assessment of heavy metal and detergent pollution in

Volume 25 – No. 8/2016, pages 2884-2890

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Fresenius Environmental Bulletin

ASSESSMENT OF HEAVY METAL AND DETERGENT POLLUTION IN GIRESUN COASTAL ZONE, TURKEY Nazmi Polat1, Tamer Akkan2* Department of Biology, Faculty of Arts and Science, Ondokuz Mayıs University, Samsun 55139, Turkey 2 Department of Biology, Faculty of Arts and Science, Giresun University, Giresun 28100, Turkey

1

detergent contamination. A large number of studies reported that many coastal regions of Turkey have been seriously polluted by heavy metals [1-6] and detergents [7-10]. Moreover some papers have been published concerning heavy metal levels in biota [11], aquatic organisms [12-15] and moss samples [16,17] of the Turkey. Boran and Altınok [18] reported that the heavy metal pollution should be taken into account in the Black Sea during the last 20 years. Moreover in some areas of Black Sea, metal concentrations in sea water exceeded the references values. Heavy metal contamination along coastlines varies with the local economic development, pollution sources and geographical conditions [19]. Up to now, heavy metal and detergent pollution in coastal ecosystems and estuary has been studied by many worldwide researchers [20-25]. Detergents are major contaminants for aquatic life. They contain various anionic surfactants as linear alkylbenzene sulfonates (LAS). LAS is the anionic surfactant used most in the formulation of detergents in developed and developing countries throughout the world. Due to their widespread use, surfactants are common constituents in municipal effluents and in the corresponding receiving seawater environments [26]. Anionic surfactants influence enzyme activities by binding to the enzyme protein. Moreover, anionic detergents affect the growth of many organisms in the aquatic life [27-29]. And, in particular, that phosphorus from detergents is one of the leading causes of blue-green algal outbreaks in aquatic systems. Pollution of the aquatic environment with heavy metals and detergent has become a serious concern during recent years [30-32]. The aim of the present study is to determine the concentrations of LAS and heavy metals in the coastline of Giresun, Turkey. It is expected that the results of this research will assist in acquiring information about the level of toxic components in this area.

ABSTRACT In this study heavy metal and anionic detergent, LAS concentrations were surveyed in the coastal surface water of Giresun, Turkey. A comprehensive study in this area was made in first time the present study. The seawater samples were collected monthly from a depth of 1 m at 8 stations (representing 24 substations) between June 2012 and May 2013. Concentrations of Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb were determined by using ICP-MS. Descriptive statistical analysis including One-way ANOVA, significance (0.05) was done. Important differences in the mean values were tested with Tukey’s multiple range test. In surface water samples, according to analysis results, the following findings were obtained for the concentration ranges of the metals (ppm); Al: 0.072-3.303, Cr: 0.057-0.360, Mn: 0.015-0.272, Fe: 8.889-18.782, Co: 0.020-0.080, Ni: 7.075-8.666, Cu: 0.043-0.230, Zn: 0.41-0.759, Cd: 0.033-0.047, Pb: 0.024-0.149 and LAS value varied between 0.887-1.987 ppm. Seasonal mean levels at each of the stations were not significantly different (p>0.05), but between the metals, there were significant differences (pNi>Al>Zn>Mn>Cu>Cr>Pb>Cd>Co in summer and Fe>Ni>Zn>Al> Cu>Cr>Pb>Cd>Mn>Co in other seasons. The sequence of the means of heavy

metals in water samples from all seasons were Fe>Ni>Zn>Al>Mn>Cu>Cr>Pb>Cd>Co (Table 1). Fe was found in higher amounts than other trace microelements. The mean concentration of Zn was next to Ni, which was found in larger concentration 2886

Volume 25 – No. 8/2016, pages 2884-2890

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TABLE 2 Pearson correlation coefficients between heavy metal levels in Giresun Coast Al Cr 1 Al -0.055 1 Cr 0.590** Mn 0.220 0.197 -0.476** Fe 0.042 0.593** Co -0.616** 0.145 Ni 0.784** Cu 0.095 -0.167 -0.710** Zn -0.075 Cd -0.451** -0.050 0.460** Pb *p< 0.05 **p< 0.01

Mn

Fe

Co

Ni

Cu

Zn

Cd

Pb

1 0.111 0.977** -0.327 0.787** -0.762** -0.435* 0.878**

1 0.083 -0.519** -0.242 0.096 -0.037 0.167

1 -0.220 0.780** -0.736** -0.293 0.922**

1 -0.110 0.146 0.475** -0.151

1 -0.696** -0.273 0.713**

1 0.355* -0.524**

1 -0.136

1

than others. The heavy metal found in the lowest concentration was Co in all stations. According to statistical analysis (One-way ANOVA) Al, Cr, Fe, Ni and Cd concentrations were significantly different between the seasonal changes, with the p-value below 0.05. Other than that, all metals showed insignificant differences between sampling stations (Table 1). Moreover Table 2 showed the statistical analysis of metal-tometal correlation matrix in terms of linear correlation coefficient (r) values (significant at 0.05 and 0.01) in water samples during all seasons, respectively. Anionic detergent (LAS) concentrations were shown in Table 3. These values were at the range of 0.887-1.987 mg/L in all samples. In summer highest and in spring lowest quantity was observed. The mean concentration of LAS was relatively high during summer than other seasons. It is also observed that the average values of detergent concentration (mg/L) in seawater 1.542±0.018 (in summer), 1.307±0.018 (in fall), 1.339±0.014 (in winter) and 1.261±0.018 (in spring), respectively. Significant relationships were found between all seasons as well as between stations.

DISCUSSION AND CONCLUSIONS The quality standards for marine water according to different countries guidelines are shown in Table 4. Cr, Fe, Ni, Cu, Zn and Cd concentrations higher than the Turkey, Canada and Russian standards. There are no quality criteria given for Co and Mn (except to Russia). On the northwestern Black Sea shelf, Cu was mainly in the dissolved phase and concentrations were higher than at shelf edge stations due to freshwater inputs [36], but Cu concentrations in seawater samples not exceed the reference interval values in this study. Balkıs et al. [37] found that amount of dissolved (Fe, Mn, Pb, Cd, Hg) and suspended (Fe, Mn, Pb, Cd, Cu) metal concentrations were above the average values recorded along the shore of Black Sea from Igneada to Hopa. Yemencioglu et al. [38] found higher accumulations of Pb than of Cd and measured dissolved forms of Mn and Fe+2-Fe+3 in seawater of the Black Sea. Many researchers reported similar values for dissolved iron concentrations of 11.169-16.754, 11.310-15.212 ppm like our results [38,39].

TABLE 3 LAS concentrations of seawater samples (mg/L) 1

2

3

4

5

6

7

8

Total

Mean±SE (Min.-Max.) n

9

9

9

9

9

9

9

9

72

Summer

1.605±0.043 (1.365-1.737)

1.625±0.034 (1.440-1.810)

1.575±0.037 (1.360-1.790)

1.315±0.028 (1.167-1.437)

1.440±0.032 (1.317-1.560)

1.510±0.037 (1.290-1.730)

1.620±0.036 (1.410-1.830)

1.645±0.053 (1.497-1.987)

1.542c±0.018 (1.167-1.987)

n

9

9

9

9

9

9

9

9

72

Fall

1.390±0.038 (1.233-1.532)

1.360±0.021 (1.280-1.451)

1.490±0.041 (1.250-1.730)

1.125±0.026 (0.964-1.234)

1.355±0.043 (1.168-1.524)

1.075±0.019 (0.980-1.170)

1.340±0.011 (1.290-1.390)

1.320±0.020 (1.263-1.447)

1.307b±0.018 (0.964-1.730)

n

9

9

9

9

9

9

9

9

72

Winter

1.510±0.016 (1.445-1.586)

1.380±0.020 (1.306-1.463)

1.360±0.017 (1.278-1.428)

1.180±0.026 (1.103-1.287)

1.310±0.015 (1.217-1.375)

1.200±0.021 (1.121-1.271)

1.440±0.024 (1.349-1.536)

1.330±0.014 (1.248-1.368)

1.339ab±0.014 (1.103-1.586)

n

9

9

9

9

9

9

9

9

72

Spring

1.370±0.020 (1.236-1.432)

1.390±0.009 (1.326-1.425)

1.350±0.018 (1.276-1.452)

0.989±0.010 (0.951-1.045)

1.290±0.008 (1.254-1.326)

1.070±0.033 (0.887-1.197)

1.330±0.016 (1.224-1.396)

1.300±0.017 (1.189-1.366)

1.261a±0.018 (0.887-1.452)

Horizontally, letters a, b and c show statistically significant differences (p < 0.05). 2887

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Volume 25 – No. 8/2016, pages 2884-2890


TABLE 4 Comparative values (ppm) for heavy metals in sea water from different countries Metal

Turkey [40]

Al Cu Cd Cr Pb Fe Se Co Mn Ni Zn Hg As

Canada [41] 0.005-0.11 0.002-0.0042 0.0002-0.00182 0.02-0.002 0.001-0.0072 0.3 0.001

0.01 0.01 0.1 0.1

0.025-0.152 0.03 0.0001 0.05

0.1 0.1 0.004 0.1 1=pH depends

Russia [41] 0.001 0.005 0.005-0.02 0.1 0.1 0.0016 0.01 0.01 0.01 0.01 0.00001

2= Hardness depends

Altas and Buyugungor [42] investigated the impact of marine activities on heavy metal pollution at 11 stations located in the middle Black Sea region. They found that heavy metal concentrations; Pb: 315-989, Cd: 2-68, Cu: 4-79, Zn: 2-821, Co: 31-341 and Ni: 49 ppb (one station). Cd and Cu levels, generally, and Pb and Zn levels sometimes, exceeded the levels of reference value given in Turkish Water Pollution Control Regulation [40]. Cevik et al. [43] reported that heavy metal concentrations in sea samples located in east black sea, Fe: 680, Cu: 19.5, Zn: 6.5, Cd: 3, Rize liman içi; Fe: 210, Cu: 7.5, Zn: 207.5, Pb: 29 at Çamburnu, Fe: 130, Zn: 12, Çayeli; Fe: 290, Cu: 9, Zn: 6, Pb: 17.5, Hopa; Fe: 340, Cu: 20.5, Zn: 81.5 Pb: 39 ppb at outside harbors in Rize. Cr, Mn and Ni were not determined during the study. Slaveykova et al. [44] determined the trace metal levels in surface and offshore waters of the Bulgaria coast in Black Sea. They found out that metal concentrations were found as nM; Cd: 0.161, Cu: 28.8, Ni: 17.5, Pb: 0.61 in surface water, Cd: 2.58, Cu: 2.83 and Ni: 10.9 in offshore water, respectively. There are limited data evaluating the LAS concentration in Turkish coasts. LAS pollution was investigated in various parts of the Turkish Sea; the highest concentration (μg/L), in Istanbul Strait as 41.05, in Çanakkale Strait as 25.02 [8], in Küçükçekmece Lagoon [45] as 1.840, in ŞileAyancık (Black Sea) as 398.78 [46], in Kadıköy [10] as 58.73 and in southeastern Black Sea [30] as 28.80. Balcıoğlu et al. [10] reported that LAS concentrations were at the range of 14.88–31.12 μg/L in January and 30.63- 58.73 μg/L in August samples collected from Turkish Straits System. Additionally, the significance difference was found in detergent concentrations between all seasons and all between stations (p