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Distributions of total metals in thesurface sediments of the Bandirma andErdek Gulfs, Marmara Sea, TurkeyAyşegül Mülayim a , Nuray Balkıs b , Hüsamettin Balkıs a &Abdullah Aksu ba Faculty of Science, Department of Biology, Istanbul University,34134 Vezneciler, Istanbul, Turkeyb Istanbul University, Institute of Marine Sciences andManagement, Chemical Oceanography, 34134 Vefa, Istanbul,Turkey

Available online: 25 Oct 2011

To cite this article: Ayşegül Mülayim, Nuray Balkıs, Hüsamettin Balkıs & Abdullah Aksu (2012):Distributions of total metals in the surface sediments of the Bandirma and Erdek Gulfs, MarmaraSea, Turkey, Toxicological & Environmental Chemistry, 94:1, 56-69

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Toxicological & Environmental ChemistryVol. 94, No. 1, January 2012, 56–69

Distributions of total metals in the surface sediments of the Bandirma and

Erdek Gulfs, Marmara Sea, Turkey

Ays� egul Mulayima*, Nuray Balk|sb, Husamettin Balk|sa and Abdullah Aksub

aFaculty of Science, Department of Biology, Istanbul University, 34134 Vezneciler, Istanbul,Turkey; bIstanbul University, Institute of Marine Sciences and Management, ChemicalOceanography, 34134 Vefa, Istanbul, Turkey

(Received 28 July 2011; final version received 17 October 2011)

The aim of this study is to determine the contents of aluminum, iron, manganese,nickel, copper, zinc, chromium, cadmium, lead, and mercury in sediments at1–30m depths of the Band|rma and Erdek Gulfs in the Southern Inner Shelf ofthe Marmara Sea. Sediment samples were collected from different depths (1m,5m, 10m, 20m, 30m) at each region in February 2008. Primary hydrographicconditions, such as temperature (6.6–14.5�C), salinity (22.6–26.875 psu), percent-age of dissolved oxygen saturation (35–83 %), and pH (8.0–8.4) were recorded foreach sampling point. Moreover the total organic carbon (0.5–2.9%) and the totalcalcium carbonate contents (0.8–60%) of sediment samples were determined. Insurface sediments of both gulfs, Pb (21–62mg kg�1) and Cd (0.52–0.86mg kg�1)contents were determined to be higher than the shale average (Pb 20mg kg�1, Cd0.2mg kg�1) while the other metal contents were measured to be lower in general.On the other hand, generally Hg (0.06–1.1mg kg�1) contents were higher than theshale average (0.3mgkg�1)at all of the examined stations in the Band|rma Gulfand lower than the shale average in the Erdek Gulf.

Keywords: Marmara Sea; Band|rma Gulf; Erdek Gulf; metal; sediment; pollution

Introduction

Metal pollution has been recognized as a serious problem for aquatic ecosystems becauseof their persistence and toxicity. Metals are not removed from water through self-purification; in addition, they accumulate in the structure of living organisms and therebybecome involved in food chain (Loska and Wiechula 2003). The transport of metals intomarine environment is caused by natural events such as precipitation and erosion as wellas anthropogenic activities (Chen and Jiao 2008). Especially, the industrial facilities thatare densely located in the coastal areas increase the transport. When the distribution ofmetals in aquatic environments is examined, it is observed that the highest amount ofaccumulation is in the bottom sediment and the organisms that live in the sediment areaffected by this situation very deeply (Forstner and Wittmann 1981). The surfacesediments are accumulation zones for contaminants, organic and inorganic materials, andalso great food sources for living organisms (Ridgway and Shimmield 2002; Algan, Balk|sand Cagatay 2004). Therefore, it is important for environmental monitoring studies toinvestigate sediment contamination.

*Corresponding author. Email: aysegulm@istanbul.edu.tr

ISSN 0277–2248 print/ISSN 1029–0486 online

� 2012 Taylor & Francis

http://dx.doi.org/10.1080/02772248.2011.633914

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The Marmara Sea has been negatively affected by considerably high levels of pollutionwhich has been due to industrial and municipal waste disposal for many years. This studywas conducted in the Band|rma and Erdek Gulfs, which are situated in the south of theMarmara Sea and on both sides of the Kap|dag Peninsula in the northwestern area ofTurkey.

There are many studies on levels of metals in sediment samples in the Marmara Sea(Bodur and Ergin 1994; Ergin 1994; Cagatay et al. 1997a; Algan et al. 1999; Tolun et al.2001; Yas� ar, Aksu, and Uslu 2001; Algan, Balk|s and Cagatay 2004; Topcuoglu,Kirbasoglu, and Yilmaz 2004; Kurun, Balk|s, and Balk|s 2007). Additionally, sedimentgeochemistry of Erdek and Band|rma Gulfs has been investigated widely by Balk|s et al.1999 and Balk|s and Cagatay 2001.

The aim of this study is to determine the contents of the metals aluminum, iron,manganese, nickel, copper, zinc, chromium, cadmium, lead, and mercury in sedimentspresent at 1–30m depths of the Band|rma and Erdek Gulfs in the Southern Inner Shelf ofMarmara Sea.

Methods

Study area

The physical oceanography of the Marmara Sea is characterized by a two-layer watercolumn. The brackish Black Sea waters, which have a salinity of 17.6, flow toward theMarmara Sea through the Bosphorus with a surface current while the Mediterranean-based waters which have a salinity of about 38.5 psu flow toward the Black Sea throughthe Dardanelles with subsurface current (Unluata et al. 1990; Yuce and Turker 1991). Thepermanent pycnocline between these two layers occur at about 25m water depth. Theresidence time of the upper layer is 4–5 months, whereas it is 6–7 years for the lower layer(Bes� iktepe et al. 1994). Of the two gulfs, the Band|rma Gulf includes the most importantport in the Southern Marmara Sea. Besides, there are lots of industrial facilities aroundthis gulf (Ozelli and Ozbaysal 2001; Koc 2002). The Erdek Gulf is dominated by fishingand agricultural activities, and particularly tourism. In addition, it is observed that theregion is affected by terrigenous, natural, and anthropogenic organic substance sources(Balk|s and Cagatay 2001). These gulfs are semi-isolated sedimentary environments, and itis known that the riverine input into these gulfs is very high (Algan, Balk|s and Cagatay2004). The source of high mercury, chrome, copper, and lead contents is the mineraldeposits behind the region; these metals are transported from these mineral deposits byrivers (Balk|s and Cagatay 2001).

Sediment and water samples were collected from the Band|rma and Erdek Gulfs, fromcoast and different depths (1m, 5m, 10m, 20m, 30m) at each region in February 2008(Figure 1).

Analytical procedures

In order to avoid contamination, surface sediment samples were taken from the middlepart of a Van Veen grab that is not in contact with its metal surface using a plastic spoon.In coastal station, plastic spoon was used for sampling. The sediment samples were kept ina deep freeze (��18�C) immediately after collection and before drying and grinding. Theseparts were dried at 45�C and prior to analysis, the crayfish and sediment samples wereground.

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The values of temperature (�C), salinity, dissolved oxygen (mgL�1), and pHdetermined in the measurements were considered in order to determine the physical–chemical properties of sea water. Temperature was measured by thermometer on the watersampler. The Mohr–Knudsen method (Ivanoff 1972) was used to measure salinity, and theWinkler method (Winkler 1888) to measure dissolved oxygen (DO). The pH value of thesea water was measured by Orion multiparameter device during the field mission.

Metal contents in samples were determined by atomic absorption spectrophotometry(AAS) (Shimadzu 6701 Flame Spectroscopy) after ‘‘total’’ digestion, in sediment samplesinvolving HNO3þHCLO4þHF acid mixture (Loring and Rantala 1992). Hg wasanalyzed using a flameless-AAS method following hot HNO3 decomposition. Theaccuracy of AAS analyses used in this study was determined through the analysis ofreference materials (Table 1). The metal values were normalized to eliminate the grain-sizeeffects using metal/Al ratios (Loring and Rantala 1992).

Total calcium carbonate contents were determined using a gasometric-volumetricmethod (Loring and Rantala 1992). Total organic carbon (TOC) was analyzed using theWalkey–Blake method, which involves titration after a wet combustion of the samples

Table 1. Accuracy of AAS analyses used in this study, as determined by analysis of referencematerials (the RSD of measured values were �7%).

Referencematerial Element

Measured value(this study) (mg kg�1)

Certified value orrange (mgkg�1)

IAEA433 Fe 42,800 40,300–41,300IAEA433 Al 78,200 76,800–79,600IAEA405 Cr 81.8 80–88IAEA433 Mn 316 312–320IAEA405 Cu 47.3 46.5–48.9QTM080MS Zn 126 148QTM081MS Ni 24.1 27.5IAEA405 Pb 76.9 72.6–77IAEA407 Hg 0.209 0.222IAEA433 Cd 0.153 0.145–0.161

Note: IAEA433, IAEA405: Marine Sediment-International Atomic Energy Agency; QTM080MS,QTM081MS: Marine Sediment-Netherlands.

Figure. 1. Sampling stations in the Band|rma and Erdek Gulfs.

58 A. Mulayim et al.

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(Gaudette et al. 1974; Loring and Rantala 1992). Mud percentage was determined by

Galehouse (1971) and Mc Manus (1988) methods.

Statistical analysis

The metal accumulations and the origins of sediment species were evaluated calculating

their enrichment factor (EF) and percentage enrichment factors (EF%).The EF was calculated according to the following equation (Zhang et al. 2007):

EF ¼ ðCX=CAlÞsamples=ðCX=CAlÞshale average

(Cx/CAl)samples Concentration rate of x metal and Al element in the sample(Cx/CAl)shale average Shale average rate of x metal and Al element according to

Krauskopf (1979).

According to Loska and Wiechula (2003), the EF%) is defined as follows:

EF % ¼ ðC� CminÞ=ðCmax=CminÞ � 100

C: mean element concentration in the surface sediment samples,Cmin: minimum concentration determined in the study,Cmax: maximum concentration determined in the study.

Contamination Factor (CF) was calculated as follows (Pekey et al. 2004):

CF ¼ Ca=Cb

Ca: metal concentration calculated in the sample,Cb: Shale average concentration of the calculated metal according to

Krauskopf (1979).

Spearman’s rank correlation coefficient (Siegel 1956) was used in order to determine

correlation between metals and other abiotic parameters such as TOC, total calcium

carbonate contents, and mud percentage.

Results

The values of depth (m), temperature (�C), salinity (psu), percentage of dissolved oxygen

saturation (%), and pH are shown in Table 2.When Table 2 is analyzed, it is obvious that temperature ranges between 6.6 and

14.5�C in the Band|rma Gulf and between 6.7 and 14.4�C in the Erdek Gulf. Salinity

ranges between 22.6 and 26.3 psu in the Band|rma Gulf and between 25.7 and 26.8 psu in

the Erdek Gulf, percentage of dissolved oxygen (DO) saturation values ranged between 35

and 76%) in the Band|rma Gulf and between 70 and 84% in the Erdek Gulf. The pH

values are close in both gulfs and are between 8.0 and 8.4.

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The results obtained from the analyses performed in order to determine the total metal,carbonate, and organic carbon values in surface sediment samples are given in Table 3 andthe correlation between TOC and CaCO3 values are given in Figure 2.

Total organic carbon values are between 0.5 and 2.8% in the Band|rma Gulf while theyrange between 1.2 and 2.9% in the Erdek Gulf. The range of total carbonate values are 1.1and 60% in the Band|rma Gulf and between 0.8 and 70% in the Erdek Gulf. Mudpercentage values are between 1.4 and 80% in the Band|rma Gulf while they rangebetween 2.1 and 9% in the Erdek Gulf. In both gulfs, the lowest values were recorded atthe stations where coastal sampling was conducted and the highest values at the stations of20m and 30m depths.

In Table 3, it is seen that in the sediment samples from the Band|rma Gulf Al values arein the range of 1.8 to 7.2%, Fe 0.4 to 2.3%, Mn 72 to 340mgkg�1, Ni5 0.01 to42mgkg�1, Cu 0.08 to 27mgkg�1, Zn 25 to 80mgkg�1, Cr 3.2 to 229mgkg�1, Cd 0.57 to0.86mg kg�1, Pb 17 to 35mgkg�1, and Hg 0.65 to 1.12mg kg�1, while in the Erdek GulfAl values are in the range of 1.4 to 8.6%, Fe 0.78 to 3.96%, Mn 84 to 370mgkg�1,Ni5 0.01 to 44mgkg�1, Cu5 0.01 to 24mgkg�1, Zn 18 to 106mgkg�1, Cr 2.2 to172mgkg�1, Cd 0.52 to 0.77mg kg�1, Pb 18 to 62, and Hg 0.06 to 0.33mg kg�1.

Correlation coefficients (r) belonging to the metal contents, total organic carbon, totalcarbonate, and mud percentage of the surface sediment samples of the Band|rma andErdek Gulfs were calculated and the results are shown in Tables 4 and 5.

In the Band|rma Gulf, an important positive correlation was found between Al and Pb(r: 0.91, p5 0.01), Fe and Ni (r: 0.91, p5 0.01), Mn and TOC (r: 0.80, p5 0.01), and animportant negative correlation between Al and CaCO3 (r: �0.83, p5 0.01) and Pb andCaCO3 (r: �0.83, p5 0.01). On the other hand, in the Erdek Gulf an important positivecorrelation was noted between Fe and Cu (r: 0.79, p5 0.01), Ni and Cu (r: 0.93, p5 0.01),Ni and Zn (r: 0.91, p5 0.01), Cu and Zn (r: 0.81, p5 0.01), TOC and mud percentage

Table 2. Ecological properties throughout the water column of the sampling stations.

StationsDepth(m)

Temperature(�C)

Salinity(psu)

Percentage of dissolvedoxygen saturation (%) pH

Band|rma GulfB1 0.5 9.6 22.57 64.4 8.4B2 0.5 8.2 25.05 76.0 8.4B3 0.5 8.9 25.57 75.9 8.3B4 1 7.0 25.83 58.8 8.0B5 5 6.6 24.92 62.1 8.2B6 10 6.6 25.57 60.4 8.2B7 20 7.0 26.30 55.8 8.3B8 30 14.5 25.57 35.2 8.1

Erdek GulfE1 0.5 10.6 25.96 70.1 8.4E2 0.5 14.4 25.83 78.8 8.1E3 0.5 8.0 25.83 81.70 8.36E4 1 6.8 26.23 73.52 8.29E5 5 6.8 25.96 83.73 8.31E6 10 6.7 26.62 71.87 8.32E7 20 6.8 25.70 76.56 8.34E8 30 6.8 26.75 73.37 8.09

60 A. Mulayim et al.

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Table

3.

Totalmetal,totalorganiccarbon(TOC)andtotalcalcium

carbonate

(CaCO

3)distributionsandmudpercentages

insurface

sedim

entsfrom

the

Band|rmaandErdek

Gulfs.

Station

Al

(%)

Fe

(%)

Mn

(mgkg�1)

Ni

(mgkg�1)

Cu

(mgkg�1)

Zn

(mgkg�1)

Cr

(mgkg�1)

Cd

(mgkg�1)

Pb

(mgkg�1)

Hg

(mgkg�1)TOC

(%)

CaCO

3

(%)

Mud

percentage(%

)

Band|rmaGulf

B1

5.63

0.73

85

50.01

8.7

40

3.2

0.57

35

–0.90

1.14

3.0

B2

4.97

0.61

116

50.01

0.08

26

40

0.82

30

–0.90

1.43

5.6

B3

2.09

0.93

73

3.97

27

25

7.6

0.86

17

1.116

0.95

8.0

1.4

B4

5.64

0.43

84

50.01

4.1

27

24

0.85

31

1.000

1.05

1.91

1.8

B5

7.23

0.82

125

0.22

0.9

29

13

0.80

35

0.978

1.18

1.43

1.8

B6

3.64

0.48

72

50.01

1.2

26

75

0.72

27

1.059

0.49

4.19

2.0

B7

1.83

1.51

266

3.3

15

57

122

0.77

26

0.874

1.99

59.56

50.0

B8

3.25

2.27

340

42

16

80

229

0.72

22

0.654

2.81

10.67

79.9

Erdek

Gulf

E1

4.31

1.32

368

7.6

5.7

47

2.2

0.62

35

0.258

1.38

5.34

2.1

E2

4.63

1.14

218

50.01

50.01

24

172

0.72

36

0.059

1.27

0.76

2.6

E3

3.58

3.96

120

22

14

45

22

0.52

18

0.334

1.72

10.29

12.4

E4

3.85

1.14

101

1.6

2.9

18

27

0.70

32

0.224

1.15

1.52

2.1

E5

1.40

0.78

84

1.9

3.20

38

22

0.74

21

0.161

2.04

59.46

15.4

E6

8.61

0.88

123

3.6

2.83

41

85

0.77

28

0.189

1.65

70.13

10.9

E7

2.47

1.85

303

15

8.1

70

138

0.56

36

0.226

2.69

56.41

36.0

E8

5.58

3.25

328

44

24

106

6.3

0.70

62

0.165

2.89

9.15

95.7

Averageshale

(Krauskopf,1979)9.2

4.7

850

80

50

90

100

0.20

20

0.300

0.8*

6.0*

Note:*From

MasonandMoore

(1982).

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(r: 0.98, p5 0.01), and an important negative correlation between Fe and Cd (r: �0.86,p5 0.01).

Discussion

DO content at all stations in the Band|rma Gulf are distinctly lower than the Erdek Gulf(Table 2). Lower DO values are linked with terrigenous domestic and industrialanthropogenic inputs to the gulf. On the other hand, since the oxygen-richMediterranean waters that flow through the Dardanelles are effective in the Erdek Gulf,DO content is higher along the water column. DO values in the Dardanelles are close to

Table 4. Correlation coefficient (r) of total metal concentration in bottom surface sediments fromthe Band|rma Gulf.

Al Fe Mn Ni Cu Zn Cr Cd Pb Hg TOC CaCO3 Mudpercentage

Al �0.60 �0.12 �0.58 �0.67* �0.07 �0.48 0.01 0.91** �0.16 �0.20 �0.83** �0.36Fe 0.70* 0.91** 0.64* 0.52 0.31 �0.17 �0.52 �0.16 0.71* 0.58 0.48Mn 0.52 0.10 0.76* 0.48 �0.25 0.0 �0.61 0.80** 0.25 0.74*Ni 0.72* 0.34 0.33 0.11 �0.66* �0.40 0.75* 0.71* 0.22Cu 0.26 0.05 0.00 �0.71* 0.26 0.43 0.64* 0.02Zn 0.43 �0.70* 0.10 �0.48 0.67* 0.25 0.70*Cr �0.22 �0.04 �0.96 0.43 0.70* 0.70*Cd �0.19 0,49 0.07 0.11 �0.63*Pb �0.34 �0.22 �0.83** �0.17Hg �0.08 0.38 �0.73*TOC 0.60 0.35CaCO3 0.28

Notes: *Correlation is significant at the 0.05 level (1-tailed).**Correlation is significant at the 0.01 level (1-tailed).

30

25

20

15

10

5

0TOC (%)

CaCO3(%) CaCO3(%)

Dep

th (

m)

30

25

20

15

10

5

0

0 5 10 15 20 25 30 35 40 45 50 55 60

0 2 4 6 8 10 12 14 16 18 20 22 24 26

0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75

0 2 4 6 8 10 12 14 16 18 20 22 24 26TOC (%)

Dep

th (

m)

Figure 2. Total organic carbon (%) and total carbonate (%) contents in bottom surface sedimentsfrom the Band|rma and Erdek Gulfs.

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saturation level depending on the salinity and temperature of water. Since the Band|rma

Gulf is separated from the open portion of the Marmara Sea by a sill of nearly 35m depth

and an inner basin of 47m depth, mixing is limited under 35m depth (Artuz and Korkmaz

1976; Yuce and Turker 1991).In both gulfs, total organic carbon content is higher than the shale average (0.8%) at

all stations except for the station of 10m depth in the Band|rma Gulf. Albayrak et al.

(2006) determined four critical TOC values in the Marmara Sea as low (0.1–0.59%),

moderate (0.6–1.19%), high (1.2–2.19%), and very high (2.2�). When compared with our

results, it is seen that the TOC values recorded are moderate, high, and very high, and they

increase as the depth increases. Especially, high and very high values constitute the

majority. It is also known that Gonen and Karabiga rivers play an important role in the

transport of both natural terrigenous and anthropogenic carbon in the Erdek Gulf (Balk|sand Cagatay 2001; Aliyev and Sari 2005). Most part of the total calcium carbonate content

consists of the shells of such benthic organisms as mollusk, algae, and foraminifera, which

are composed of carbonate (Algan 2000). High values were determined at the stations of

20 and 30m depths in the Band|rma Gulf and at the stations of 5, 10, and 20m depths in

the Erdek Gulf. Since total calcium carbonate content is higher than 30%, it is thought

that the sediment is biogenic (Ergin et al. 1991).The total metal analysis in both gulfs shows that the amounts of Al, Fe, Mn, Ni, and

Cu are below the shale average (Krauskopf 1979). While the amount of Zn is higher than

the shale average only at station E8 in the Erdek Gulf, the amount of Cr is higher than the

shale average at stations E2 and E7 in the Erdek Gulf and stations B7 and B8 in the

Band|rma Gulf. The mud percentages at stations 7 and 8, which are at 20 and 30m depths

are higher than the other stations. It is known that metal accumulation in fine-grained

sediments is higher (Horowitz and Elrick 1987; Ankley et al. 1993; Chouba et al. 2007). On

the other hand, the amounts of Cd and Pb are higher than the shale avreage (Krauskopf,

1979) in both gulfs. While Hg content is higher than the shale average at all stations in the

Band|rma Gulf, they are lower than the shale average except for one station (E3) in the

Table 5. Correlation coefficient (r) of total metal concentration in bottom surface sediments fromthe Erdek Gulf.

Al Fe Mn Ni Cu Zn Cr Cd Pb Hg TOC CaCO3 Mudpercentage

Al 0.00 0.45 0.02 �0.24 0.10 0.05 0.40 0.43 �0.79* �0.19 �0.17 �0.17Fe 0.49 0.78* 0.79** 0.66* �0.20 �0.86** 0.23 �0.01 0.37 �0.23 0.34Mn 0.45 0.33 0.71* �0.21 �0.32 0.71* �0.38 0.21 �0.26 0.14Ni 0.93** 0.91** �0.48 �0.58 0.07 �0.21 0.76* 0.33 0.67*Cu 0.81** �0.57 �0.68* 0.07 0 0.74* 0.17 0.64*Zn �0.41 �0.47 0.36 0.05 0.79* 0.29 0.69*Cr 0.18 0.12 �0.45 �0.26 �0.05 �0.10Cd 0.00 �0.34 �0.18 0.24 �0.11Pb �0.74* 0.14 �0.50 0.19Hg 0.19 0.43 0.71TOC 0.57 0.98**CaCO3 0.52

Notes: *Correlation is significant at the 0.05 level (1-tailed).**Correlation is significant at the 0.01 level (1-tailed).

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Erdek Gulf (Table 4). The values higher than the shale average in the Band|rma Gulf arelinked with terrigenous anthropogenic inputs.

The metal accumulations and origins of sediment species were evaluated calculatingtheir EF values and EF% (Table 6).

A 0.55EF5 1.5 suggests that the trace metals may be entirely from crustal materialsor natural weathering processes. EF4 1.5 suggests that a significant portion of the tracemetals is provided by other sources (Zhang et al. 2007). EFs of Cd, Pb, and Hg were foundto be higher than 1.5 in the sediments from all stations (Table 6). These high values are dueto anthropogenic sources (domestic and industrial inputs). In contrast, EFs of Fe, Ni, Mn,Cu were determined to be lower than 1.5 generally at all stations. These results suggest thepresence of natural (terrigenous) inputs. It is seen that EF of Zn at stations E5, E7, B6, B7,B8, and EF of Cr at stations E2, E7, B6, B7, and B8 are higher than 1.5. When EF% areanalyzed, it is evident that the metal which shows the highest enrichment in the Band|rmaGulf is Hg (63.20%), and it is followed by Cd (65.52%), Pb (58.71%), and Al (45.37%),respectively. On the other hand, the highest EF% in the Erdek Gulf is determined in Cd(60%), Hg (52%), Mn (42.88%), and Al (40.22%), respectively.

The metal pollutions and origins of sediment species were evaluated calculating theirCF values (Table 7).

CF is classified into 4 groups in Pekey et al. (2004). If CF5 1, there is no metalenrichment by natural or anthropogenic inputs; 1�CF5 3 for a particular metal meansthat the sediment is moderately contaminated by the element; 3�CF5 6 means that thereis considerable contamination, and if CF4 6 then there is very high contamination forthat metal. Accordingly, CFs of Al, Fe, Mn, Ni, and Cu were determined to be lower than

Table 6. Metal enrichment factors (EF) and percentage enrichment factors (EF%) of the Band|rmaand Erdek Gulfs.

EF

Stations Al Fe Mn Ni Cu Zn Cr Cd Pb Hg

BANDIRMA GULFB1 0.25 0.16 50.01 0.29 0.73 0.05 5.06 2.83 –B2 0.24 0.25 50.01 0.002 0.54 0.74 8.25 2.81 –B3 0.87 0.38 0.22 2.35 1.24 0.33 20.57 3.75 17.66B4 0.15 0.16 50.01 0.13 0.49 0.39 7.54 2.53 5.66B5 0.22 0.19 0.003 0.02 0.40 0.16 5.53 2.26 4.33B6 0.26 0.21 50.01 0.06 0.74 1.90 9.89 3.39 9.66B7 1.61 1.57 0.21 1.46 3.18 6.14 21.04 6.55 15.66B8 1.37 1.13 1.50 0.88 2.5 6.49 11.08 3.05 6.66EF% 45.37 29.35 27.19 14.69 33.08 24.55 26.99 65.52 58.71 63.20

ERDEK GULFE1 0.60 0.92 0.20 0.24 1.11 0.05 7.19 3.69 2.00E2 0.48 0.51 50.01 50.01 0.54 3.41 7.78 3.60 0.33E3 2.16 0.36 0.72 0.73 1.29 0.57 7.26 2.37 3.00E4 0.58 0.29 0.05 0.14 0.47 0.65 9.09 3.83 1.66E5 1.09 0.65 0.15 0.42 2.78 1.47 26.43 6.84 3.66E6 0.20 0.16 0.05 0.06 0.49 0.91 4.47 1.47 0.66E7 1.47 1.33 0.70 0.60 2.92 5.13 11.34 6.67 3.00E8 1.14 0.64 0.90 0.79 1.95 0.10 6.27 5.10 1.00EF% 40.22 31.76 42.88 27.39 31.67 34.95 7.16 60 34.43 52

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1. CF of Zn is between 1 and 3 at station E8, and CF of Cr is in the same range at stationsE2, E7, B7, and B8, and both CFs are lower than 1 at all the other stations. In the ErdekGulf, CF of Cd is between 1 and 3 at stations E3 and E7 and between 3 and 6 at all theother stations. When the Band|rma Gulf is concerned, it is between 3 and 6 at all stationsexcept for B1, where it is between 1 and 3. CF of Pb is lower than 1 at stations E3 andB3 and between 3 and 6 at station E8. It is between 1 and 3 at all the other stations(Table 7).The results of our study were compared with the results of the other studiesconducted in the Marmara Sea (Table 8). According to this comparison, geochemicalcharacteristics of the surface sediment samples in the Marmara Sea have shown similarvariations in the last years.

Conclusions

In the surface sediments of the Erdek and Band|rma Gulfs, Pb, Cd, and Hg contents arehigher than the shale average at all stations. In both gulfs, EFs of Pb and Cd are higherthan 1.5. EFs%) of Hg, Cd, Pb, and Al in the Band|rma Gulf and EFs% of Cd, Hg, Mn,and Al in the Erdek Gulf are higher than the other metals. Higher values suggest thepresence of terrigenous anthropogenic (domestic and industrial) inputs. These anthropo-genic inputs are brought to the marine environment by the rivers that carry domestic andindustrial waste and are stored undiluted in these regions which are semi-isolated gulfs. Inaddition, in the drainage areas of Gonen and Biga rivers that end in the Erdek Gulf, thereare Fe, Cu–Pb–Zn, Pb, Pb–Zn mineral deposits, and/or mineral zones (Mineral DepositsMap of Turkey, General Directorate of Mineral Research and Exploration in Turkey2011, Scale 1: 2.000.000). The transport from these mineral zones by wind, rain, and riversalso has influence on metal distributions in gulf sediments. When CFs of the sediments areanalyzed, it is seen that there is moderate contamination (1�CF5 3) for Pb and

Table 7. Contamination factors (CF) of the Band|rma and Erdek Gulfs.

CF

Station Al Fe Mn Ni Cu Zn Cr Cd Pb Hg

B1 0.61 0.16 0.10 50.01 0.17 0.44 0.03 2.85 1.73 –B2 0.54 0.13 0.14 50.01 0.002 0.29 0.40 4.1 1.52 –B3 0.23 0.20 0.09 0.05 0.53 0.28 0.08 4.3 0.85 3.73B4 0.61 0.09 0.10 50.01 0.08 0.30 0.24 4.25 1.55 3.33B5 0.79 0.17 0.15 0.003 0.02 0.32 0.12 4 1.77 3.26B6 0.40 0.10 0.09 50.01 0.02 0.29 0.75 3.6 1.34 3.53B7 0.20 0.32 0.31 0.04 0.29 0.63 1.22 3.85 1.30 2.90B8 0.35 0.48 0.40 0.53 0.31 0.89 2.29 3.6 1.08 2.16

E1 0.47 0.28 0.43 0.09 0.11 0.52 0.02 3.1 1.72 0.86E2 0.50 0.24 0.26 50.01 50.01 0.27 1.72 3.6 1.81 0.20E3 0.39 0.84 0.14 0.28 0.28 0.50 0.22 2.6 0.92 1.10E4 0.42 0.24 0.12 0.02 0.06 0.20 0.27 3.5 1.60 0.73E5 0.15 0.17 0.10 0.02 0.06 0.42 0.22 3.7 1.04 0.53E6 0.94 0.19 0.15 0.04 0.06 0.46 0.85 3.85 1.37 0.63E7 0.27 0.39 0.36 0.19 0.16 0.78 1.38 2.8 1.79 0.93E8 0.61 0.69 0.39 0.54 0.48 1.18 0.06 3.5 3.09 0.56

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Table

8.

Averageandrangeoftotalmetal,inorganicandorganiccarbonconcentrationsin

bulk

surface

sedim

ents

from

differentpartsoftheMarm

ara

Sea.

Location

(Reference)

CaCO

3(%

)TOC

(%)

Al(%

)Fe(%

)Mn

(mgkg�1)

Ni

(mgkg�1)

Cu

(mgkg�1)

Zn

(mgkg�1)

Cr

(mgkg�1)

Cd

(mgkg�1)

Pb

(mgkg�1)

Hg

(mgkg�1)

Band|rmaGulf

(thisstudy)

11.04

(1.14–59.56)

1.27

(0.49–2.81)

4.28

(1.83–7.23)

0.97

(0.43–2.27)

145.05

(72.3–339.78)

6.22

(50.01–42.28)

8.96

(0.08–26.68)

38.77

(25.39–79.88)

64.17

(3.17–229.16)

0.76

(0.57–0.86)

27.82

(17.03–35.41)

0.95

(0.65–1.12)

Erdek

Gulf

(thisstudy)

26.63

(0.76–70.13)

1.84

(1.15–2.89)

4.30

(1.40–8.61)

1.79

(0.78–3.96)

205.85

(84–368.14)

11.94

(50.01–43.57)

7.63

(50.01–24.07)

48.79

(17.88–106.31)

14.32

(2.19–171.63)

0.67

(0.52–0.77)

33.35

(18.42–61.78)

0.202

(0.059–0.334)

Erdek

Bay

(Balk|sandCagatay

2001)

12.9

(1.4–72.0)

0.9

(0.2–1.5)

7.2

(1.1–9.2)

3.0

(0.8–4.6)

384

(168–746)

52

(8–149)

28

(3–52)

125

(34–272)

95

(11–238)

N.A

.40

(19–61)

0.50

(0.042–0.310)

Northerninner

shelfof

theSea

ofMarm

ara

(Kurun,Balk|s,and

Balk|s2007)

1.05

(0.2–2.3)

13.40

(2.5–37.3)

10.69

(0.07–33.71)

3.94

(1–7.9)

902.9

(412.1–1310.4)

37.8

(14.3–62.3)

19.8

(3–52.6)

31.24

(10.8–55.1)

N.A

.N.A

.17.52

(4.8–29.4)

0.088

(0.01–0.27)

IzmitGulf

(Ergin

etal.1991)

17

(2–45)

�(0.6-2.0)

N.A

.2.69

(1.4–4.0)

186

(112–678)

68

(34–98)

26

(13–49)

75

(45–114)

32

(6–81)

N.A

.36

(23–52)

N.A

.

Gem

likGulf

(Balk|set

al.1999)

8.0

(4.7–18.0)

1.3

(50.1–2.5)

7.1

(3.7–8.7)

4.1

2.6–5.1

613

(360–2610)

76

(15–173)

42

(6–107)

175

(33–410)

109

(53–152)

N.A

.43

(17–85)

N.A

.

Gem

likGulf

(Unlu

etal.2008)

N.A

.0.1–3.1

N.A

.3.5–6.3

300–1560

35–165

22–58

88–185

11771–181

50.02

50.1–67

N.A

Northernshelf

(Cagatayet

al.1997)

21.0

(8.0–55.0)

1.4

(0.5–2.5)

5.5

(2.4–7.6)

3.2

(1.7–4.5)

363

(101–616)

N.A

.21

(7–44)

71

(38–131)

N.A

.N.A

.23

(11–35)

N.A

.

_ IstanbulMetropolitan

offshore

(Algan

etal.1999)

26.0

(3.7–64.2)

1.3

(0.2–2.6)

5.5

(0.8–8.0)

2.6

(2.0–4.1)

229

(100–540)

32

(5–41)

35

(5–80)

92

(48–237)

118

(11–509)

N.A

.34

(12–58)

0.31

(0.084–0.53)

NorthernCoast

ofthe

Marm

ara

Sea

(Topcuoglu,

Kirbasoglu,and

Yilmaz2004)

N.A

.N.A

.N.A

.1.09

(0.6–1.49)

343.56

(273.6–384.2)

38.57

(20.53–53.88)

20.03

(12.7–30.6)

42.86

(34.1–50.9)

47.75

(27.21–61.54)

0.18

(50.02–0.50)

N.A

.N.A

.

Marm

ara

Sea

(BodurandErgin

1994)

13.0

(7.0–36.0)

1.0%

(0.1–2.16)

N.A

.3.31

(1.1–4.7)

1178

(196–5720)

94

(29–161)

33

(12–92)

91

(43–149)

116

(58–166)

N.A

.47

(25–92)

N.A

.

Averageshale

(Krauskopf1979)

6.0*

0.8*

9.2

4.7

850

80

50

90

100

0.20

20

0.300

Notes:N.A

.:notanalyzedin

study.

*From

MasonandMoore

(1982).

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significant contamination (3�CF5 6) for Cd. On the other hand, Al, Fe, Mn, Ni, and Cucontents are lower than the shale average at all stations in both gulfs while Cr and Zncontents are mostly lower than the shale average. Lower EF values for these metals suggestthe presence of natural, in other words mineral origin, inputs. The fact that CFs of Al, Fe,

Mn, Ni, Cu, Cr, and Zn are lower than 1 supports the idea that there is no metalenrichment. On the other hand, the metal contents that are lower than the shale average islinked with the high level of carbonate content in the sediment samples. In other words,carbonated material plays a diluting role in metal accumulation in the sediments. At thesampling locations in both gulfs, Al, Fe, and Mn contents are lower than the shale averagesince the sediment is corse-grained. At the study stations, as depth increases mudpercentage also increases; however, the substrate is a mixture of mud and shell.

In conclusion, the main source of the metal in the southern shelf is anthropogenicinputs to the region. Industrial wastewater that is discharged from the industrial facilitiesaround the gulf and domestic wastewater are carried by the rivers to the gulfs anddistributed.

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