavy metal concentrations (mg g
1
snail were generally higher than muscle tissues of the same organism. However, Co and Cu concentrations were found significantly higher in muscle tissue than the soft part of sea snail collected from the Rize station. The Ni concentration was also high in muscle tissue of the sea snail in Rize station. At the same time, Cu, Co and Ni concentrations were higher in mussel species collected from the Rize station than other stations. On the other hand, the Zn, Cd and Pb were detected higher levels in Amasra mussel samples. The data for heavy metals in fish species are presented in Table 5. With the exceptional Ni difference was observed in the concentration of the metals in anchovy fish samples collected from western and eastern Black Sea stations. The Ni concentration of anchovy fish sample collected from Pers¸embe station during 1997 was much higher than other fish samples. But, the heavy metal concentrations in anchovy fish were not significantly changed from 1997 to 1998 at the same station. The Cd, Co, Cr, Ni and Pb concentrations in other fish samples, except bass, were found below the detection limit. The Zn, Fe and Mn concentrations in all fish samples were similar. However, Cu levels were much higher in shad fish and whiting fish collected from the I˙g˘neada and Rize stations. Lead was detected only in the Pers¸embe anchovy fish sample. The heavy metal concentrations in sediments are shown in Table 6. The Co, Fe, Mn and Cu concentrations decreased from I˙g˘neada to Kilyos and increased from Amasra to Rize. No correlation could be made regarding Cd, Cr, Ni, Zn and Pb in sediment samples collected from the stations. However, the maximum concentrations of Co, Zn, Fe, Mn, Cu and Cr, Ni in sediment samples were found in Rize and
dry wt) in sea snail samples
Stations
Samples
Cd
Co
Cr
Ni
Zn
Fe
Mn
Pb
Cu
R. Feneri Mar. 1998
Soft part Muscle Soft part Muscle Soft part Muscle Soft part Muscle
41.13 ± 0.08 1.78 ± 0.04 15.59 ± 0.07 2.19 ± 0.02 2.01 ± 0.03 0.37 ± 0.03 30.69 ± 0.15 < 0.02
< 0.05 < 0.05 0.5 ± 0.19 0.2 ± 0.10 0.7 ± 0.19 0.3 ± 0.05 < 0.05 6.9 ± 4.4
< 0.06 < 0.06 0.73 ± 0.40 0.62 ± 0.04 1.45 ± 0.04 0.47 ± 0.01 < 0.06 < 0.06
3.74 ± 0.08 < 0.01 < 0.01 < 0.01 1.17 ± 0.29 < 0.01 3.74 ± 0.59 5.83 ± 0.92
230.4 ± 0.9 202.2 ± 0.4 255.9 ± 0.8 40.6 ± 0.2 73.3 ± 0.9 44.6 ± 0.1 200.9 ± 0.6 68.3 ± 0.3
550 ± 3 138 ± 1 134 ± 1 27 ± 1 87 ± 4 98 ± 1 170 ± 1 99 ± 2
10.01 ± 0.05 5.53 ± 0.03 3.90 ± 0.04 1.94 ± 0.01 6.80 ± 0.06 3.48 ± 0.03 4.45 ± 0.04 3.61 ± 0.09
< 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5
41.02 ± 0.01 8.34 ± 0.01 36.19 ± 0.03 17.01 ± 0.03 72.20 ± 0.28 35.02 ± 0.14 47.44 ± 0.21 57.83 ± 0.19
Amasra Dec. 1997 Pers¸embe Dec. 1997 Rize Jun. 1998
524
S. Topcuog˘lu et al. / Environment International 27 (2002) 521–526
Table 4 Heavy metal concentrations (mg g Metal I˙g˘neada Feb. 1998 Cd Co Cr Ni Zn Fe Mn Pb Cu
1
3.25 ± 0.06 < 0.05 < 0.06 6.66 ± 0.44 233.4 ± 0.7 151 ± 1 6.21 ± 0.02 < 0.05 9.07 ± 0.01
dry wt) in mussel samples Kilyos Mar. 1998
R.Feneri Mar. 1998
Amasra Dec. 1997
2.76 ± 0.01 4.89 ± 1.83 < 0.06 11.08 ± 0.64 134.8 ± 0.8 574 ± 1 11.84 ± 0.04 < 0.05 7.21 ± 0.01
2.60 ± 0.06 < 0.05 < 0.06 4.97 ± 0.34 174.5 ± 0.7 256 ± 2 8.12 ± 0.02 < 0.05 8.12 ± 0.02
6.44 ± 0.01 2.68 ± 0.11 7.58 ± 0.28 4.17 ± 0.25 512.5 ± 2.6 355 ± 1 10.11 ± 0.05 2.60 ± 1.1 7.26 ± 0.02
Sinop stations, respectively. The Pb concentration was high in Pers¸embe station. These results indicate that Rize and ˙Ig˘neada sediments are more polluted than those at Kilyos, Amasra, Sinop and Pers¸embe.
4. Discussion Concentrations of some heavy metals in macroalgae species have been reported for the Black Sea (Gu¨ven et al., 1992, 1998; Topcuog˘lu et al., 1998) and Bosphorus (Kut et al., 2000) for C. barbata and U. lactuca. In present study, Cd in C. barbata at I˙g˘neada, Co in C. barbata and U. lactuca at Kilyos and Cr in C. barbata at Kilyos and Sinop stations are higher than were found in the same species and same locations in the previous studies. The concentrations of the metals are also higher than Bosphorus region. Moreover, Cu contents in the algae species in the present study are dramatically increased relative previous results for samples collected before 1994. On the other hand, Pb concentrations decreased during the past 5 years after preventative measures were enforced by the Turkish Coast Guard for discharging ballast and bilge water from ships. It is not possible to compare concentrations reported from other marine environments with those reported here. The wide variations of metal concentrations observed due to seasonal changes and to the chemical – physical characteristic of the sampling sites (Favero et al., 1996). Moreover, the influence of the systematic position and chemical composition of algae species on the uptake of metals have been investigated by many authors (Sivalingam, 1978; Topcuog˘lu and Fowler, 1984). Table 5 Heavy metal concentrations (mg g
1
Sinop Dec. 1997 1.79 ± 0.01 1.79 ± 0.01 2.20 ± 0.06 4.02 ± 0.19 256.4 ± 1.3 598 ± 7 22.8 ± 0.11 0.31 ± 0.19 8.01 ± 0.02
Rize Jun. 1998 < 0.02 5.36 ± 0.33 < 0.06 24.07 ± 0.26 78.12 ± 0.15 511 ± 3 5.66 ± 0.07 < 0.05 11.52 ± 0.02
In a previous study, the heavy metal concentrations were investigated in muscle tissue of sea snail collected from the Bosphorus and eastern Black Sea region during 1987 and 1988 (Topcuog˘lu et al., 1994). Their results indicated that the metal concentrations were higher in the Bosphorus than the Black Sea (except Ni). Contrary to the early findings, the Co, Cr and Cu concentrations are higher in the Black Sea stations than Bosphorus station (R. Feneri). When comparing the previous results with the presented in the Black Sea the Cd, Co, Cr, Ni, Zn and Mn concentrations increased, Pb decreased and Cu concentrations not changed during past 10 years. Comparison of the data in Table 4 shows that heavy metal levels in mussel samples at R. Feneri are lower than other stations. This result also showed that the Bosphorus region was less polluted than Turkish Black Sea coast. On the other hand, Zn, Fe and Cr concentrations in mussel at Kilyos station in the present study significantly decreased than the concentrations for the mussel collected from the Kilyos in 1993 (Topcuog˘lu et al., 1998). However, Co concentration not changed during past 5 years. In general, the concentrations of Mn, Cu and Cd in mussels collected from the Romanian Black Sea coast agree well with the present result (Bologa et al., 1988). Only in the case of our Cu data was the opposite trend noted. The present data for all stations indicates that Cu concentration tended to increase in all organisms during 1997 and 1998. The Cu concentrations of the mussel samples at the different stations of the Black Sea are similar to those reported for coastal area of Saronikos Gulf in Aegean Sea and other Mediterranean areas (Bei et al., 1998; UNEP, 1996). The fish production of Turkey from the Black Sea in 1995 was 442,000 tones annually (TSI, 1997). More than 80% of the fish caught is anchovy. The heavy metal levels in
dry wt) in fish samples
Stations
Samples
Cd
Co
Cr
Ni
Zn
Fe
Mn
Pb
Cu
I˙g˘neada Amasra Pers¸embe
Shad Feb. 1998 Anchovy Dec. 1997 Anchovy Dec. 1997 Bass Dec. 1997 Anchovy Dec. 1998 Whiting Dec. 1998 Whiting Jun. 1998
< 0.02 0.10 ± 0.01 0.16 ± 0.04 0.24 ± 0.02 0.15 ± 0.03 < 0.02 < 0.02
< 0.05 0.40 ± 0.18 0.24 ± 0.02 0.24 ± 0.13 0.30 ± 0.08 < 0.05 < 0.05
< 0.06 0.33 ± 0.02 0.84 ± 0.59 0.18 ± 0.01 0.76 ± 0.44 < 0.06 < 0.06
< 0.01 < 0.01 2.04 ± 0.25 0.06 ± 0.03 < 0.01 < 0.01 < 0.01
26.4 ± 0.2 35.7 ± 0.4 40.3 ± 0.1 25.7 ± 0.1 44.2 ± 0.2 43.1 ± 0.1 30.2 ± 0.1
48 ± 1 44 ± 1 37 ± 1 30 ± 1 61 ± 1 57 ± 1 46 ± 1
1.47 ± 0.02 2.23 ± 0.03 1.81 ± 0.03 0.69 ± 0.01 2.99 ± 0.05 3.56 ± 0.09 2.22 ± 0.04
< 0.05 < 0.05 0.6 ± 0.1 < 0.05 < 0.05 < 0.05 < 0.05
4.23 ± 0.10 2.21 ± 0.11 2.81 ± 0.02 1.01 ± 0.02 3.09 ± 0.05 1.86 ± 0.04 4.54 ± 0.11
Rize
S. Topcuog˘lu et al. / Environment International 27 (2002) 521–526 Table 6 Heavy metal concentrations (mg g
1
525
dry wt) in sediment samples
Stations
Cd
Co
Cr
Ni
Zn
Fe %
Mn
Pb
Cu
I˙g˘neada Feb. 1998 Kilyos Mar. 1998 Amasra Dec. 1997 Sinop Dec. 1997 Pers¸embe Dec. 1997 Rize Jun. 1998
< 0.02 < 0.02 0.73 ± 0.08 0.89 ± 0.11 0.93 ± 0.04 < 0.02
21.45 ± 4.44 < 0.05 8.28 ± 0.51 13.40 ± 0.71 16.8 ± 0.97 36.44 ± 10.5
74.7 ± 1.4 10.8 ± 0.2 58.5 ± 0.4 115.5 ± 0.5 21.8 ± 0.1 38.88 ± 0.34
31.57 ± 0.51 13.55 ± 0.38 33.50 ± 0.77 65.20 ± 0.71 18.50 ± 0.22 37.26 ± 0.38
119.3 ± 0.7 33.9 ± 0.1 92.6 ± 0.37 91.5 ± 0.45 82.9 ± 0.16 267.4 ± 0.26
2.9 0.5 2.7 3.5 4.4 5.4
519.1 ± 4.5 206.6 ± 1.0 338.2 ± 0.3 424.3 ± 1.3 514.1 ± 1.1 870.3 ± 3.5
< 0.05 < 0.05 21.4 ± 5.6 15.1 ± 2.9 31.1 ± 2.0 < 0.05
13.57 ± 0.08 4.00 ± 0.02 27.60 ± 0.24 37.3 ± 0.14 69.9 ± 0.20 95.5 ± 0.19
anchovy and some fish species in the Black Sea have been investigated during the period of 1987 –1989 (Topcuog˘lu et al., 1990b, 1995a). The results presented above clearly indicated that Cd, Pb and Cu concentrations in anchovy fish are slightly decreased, but Co, Fe, Zn, Cr, Mn and Ni concentrations have not changed when compared with the previous data. At the same time, the heavy metal concentrations in shad, bass and whiting fish samples are generally lower than goatfish, red mullet and turbot fish collected from the Igneada, Sinop and Trabzon regions during 1987. The heavy metal concentrations in several fish species from the Mamaia Bay of the Romanian Black Sea sector were determined by Bologa et al. (1988). The range of metal concentrations were as follows: Mn, 4.47 – 5.85; Fe, 52– 86– 66.18; Cu, 12.24 – 17.86; Cd, 13.62– 16.77 and Pb, 4.01– 5.56 mg g 1 (dry wt). This ranges in the present data are: Mn, 0.69 – 3.56; Fe, 37 – 61; Cu, 1.01 – 4.54; Cd, < 0.02– 0.24 and Pb, < 0.05– 0.6 mg g 1. Much lower concentrations of Mn, Cu, Cd and Pb were found at the stations of the Turkish Black Sea region. Recently, no similar published data in scientific literature from the Black Sea. For this reason, it is impossible to write any conclusion about metal levels in the Black Sea fish. At the same time, the comparison of heavy metal concentrations in fish with other studies carried out in different marine environments are also difficult because of differences in fish species, types of tissue analyzed, methodologies and other factors. The concentrations of Co, Cr, Zn and Fe in sediment samples at the Kilyos, Riva, S¸ile and Sinop stations were investigated after collected in 1993 (Topcuog˘lu et al., 1995b; Gu¨ven et al., 1998). When compared the results at the Kilyos and Sinop stations of the previous studies with the presented findings Cr and Zn and Co, Zn and Fe levels seemed increased, respectively. On the other hand, Co and Cr concentrations in Kilyos and S¸ile stations are decreased. The heavy metal levels in the Bosphorus and Marmara Sea sediments were also investigated during the period of 1990– 1994 (Gu¨ven et al., 1992; Esen et al., 1999; Kut et al., 2000). The Cd and Pb concentrations in the sediment samples of the present study were lower than the Bosphorus sediments. The Mn concentration is high than Bosphorus sediment. In general, the Co, Cr, Ni, Zn, Fe and Cu in our results are higher in Igneada, Sinop, Persembe and Rize stations than Bosphorus and Marmara Sea sediments. The Cr concentration in Sinop station sediment indicated that this area was heavily polluted and approaching the
‘‘severe effect level’’ when compared with the Sediment Quality Guidelines of the Ontario Ministry (Persaud et al., 1992). The concentrations of Mn, Pb and Cu in the sediment samples in this study are generally higher than the concentrations found in the northern sector of the Romanian marine environment (Bologa et al., 1988), while Cd, Pb and Cu concentrations are lower than in the sediment collected from the southern sector. The macroalgae and mussel species are most extensively used for monitoring heavy metal contamination in estuarine and seashore areas. There are no published data for use of sea snail as indicator in metal pollution. The previous study indicated that the use of the sea snail species for monitoring of heavy metals on the shoreline of the Black sea marine environment would be valuable tool (Onat and Topcuog˘lu, 1999). The regional variations in heavy metal concentrations among the Black Sea stations were evident in all species examined beside of the sediment results. At the same time, we found significant differences in heavy metal concentrations in different organisms at the same stations. On the other hand, some authors have noted no differences between the metal concentrations in similar organisms in the same area (Fowler, 1986). Heavy metals in the near shore sediments in the eastern Black Sea that might be related to agricultural and industrial activities of the region specially from mining practices. At the same time, elevated concentrations of some heavy metals can be related to geology of the sediment source. On the other hand, the heavy metal concentrations in the western Black Sea region influenced by the rivers and atmospheric precipitation. Furthermore, Heiny and Tate (1997) indicated that the concentrations of trace elements in fish tissue are also related to concentrations of elements in sediment. Heavy metal levels in macroalgae did not follow the same patterns as concentrations in sediment at the same station. On the other hand, concentrations of Cd, Co, Cr, Zn, Fe, Mn and Cu in sea snail, mussel and fish samples related to sediment results in the examined stations.
5. Conclusion The results presented above clearly demonstrated that the Turkish Black Sea coast is facing heavy metal pollution. The metal concentrations in macroalgae, sea snail, mussel and sediment samples are very high. On the other hand,
526
S. Topcuog˘lu et al. / Environment International 27 (2002) 521–526
some heavy metal levels decreased in fish species specially anchovy fish. Moreover, lead concentrations in biota samples found below detection limit after preventive measures were enforced by the Turkish Coastal Guard for discharging ballast and bilge waters from ship. Acknowledgments Thanks are due to IAEA projects (Research Contract No. 9712/RO and Technical Co-operation Contract No. TUR/2/012) for supporting samples collection and instrumental assistance. We also thank to I˙. Akkurt for this valuable assistance. References Bei F, Catsiki VA, Strongyloudi E. Seasonal and spatial variation of Cu, Cr, Ni and Pb concentrations in Mytillus galloprovincialis of Saronikos Gulf, Greece. Rapp Comm Int Mer Me´dit 1998;35:230 – 1. Bologa AS, Apas M, Cociasu A, Cuingioglu E, Patrascu V, Piescu I, Popa L. Present level of contaminants in Romanian Black Sea Sector Marine pollution. Proceeding of a symposium held in Monaco, 5 – 9 Oct. 1998. IAEA SM-354/26: 58 – 63; 1988. Esen N, Topcuog˘lu S, Eg˘illi E, Kut D. Comparison of trace metal concentrations in sediments and algae samples from the Ku¨c¸u¨kc¸ekmece Lagoon and Marmara Sea. 1999;240(2):673 – 676. Favero N, Cattalini F, Bertaggia D, Albergoni V. Metal accumulation in a biological indicator (Ulva rigida) from the lagoon of Venice (Italy). Arch Environ Contam Toxicol 1996;31:9 – 18. Fowler SW. Trace metal monitoring of pelagic organisms from the open Mediterranean sea. Environ Monit Assess 1986;7:59 – 78. Gu¨ven KC, Topcuog˘lu S, Kut D, Esen N, Erentu¨rk N, Saygı N, Cevher E, ¨ ztu¨rk B. Metal uptake by Black Sea algae. Bot Mar Gu¨vener B, O 1992;35:337 – 40. Gu¨ven KC, Okus¸ E, Topcuog˘lu S, Esen N, Ku¨c¸kcezzar R, Seddigh E, Kut D. Heavy metal accumulation in algae and sediments of the Black Sea Coast of Turkey. Toxicol Environ Chem 1998;67:435 – 40. ¨ lmez I˙, Balkas TI, Tuncel G. Chemical Hacisalihog˘lu G, Eliyakut F, O composition of particles in the Black Sea atmosphere. Atmos Environ 1992;264:3207 – 18.
Heiny JS, Tate CM. Concentration, distribution, and comparison of selected trace elements in bed sediment and fish tissue in the South Platte River basin, USA, 1992 – 1993. Arch Environ Contam Toxicol 1997;32: 246 – 59. Kut D, Topcuog˘lu S, Esen N, Ku¨c¸u¨kcezzar R, Gu¨ven KC. Trace metals in marine algae and sediment samples from the Bosphorus. Water, Air, Soil Pollut 2000;118:27 – 33. Onat B, Topcuog˘lu S. A laboratory study of Zn and 134 Cs depuration by the sea snail (Rapana venosa). J Environ Radioact 1999;46:201 – 6. Persaud D, Jaagumagi R, Hayton A. Guidelines for the protection and management of aquatic sediment quality in Ontario. Log 92-2309067, PIBS 1962, Queen’s Printer for Ontario, 1992. Polikarpov GG, Zaitsev YP, Zats VI, Radchenko LA. Pollution of the Black Sea (levels and sources). In: Gu¨ven KC, editor. Proceedings of the Black Sea Symposium, 16 – 18 Sep. 1991, I˙stanbul. 1994;15 – 42. Sivalingam PM. Biodeposited trace metals and mineral content studies of some tropical marine algae. Bot Mar 1978;21:327 – 30. Topcuog˘lu S, Fowler SW. Factors affecting the biokinetics of technetium (95mTc) in marine macroalgae. Mar Environ Res 1984;12:25 – 43. Topcuog˘lu S, Saygı N, Erentu¨rk N, Bulut AM. The toxicity study in barrel wastes thrown into the Black Sea Report of C¸ekmece Nuclear Research and Training Center, AR-276, 1990a (in Turkish). Topcuog˘lu S, Erentu¨rk N, Saygı N, Kut D, Esen N, Ba˛sari A, Seddigh E. Trace metal levels of fish from the Marmara and Black Sea. Toxicol Environ Chem 1990b;29:95 – 9. Topcuog˘lu S, Erentu¨rk N, Esen N, Saygı N, Kut D, Seddigh E, Bas˛sari A. The toxic element levels in oyster and sea snail. J Sci Fac Ege Univ, Ser B 1994;16(1):239 – 41 (in Turkish). Topcuog˘lu S, Kut D, Erentu¨rk N, Esen N, Saygı N. Some element levels in anchovy, bluefish, Atlantic mackerel and dolphin. Tr J Eng Environ Sci 1995a;19:307 – 10 (in Turkish). Topcuog˘lu S, Kut D, Esen N, Ku¨c¸u¨kcezzar R. Radioactivity and trace element levels in sediments of the Black Sea. Rapp Comm Int Mer Me´dit 1995b;34:232. Topcuog˘lu S, Esen N, Eg˘illi E, Gu¨ngo¨r N, Kut, D. Trace elements and 1137 Cs in macroalgae and mussel from the Kilyos in Black Sea. In: International Symposium on Marine Pollution, Monaco, 5 – 9 Oct. 1998, IAEA-SM-354/30, 1998;283 – 284. TSI (Turkish Statistic Institute). Statistic of Water Products. ISBN 1003 – 6177, 1997 (in Turkish). UNEP. Assessment of the state of pollution of the Mediterranean Sea by zinc, copper and their compounds. MAP Tech Rep Ser 1996;105: 65 – 70. UNEP. Black Sea biological diversity Turkey. Black Sea Environ Ser 1998;9:56 – 62.