Copper, Zinc and Lead Concentrations of Epipelic

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Annual Book of ASTM Standards, D 19, 1985, pp. ... Sivrice l esi Tarafιndaki Koy'un Temiz ve Kirli. ... Doktora Tezi, Firat Üniversitesi Fen Bilimleri Enstitüsü,.

ISSN 10674136, Russian Journal of Ecology, 2013, Vol. 44, No. 4, pp. 349–352. © Pleiades Publishing, Ltd., 2013.

BRIEF COMMUNICATIONS

Copper, Zinc and Lead Concentrations of Epipelic Diatom Frustules in Porsuk Stream (Sakarya River Basin, Turkey)1 Cem Tokatlia, Esengul Kosea, Arzu Cicekb, and Kazim Uysala a Dumlupinar b

University, Faculty of Science, Department of Biology, Kütahya, Turkey Anadolu University, Applied Environmental Research Centre, Eski¸sehir, Turkey email: [email protected] Received July 2, 2012

Keywords: Copper, Epipelic diatoms, Frustules, Lead, Porsuk Stream, Zinc DOI: 10.1134/S1067413613040139 1

INTRODUCTION

MATERIAL AND METHOD

In recent years, anthropogenic activities continu ously increase the amount of heavy metals in the envi ronment, especially in aquatic ecosystem. Pollution of heavy metals in aquatic ecosystem is growing at an alarming rate and has become an important worldwide problem, so attention has been drawn to the levels of heavy metals in freshwater and aquatic organisms (Mombeshora et al., 1981; Malik et al., 2010). As heavy metals cannot be degraded, they are deposited, assimilated or incorporated in water, sediment and aquatic animals and thus, causing heavy metal pollu tion in water bodies (Malik et al., 2010; Linnik and Zubenko, 2000).

2.1. Study Area and Collection of Samples

Diatoms are an important group of water ecosys tems, they form a large part of the benthos (often 90– 95%) and therefore they are an important part of water quality monitoring and a huge advantage of the benthic diatoms is that they can be found in every sur face water at any time (Tokath and Dayio g lu, 2011). Diatoms which are the most important source of oxy gen and nutrient for all aquatic systems have a high ecological value (Yildiz, 1984). ˆ

Porsuk Stream, which contains a dam lake on the stream basin, is the longest branch of Sakarya River (448 km). Sakarya River is the biggest river of North west Anatolia and the third longest river of Turkey (884 km). Porsuk Stream is exposed to industrial, agri cultural and domestic wastes and carries this pollution to the Black Sea through Sakarya River (Büyüker¸s an and Efelerli, 2006). The aim of this study is determine to copper, zinc and lead levels in water, sediment and epipelic diatom frustules obtained from Porsuk Stream and to assess the pollution of system. 1 The article is published in the original.

The stations selected on the Porsuk Stream are shown on the map (Fig. 1). Sediment and water sam ples were collected seasonally from all stations by using sediment dipper, Ekman grab and suitable con tainers. Epipelic diatom samples collected from over sediment by using a glass pipe (Raund, 1981). Then the diatoms were cleaned with sulfuric and nitric acid for the elimination of organic contents (Yildirim, 1995). 2.2.Chemical Analysis Sediment and diatom samples were dried for 3 h at 105°C. 0.25 g of each sample was placed in Pyrex reac tors of a CEM Mars Xpress 5 microwave digestion unit. HCIO4 : HNO3 acids of 1:3 proportions were inserted in the reactors respectively. Samples were mineralized at 200°C for thirty minutes. Afterwards, the samples were filtered in such a way as to make their volumes to 100 mL with ultrapure distilled water. Water samples of 0.5 liter in volume were taken at each sampling point and was adjusted to pH 2 with 2 mL of HNO3 being added to each. Element levels in samples were determined by ICPOES (Varian 720 ES). The element analyses were recorded as means tripli cate measurements (ASTM, 1985; APHA, 1992; EPA, 1998; EPA, 2001). 2.3.Statistical Analysis Cluster similarity and distance analysis and Box plot deviation diagrams were applied to the results by using the Past package program. The graphics of water, sediment and epipelic diatom frustules were made by using the Microsoft office 2007 package program.

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Sakarya river Porsuk Stream Porsuk Dam P2 Lake P1 KÜTAHYA

P3

ALPU

BEYLIKOVA YUNUSEMRE

AGAÇKOY

ANKARA

N

EYMIR

1/100000

Fig. 1. Study area.

3. RESULTS AND DISCUSSION

spring season, all our stations have I. Class water qual ity in terms of Zn levels and have II. Class water quality in terms of Cu (0.02–0.05 mg/L) levels. In all seasons P2 and P3 stations have II. Class (0.01–0.02 mg/L) and PI station has III. Class (0.02–0.05 mg/L) water quality in terms of Pb levels.

Cu, Zn and Pb accumulations of water, sediment and diatom frustules in Porsuk Stream are given in Table 1. The highest metal concentrations of water were deter mined as; Cu (0.039 mg/L) levels in P3 station in spring season, Zn (0.092 mg/L) and Pb (0.027 mg/L) levels in PI station in autumn season. The lowest metal concen trations of water were determined as; Zn (0.028 mg/L) levels in P2 station in spring season, Cu (0.007 mg/L) and Pb (0.012 mg/L) levels in P2 station in autumn season. According to the Water Pollution Control Regulation in Turkey (SKKY, 2004), all our stations have I. Class water quality in autumn season in terms of Zn ( water respectively. The diagram of Cluster similarity and distance analysis is given in Fig. 2. According to the Cluster similarity and distance analysis based on the Cu, Zn and Pb values of water, sediment and epipelic diatom frustules in Porsuk Stream, PI and P3 stations show the highest similarity (61%) and P1 and P2 stations show the lowest similarity (31.7%). Boxplots deviation diagrams show the range and mean concentrations and seasonal deviations of Cu, Zn and Pb levels of water, sediment and epipelic dia tom frustules in Porsuk Stream. According to the box plot diagram, the deviation of metal accumulations in water, observed in autumn season is higher than the deviation observed in spring season. The deviation of metal accumulations in sediment and epipelic diatom frustules show similarity according to seasons and a high deviation between upper quartile (Q3) and maxi mum values of boxplots were observed for metal levels of sediment and diatom frustules (Fig. 3). Copper and its compounds are naturally present in the earth’s crust. Natural discharges to air and water may therefore be significant. Both natural and anthro pogenic sources contribute Cu to water, like natural weathering of soil, atmospheric deposition and dis charges from industry and wastewater treatment plants. But it is known that the major source of Cu is from land runoff through natural weathering (USDHHS, 1990). Cu levels in river waters range from 0.0006 to 0.4 mg/L, with a median of 0.01 mg/L. Dis solved Cu levels in uncontaminated freshwaters usu ally range from 0.0005 to 0.01 mg/L, increasing to >0.002 mg/L in urban areas (Moore and Ramamoor thy, 1984). Mean copper concentrations in freshwater sediments ranged from 12 to 57 mg/kg (Spear and Pierce, 1979). Copper concentrations in uncontami nated environments are generally less than 50 mg/kg dry weigth, while concentrations in polluted environ ments can be several 1000 mg/kg (Harrison and Bishop, 1984). In this study, the Cu values of sediment found that very close to the critical levels. In addition to the geologic structure of the Porsuk Stream Basin, almost entire the stream affected by anthropogenic activities. Zinc and its compounds are ubiquitous in the envi ronment and occur in the earth’s crust at an average concentration of about 70 mg/kg (Thomas, 1991). It is known that, the largest input of Zn to water results from erosion of soil particles containing natural traces of Zn and also the primary anthropogenic sources of Zn in the environment are from metal smelters and mining activities (EPA, 1980; ATSDR, 1995). Effects of both anthropogenic and climatic features are caus ing erosion around the basin and also an important part of mineral deposits of Turkey are located in the Porsuk Stream Basin. 2013

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REFERENCES Agency for Toxic Substances and Disease Registry (ATSDR), Toxicological Profile for Copper, U.S. Depart ment of Health and Human Services, Public Health Ser vice, 1990, TP9008. Agency for Toxic Substances and Disease Registry (ATSDR), Toxicological Profile for Zinc, Atlanta, GA: U.S. Department of Health and Human Services, 1995. Agency for Toxic Substances and Disease Registry (ATSDR), Toxicological Profile for Lead, Atlanta, GA: U.S. Department of Health and Human Services, 2007. American Public Health Association (APHA), Standard Methods for the Examination of Water and Wastewater, 18th ed., Greenberg, A.E., Clesceri, L.S., and Eato, A.D., Eds., Washington, DC: APHA, 1992. American Society of Testing and Materials (ASTM), Prepara tion of biological samples for inorganic chemical analysis, in Annual Book of ASTM Standards, D19, 1985, pp. 740–747.

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As a result, the study clearly indicates that, the epipelic diatom frustules accumulate Cu, Zn and Pb trace elements more their environments and they can easily affect from changes of water quality and accu mulations of sediment. We also determined that, Cu, Zn and Pb accumulations of Porsuk Stream have reached critical limit values and this pollution is the most important threatening and limiting factor for all aquatic life in Porsuk Stream especially outputs of Kütahya and Eski¸s ehir provinces.

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4. CONCLUSION

Büyüker¸s en, Y. and Efelerli, S., Porsuk havzasi su yönetimi ve eski¸s ehir Öornegi, TMMOB–Imo Su Kongresi, 2006. EPA, Exposure and Risk Assessment for Zinc, Washington, DC: U.S. Environmental Protection Agency, Office of Water Regulations and Standards (WH553), 1980. EPA440481016. PB85212009. EPA METHOD 3051: Microwave Assisted Acid Digestion of Sediments, Sludges, Soils, and Oils, Washington, DC: U.S. Environmental Protection Agency, 1998. EPA METHOD 200.7: Determination of Metals and Trace Elements in Water and Wastes by Inductively Coupled Plasma–Atomic Emission Spectrometry, Washington, DC: U.S. Environmental Protection Agency, 2001 Harrison, F.L. and Bishop, D.J., A Review of the Impact of Copper Released into Freshwater Environments, Livermore, CA: Lawrence Livermore National Laboratory, 1984, NUREG/CR3478 UCRL53488 RE. Linnik P.M. and Zubenko, I.B., Role of bottom sediments in the secondary pollution of aquatic environments by heavy metal compounds, Lake Reserv. Res. Manag., 2000, vol. 5, no. 1, pp. 11–21. MacDonald, D.D., Ingersoll, C.G., and Berger, T.A., Development and evaluation of consensusbased sediment quality guidelines for freshwater ecosystems, Arch. Environ. Contam. Toxicol., 2000, vol. 39, pp. 20–31. Malik, N., Biswas, A.K., Qureshi, T.A., Borana, K., and Virha, R., Bioaccumulation of heavy metals in fish tissues of a freshwater lake of Bhopal, Environ. Monit. Assess., 2010, vol. 160, pp. 267–267. Mombeshora, C., Ajayi, S.O., and Osibanjo, O., Pollution studies on Nigerian Rivers: Toxic heavy metal status of surface water in Ibadan City, Environ. Int., 1981, vol. 5, pp. 49–53. Moore, J.W. and Ramamoorthy, S., Heavy Metals in Natu ral Waters, New York: Springer, 1984. Round, F.E., The Ecology of Algae, Cambridge: Cambridge Univ. Press, 1981. Spear, P.A., and Pierce, R.C., Copper in the Aquatic Envi ronment: Chemistry, Distribution and Toxicology, Ottawa: NRCC Associate Committee on Scientific Criteria for Environmental Quality, 1979. SKKY, Su kirliligi kontrolü yönetmeligi, 31 Arahk 2004 tarihli Resmi Gazete no. 25687. http://www.cevreorman.gov.tr/yasa/ y/25687 Thomas, D.W., in Metals and Their Compounds in the Envi ronment, Merian, E., Ed., Weinheim, Germany: VCH, 1991, pp. 1309–1342. Tokath, C., Dayioglu, H., Use of epilithic diatoms to eval uate water quality of Murat Stream (Sakarya River Basin, Kiitahya): Different saprobity levels and Ph status, J. Appl. Biol. Sci., 2011, vol. 5, no. 2, pp. 55–60. Tokath, C., Köse, E., Arslan, N., Qicek, A., Uysal, K., Por suk baraj golii epipelik diyatome frustullerinde makro ve mikro element konsantrasyonlan, Tanm Bilimleri Arastirma Dergisi, 2011, vol. 4, no. 2, pp. 1–6. Yildirim, V., Yιldιrιm, V., 1995. Hazar Gölü (Gölcük) Sivrice I·l¸cesi Tarafιndaki Koy’un Temiz ve Kirli. Kesimler inde Fitoplankton ve Bentik Alg Florasιnιn Ara¸s tιrιlmas, Doktora Tezi, Firat Üniversitesi Fen Bilimleri Enstitüsü, Elazi g, 1995. Yildiz, K., Meram Cayi Alg Topluluklari Üzerine Ara¸s tir malar. Kisim II: Tas ve Qesitli Bitkiler Uzerinde Ya¸s ayan Alg Toplulugu, SÜ FenEdeb. Fak. Dergisi, 1984, vol. 3, pp. 218–222.

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Lead occurs naturally in the environment. In con trast to zinc and copper, most of the high levels of Pb found throughout the environment come from human activities. Sources of lead in surface water or sediment include deposits of leadcontaining dust from the atmosphere, waste water from industries, urban runoff and mining piles (ATSDR, 2007). Porsuk Stream is affected by all these sources of Pb. Although PI station was the closest region to the source of Porsuk Stream, we determined that, the most contaminated area was PI station. PI station was located just before from the Porsuk Dam Lake and after the prov ince of Kütahya, so this region is exposed to organic and inorganic pollution especially sewage and wastes from industrial companies in the province of Kütahya. P2 station was located just after from Porsuk Dam Lake and just before the province of Eski¸s ehir. Porsuk Stream has left a large part of pollution contents to the dam lake, so P2 station was comparatively clean, if we compare the stations. P3 station was located after the province of Eskise hir and as the first station, exposed to sewage and wastes from industrial companies in the province of Eskisehir. Therefore, though not up to the first station, the region is also under pressure from pollution.

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