Heavy metals in Yeniçağa Lake and its potential sources: soil, water, sediment, and plankton

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Environ Monit Assess (2012) 184:1379–1389 DOI 10.1007/s10661-011-2048-0 Heavy metals in Yeniça ˘ ga Lake and its potential sources: soil, water, sediment, and plankton Yasemin Saygı · Sibel Atasagun Yi ˘ git Received: 7 September 2010 / Accepted: 18 March 2011 / Published online: 15 April 2011 © Springer Science+Business Media B.V. 2011 Abstract The distribution and accumulation of heavy metals (Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Mo, Cd, Sn, Ba, Pb) in the water, sediments, plankton of Yeniça ˘ ga Lake, and its potential sources (creeks, sewage, artesian well, soil) were investigated during 1-year study period as month- ly or seasonally. Element analyses were per- formed by ICP–MS. Results showed that the trace and toxic elements (Al, As, Mn, Pb, Fe) concen- tration in lake water and/or its feeding sources were above the recommended water standards (WHO, EC, EPA, TS-266). It was found that the maximum accumulation of the heavy metals iron, aluminum, manganese, zinc, and barium in the sediment of Yeniça ˘ ga Lake. The accumulation order of trace metals were Fe > Al > Mn > Zn > Ba > Ni > Cr > As > Cu > Pb > Co > Mo > Sn > Cd in the lake, creeks sediment, and soil samples. The similar results suggest that the accumula- tion of heavy metals in the sediment is a natural process. Metals accumulated in the lake are natu- rally mixed from the soil. However, the presence Y. Saygı (B ) Biology Department, Faculty of Science, Hacettepe University, Beytepe 06800, Ankara, Turkey e-mail: [email protected] S. A. Yi ˘ git Biology Department, Faculty of Science, Ankara University, Be¸ sevler 06100, Ankara, Turkey of heavy metals in the analysis of artesian well water and sewage reveals that the transportation occurs also from the groundwater to the lake. The results obtained in plankton in Yeniça ˘ ga Lake showed that aluminum, iron, manganese, zinc, and barium were most accumulated elements in the plankton. The lower averages of lead prevalent in the water and sediment during some months were seen to have a significant mean accumulation in the plankton. Keywords Heavy metals · Bioaccumulation · Water · Sediment · Plankton · ICP–MS · Yeniça ˘ ga Lake Introduction The contamination of fresh waters with a wide range of pollutants has become a matter of great concern over the last few decades, not only be- cause of the threat public water supplies but also with the damage caused to the aquatic life. There- fore, studies related with metals have been receiv- ing increased worldwide attention, and the litera- ture has many publications on this. Heavy metal constitutes a major problem with regard to envi- ronmental contamination because they are toxic and tend to accumulate in living organisms (Bury et al. 2003). Heavy metals are produced from a variety of natural and anthropogenic sources. In

Transcript of Heavy metals in Yeniçağa Lake and its potential sources: soil, water, sediment, and plankton

Environ Monit Assess (2012) 184:1379–1389DOI 10.1007/s10661-011-2048-0

Heavy metals in Yeniçaga Lake and its potential sources:soil, water, sediment, and plankton

Yasemin Saygı · Sibel Atasagun Yigit

Received: 7 September 2010 / Accepted: 18 March 2011 / Published online: 15 April 2011© Springer Science+Business Media B.V. 2011

Abstract The distribution and accumulation ofheavy metals (Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, As,Mo, Cd, Sn, Ba, Pb) in the water, sediments,plankton of Yeniçaga Lake, and its potentialsources (creeks, sewage, artesian well, soil) wereinvestigated during 1-year study period as month-ly or seasonally. Element analyses were per-formed by ICP–MS. Results showed that the traceand toxic elements (Al, As, Mn, Pb, Fe) concen-tration in lake water and/or its feeding sourceswere above the recommended water standards(WHO, EC, EPA, TS-266). It was found that themaximum accumulation of the heavy metals iron,aluminum, manganese, zinc, and barium in thesediment of Yeniçaga Lake. The accumulationorder of trace metals were Fe > Al > Mn > Zn >

Ba > Ni > Cr > As > Cu > Pb > Co > Mo > Sn >

Cd in the lake, creeks sediment, and soil samples.The similar results suggest that the accumula-tion of heavy metals in the sediment is a naturalprocess. Metals accumulated in the lake are natu-rally mixed from the soil. However, the presence

Y. Saygı (B)Biology Department, Faculty of Science,Hacettepe University, Beytepe 06800, Ankara, Turkeye-mail: [email protected]

S. A. YigitBiology Department, Faculty of Science,Ankara University, Besevler 06100, Ankara, Turkey

of heavy metals in the analysis of artesian wellwater and sewage reveals that the transportationoccurs also from the groundwater to the lake. Theresults obtained in plankton in Yeniçaga Lakeshowed that aluminum, iron, manganese, zinc, andbarium were most accumulated elements in theplankton. The lower averages of lead prevalent inthe water and sediment during some months wereseen to have a significant mean accumulation inthe plankton.

Keywords Heavy metals · Bioaccumulation ·Water · Sediment · Plankton · ICP–MS ·Yeniçaga Lake

Introduction

The contamination of fresh waters with a widerange of pollutants has become a matter of greatconcern over the last few decades, not only be-cause of the threat public water supplies but alsowith the damage caused to the aquatic life. There-fore, studies related with metals have been receiv-ing increased worldwide attention, and the litera-ture has many publications on this. Heavy metalconstitutes a major problem with regard to envi-ronmental contamination because they are toxicand tend to accumulate in living organisms (Buryet al. 2003). Heavy metals are produced from avariety of natural and anthropogenic sources. In

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aquatic environments, however, metal pollutioncan result from direct atmospheric deposition, ge-ologic weathering, or through discharge of agricul-tural, municipal, residential, or industrial products(Förstner and Wittmann 1981).

Heavy metals may affect organisms directly byaccumulating in the body or indirectly by trans-ferring to the next trophic level of food chain.The high accumulation in these components canresult in serious ecological degradations. One ofthe most serious consequences of their persistenceis the biological amplification of metal in foodchain.

Yeniçaga Lake is a candidate for Ramsar Con-vention because its habitats supports for at least183 bird species (Ertan et al. 1989), 345 planttaxa (Sümer 2002), four fish species (Demirkalpand Saygı 2001), and many zooplankton taxa(Saygı 2005; Saygı and Yigit 2005; Külköylüogluet al. 2007). However, the quality of surface waterof Yeniçaga Lake has diminished over the lastdecades as a result of increased anthropogenicfactors. The lake continuously receives significantamounts of nutrient-rich water from two main

creeks (Kuzuviran and Deliler), because domesticwastewater is still directly being discharged tocreeks without treatment (Fig. 1). Additionally,untreated municipal wastewater and nutrient-richwater from a slaughterhouse located on the east-ern coast of the lake is increased the levels ofpollution in the lake. Such simultaneous activitiesreduced water quality and disrupt the biodiversityin the lake (Saygı and Demirkalp 2004a, b).

Another environmental issue for the lake is theartesian wells that its water discharges throughcreeks or superficial drainage into the lake.Metal contain of artesian water was analyzed byYeniçaga municipals, but results were not ex-plained by official authority. Although earlierstudies on the Yeniçaga Lake focused only ecosys-tem analyses, including physicochemical waterquality, productivity analyses, biodiversity (Saygı2000, 2005; Demirkalp and Saygı 2001; Saygı andDemirkalp 2004a, b, 2005; Saygı and Yigit 2005;Külköylüoglu et al. 2007), general pictures of themetal sources, their distribution, and bioavail-ability in the lake are not studied. Taking intoconsideration to metal contain of artesian water,

Fig. 1 Map of YeniçagaLake and samplingstations

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accumulation of metals is expected in all compo-nents of the lake, creeks and near milieu. There-fore, in the present study, we characterized (1)metal content of water, sediment, and planktonin the lake; (2) potential sources of pollutantsincluding water and sediment of creeks, artesian,and sewage waters and soil over a period of 1 yearas monthly intervals or seasonally.

Material and methods

Study area

Yeniçaga Lake is located at 976 m above sea levelin the Western Black Sea region in Turkey (40◦47′N, 32◦02′ E). The lake basin occurs in a depressionof 7 × 2.5 km size formed after tectonic activitiesduring the early Quaternary and the lake is lo-cated on the North Anatolian Fault Zone (Lahn1948; Erinç et al. 1962; Pekcan 1993). Since itsformation, it appears that the lake surface areahas been reduced about threefold to its presentsize. Today Yeniçaga Lake is shallow, endorheik,and eutrophic lake with a maximum depth 5.2 m(Saygı and Demirkalp 2004a, b). However, an ar-tificial channel was constructed on the Asagıdereand operated between 1965 and 1990 in order tocontrol overflowing from the lake (Fig. 1). Thisartificial channel has been closed completely dueto excessive decrease of the lake water since 1990.Crop, sugar, beet, and potato are mainly culti-vated products in the catchment area of the lake,and the environment of the lake has rich peatdeposits.

Sampling of water, sediment, soil, and plankton

The sampling strategy was designed to coverall significant water courses and their bottomsediment. This included all significant sourceswhich fed into Yeniçaga Lake, e.g., Kuzuviranand Deliler creeks, municipal wastewater, artesianwells water, and soil.

Water, sediment, and plankton sampling wascarried out from March 2008 to February 2009as monthly intervals at three stations in YeniçagaLake. Sampling stations are mainly located in

front of creeks (B1, B2) and municipal wastewater outlets (B3). Water and sediment samplesfrom the creeks (C1, C2), sewage (S1), artesianwells (A1, A2), and soil (S2, S3) were collectedseasonal periods.

Water samples were collected from surface andbottom using Hydrobios Water Sampler. For tracemetal analyses 250 ml subsample was immediatelyfiltered through Whatman 0.45-μm glass fiberfilter and transferred into acid cleaned polypropy-lene bottles and then, acidified with the concen-trated nitric acid. Sediment samples were col-lected with Ekman Bottom Sampler from the top20 cm layer of the bottom and stored in acid-cleaned plastic container. Plankton sampling werecarried out with the aid of Hydrobios planktonnet (30 μm mesh size) by horizontal at each sta-tion. All samples were stored in an icebox duringtransport.

Laboratory procedures and analyses

The soil and sediment samples were dried at100◦C for 24 h, homogenized with a pestle, passedthrough 1 mm sieve, and each of the weighedsamples were transferred into a glass flask, and di-gested with HClO4 and HCl on a hot plate at 80◦C.The digests were left to cool at room temperatureand diluted with 10 N HCl (Bernhard 1976).

Plankton samples were passed through What-man 0.45-μm glass fiber filter, dried at 100◦C for24 h, and then weighted. After burning in the ashoven, the samples were digested with 1.5 N HCl ona hot plate at 80◦C. Digest was diluted to 100 mlwith distillate deionizer water (Bernhard 1976).

To determine trace metal concentration in wa-ter, sediment, soil, and plankton, analyses of sam-ples (Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Mo,Cd, Sn, Ba, Pb) were carried out using Induc-tively Coupled Plasma–Mass Spectrophotometry(ICP–MS Thermo Elemental X7). The accuracyof chemical analyses of water, sediment, andplankton was checked using a standard refer-ence (16401643 E) and blank. One-way ANOVAand/or post hoc LSD test performed by usingSPSS 16.0 software was applied to compare metalconcentrations at different sites (B1–B3) of water,sediment, and plankton.

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Results and discussion

The study conducted at Yeniçaga Lake identifiedthe average levels of heavy metals found in thewater by month. These were arranged accordingto metal concentration from the highest to lowestvalues as: Ba > Mn > Fe > Al > Zn > As > Cd >

Pb > Ni > Cr > Co > Mo > Sn > Cu. Seasonalchanges were observed in the heavy metals ana-lyzed on a monthly basis (p < 0.05). The metalsfound to show the highest monthly fluctuationwere manganese, iron, zinc, barium, aluminum,nickel, and chromium. While copper and tin weredetected in the water in only a few months, iron,zinc, lead, nickel, chromium, arsenic, and bariumlevels in the water were measured at their highestlevels in the summer (Table 1). According to thedistribution of heavy metals to the station, thedifference in the measurements between stationsfor some of the heavy metals (Al, Mn, Cu, Zn,Cd, Pb) was found to be significant (p < 0.05;Table 4).

The heavy metals predominantly found in thewater of Yeniçaga Lake were measured as barium26.6–148.3 μg/l, manganese 0.7–246.5 μg/l, iron12.1–140.9 μg/l, aluminum 15.8–54.2 μg/l, zinc 4.8–110.6 μg/l, arsenic 2.7–26.9 μg/l, and lead 0.7–30.1 μg/l. In the months of the study, other heavymetals found in the water (Cr, Co, Ni, Cu, Mo, Cd,Sn) were detected to be between 0.1 and 9.7 μg/l(Table 1). The results of analysis conducted on wa-ter samples taken from the Deliler and KuzuviranCreeks which feed Yeniçaga Lake, sewage, andtwo artesian wells located near the Deliler showedthat these sources of the lake were responsiblefor heavy metal input into the lake (Table 1).Aluminum, chromium, manganese, cobalt, nickel,copper, zinc, molybdenum, cadmium, tin, and leadlevels were found to be the highest in sewage(S1), while iron, arsenic, and barium were foundat higher concentrations in the artesian well No:2(A2). Although most of the highest concentra-tions of heavy metals were detected in the sewage,the other sources also accounted for a significantproportion of the entry into the lake. In particu-lar, the heavy metal ratio in the artesian wells isnoteworthy. Although A2 is no longer used, theartesian wells A1 and A2 located in the immediatevicinity of Deliler Stream, because they have not

been completely cut off, continue to carry waterthrough the creek or surface water drainage to thelake. It was learned that the water from A1 was inthe past used as the district’s water supply, utilizedfor the purpose of human consumption. However,this water was found to be unsuitable for con-sumption in analysis conducted by the YeniçagaMunicipality and has been excluded from use.

According to information obtained by theYeniçaga County Construction Department, itwas also discovered that six artesian wells aroundthe Kuzuviran Creek, opened in the past foruse and now deemed unfit for human consump-tion, are the entrance point for water into theKuzuviran Creek. Although the wells themselveshave not been analyzed, it is likely that analysisof the wells would reveal that they are the entrypoint for heavy metal into the Kuzuviran Creek.The results obtained from the sources feedingYeniçaga Lake revealed that the integration con-duit for heavy metal carried into the lake mustbe from both the ground water to the stream andsurface drainage.

Heavy metal results found in the water inYeniçaga Lake and the springs feeding the lakewere compared with TS-266 (2005), EC (1998),WHO (2009), and EPA (2009) standards. Ac-cording to these standards, the concentration ofaluminum, manganese, arsenic, and lead foundduring some months in measurements taken fromstations in Yeniçaga Lake have been identifiedto be above the acceptable level given in thesestandards. It was found that in the sources feedingYeniçaga Lake, the concentration levels of alu-minum, manganese, iron, arsenic, and lead foundin water in the sewage, manganese concentrationlevels found in A1, aluminum, manganese, iron,and arsenic concentration levels in A2, and alu-minum and manganese concentration levels in thecreek were above permissible limits set out in thestandards (Table 1).

It was found that the maximum accumulationof the heavy metals iron, aluminum, manganese,zinc, and barium in the sediment in YeniçagaLake during the study period occurred accord-ing to seasonal changes (Table 2). The heavymetals were measured at the following levels atstations operating in Yeniçaga Lake: aluminum,iron, 942–3572 μg/g, manganese, zinc and barium

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Table 1 The concentration of heavy metals in water (μg/l) in Yeniçaga Lake and its potential sources compared withrecommended limit

Al Cr Mn Fe Co Ni Cu

March 08 17.2 ± 0.8 0.00 246.5 ± 43 0.00 0.3 ± 0.1 0.00 0.00April 53.7 ± 56.1 2.6 ± 0.6 12.8 ± 7 48.9 ± 8.2 0.5 ± 0.0 6.6 ± 1.5 0.1 ± 0.1May 20.0 ± 0.17 0.4 ± 0.5 153.6 ± 13.6 44.1 ± 24.5 0.4 ± 0.04 0.00 0.00June 28.1 ± 7.7 1.9 ± 0.6 196.6 ± 31.4 47.9 ± 25.0 0.4 ± 0.0 0.00 0.00July 16.3 ± 2.11 5.5 ± 2.95 30.0 ± 27.3 42.3 ± 3.6 0.4 ± 0.03 4.8 ± 0.05 0.1 ± 0.2August 15.8 ± 1.4 7.6 ± 3.7 5.9 ± 1.9 140.9 ± 10.3 0.5 ± 0.0 9.7 ± 0.7 0.00September 30.3 ± 5.6 1.8 ± 0.3 0.7 ± 0.7 30.3 ± 8.9 0.4 ± 0.1 4.2 ± 2.2 0.00October 26.2 ± 0.9 1.8 ± 0.1 1.3 ± 0.4 12.1 ± 21.0 0.5 ± 0.0 4.1 ± 0.7 0.00November 54.2 ± 38.2 1.8 ± 0.3 144.6 ± 16.4 60.5 ± 49.6 0.5 ± 0.0 3.8 ± 0.6 0.00December 35.3 ± 15.8 0.00 57.5 ± 15.6 29.3 ± 8.5 0.4 ± 0.0 4.1 ± 0.3 0.00February 09 18.7 ± 10.6 0.5 ± 0.2 9.6 ± 8.0 47.0 ± 2.4 0.2 ± 0.0 0.00 0.6 ± 1.0Deliler 29 ± 21 2.59 ± 1.88 236 ± 256 74 ± 99 0.83 ± 0.40 5.53 ± 4.79 0.40 ± 0.70Kuzuviran 21 ± 5 1.95 ± 1.90 34 ± 34.3 84 ± 57 0.49 ± 0.14 3.34 ± 3.63 0.00Sewage 42 ± 13 13.9 ± 17 586 ± 176 353 ± 262 1.55 ± 0.10 15.9 ± 10.6 3.77 ± 3.50Artesian 1 14 ± 3 2.69 ± 3.80 262 ± 365 119 ± 25 0.28 ± 0.12 2.95 ± 4.17 0.00Artesian 2 23 ± 5 3.5 ± 1.8 374 ± 38 1413 ± 226 0.5 ± 0.2 1.5 ± 1.8 0.00TS 266 50 50 200 20 2000EC (1998) 50 50 200 20 2000WHO (2009) 20 50 100 300 40 20 2000EPA (2009) 100 50 300 1300

Zn As Mo Cd Sn Ba Pb

March 08 14.6 ± 6.1 18.2 ± 1.3 0.00 2.6 ± 0.97 0.00 66.5 ± 9.8 0.00April 18.4 ± 9.9 16.2 ± 0.1 0.5 ± 0.0 0.00 0.00 51.2 ± 12.3 1.4 ± 0.8May 22.3 ± 31.9 18.3 ± 1.11 0.4 ± 0.04 0.04 ± 0.02 0.00 73.5 ± 2.04 0.00June 21.2 ± 2.4 26.5 ± 1.8 6.8 ± 0.9 0.00 0.00 79.6 ± 5.7 0.00July 21.5 ± 1.9 26.9 ± 0.6 0.00 0.2 ± 0.08 2.3 ± 0.06 129.4 ± 15.0 10.7 ± 1.6August 110.6 ± 58.3 26.6 ± 0.9 0.00 0.4 ± 0.3 0.1 ± 0.1 114.7 ± 5.1 30.1 ± 18.4September 4.8 ± 6.9 6.5 ± 0.5 0.2 ± 0.2 0.00 0.00 148.3 ± 7.8 0.9 ± 0.2October 21.6 ± 26.0 4.5 ± 0.3 0.2 ± 0.3 0.05 ± 0.1 0.00 98.4 ± 22.8 0.7 ± 0.03November 10.4 ± 4.8 5.5 ± 0.2 0.3 ± 0.3 0.00 0.3 ± 0.5 74.8 ± 1.9 0.9 ± 0.1December 19.1 ± 14.8 3.2 ± 0.2 0.00 0.1 ± 0.1 0.00 77.6 ± 3.3 1.8 ± 0.1February 09 33.5 ± 19.9 2.7 ± 1.3 0.00 0.00 0.00 26.6 ± 5.2 1.6 ± 1.1Deliler 43 ± 33 3.92 ± 2.18 0.13 ± 0.22 0.00 0.02 ± 0.04 165 ± 55 4.70 ± 7.97Kuzuviran 27 ± 26 8.43 ± 12.3 0.04 ± 0.07 0.08 ± 0.11 0.03 ± 0.05 148 ± 25 4.33 ± 6.65Sewage 244 ± 216 15.7 ± 0.30 0.85 ± 0.80 0.36 ± 0.30 0.26 ± 0.02 206 ± 48 21 ± 34.9Artesian 1 107 ± 151 8.26 ± 10.7 0.32 ± 0.45 0.09 ± 0.13 0.00 234 ± 41 8.04 ± 11.4Artesian 2 8.6 ± 17 82 ± 5.6 0.2 ± 0.01 0.00 0.00 242 ± 27 0.9 ± 0.5TS 266 10 10EC (1998) 10 5 10WHO (2009) 3000 10 70 3 700 10EPA (2009) 5000 10 3 2000 15

1–961 μg/g, chromium, cobalt, nickel, copper, ar-senic, lead, 4–103 μg/g. The heavy metals that hadleast accumulated in the sediment were found tobe molybdenum, cadmium, and tin. Upon investi-gation, according to station, of the distribution ofheavy metals found in the sediment of YeniçagaLake, collected in the study period March 2008 to

February 2009, a significant difference was seento exist between stations (p < 0.05). Higher con-centrations of copper, cobalt, nickel, aluminum,and iron were detected at station 2 (B2) than atother stations. Barium and manganese in generalwere measured at higher concentrations at station3 (B3; Table 4).

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Table 2 The concentration of heavy metals in sediment (μg/g d.w.) in Yeniçaga Lake and its potential sources comparedwith recommended limit

Al Cr Mn Fe Co Ni Cu

March 08 2576 ± 612 88 ± 9.27 383 ± 41 3572 ± 902 17 ± 2.45 100 ± 21 34 ± 2.95April 2001 ± 37 89 ± 14.40 961 ± 90 2117 ± 206 18 ± 3.68 103 ± 27 32 ± 4.29May 1698 ± 439 77 ± 25.75 844 ± 171 1839 ± 581 17 ± 5.04 82 ± 39 24 ± 11.17June 1406 ± 100 86 ± 29.11 775 ± 142 1810 ± 333 16 ± 4.02 76 ± 28 24 ± 5.63July 1162 ± 250 79 ± 20.16 842 ± 255 2425 ± 659 18 ± 5.55 94 ± 36 29 ± 9.59August 942 ± 238 65 ± 22.60 688 ± 135 1968 ± 570 15 ± 4.58 77 ± 38 23 ± 8.68September 1760 ± 81 57 ± 13.86 615 ± 104 3433 ± 669 17 ± 3.13 56 ± 28 21 ± 5.95October 1552 ± 59 52 ± 12.60 657 ± 86 3220 ± 740 16 ± 3.65 54 ± 30 20 ± 5.30November 1495 ± 219 50 ± 21.26 564 ± 133 2990 ± 885 15 ± 3.96 50 ± 33 18 ± 7.99December 1563 ± 250 48 ± 16.45 575 ± 105 3157 ± 892 15 ± 3.74 51 ± 31 22 ± 8.52February 09 1706 ± 270 50 ± 18.14 604 ± 61 3237 ± 907 15 ± 4.20 53 ± 33 22 ± 9.84Kuzuviran 825 ± 205 51 ± 10.6 424 ± 180 1813 ± 637 13 ± 2.9 52 ± 24.5 12 ± 7.7Deliler 1199 ± 543 66 ± 21.2 549 ± 228 2360 ± 1119 16 ± 4.6 76 ± 29.6 21 ± 8.1Soil 2034 ± 793 57 ± 15 799 ± 76 4026 ± 190 17 ± 3 62 ± 37 28 ± 1.3PEC 111 49 149EPA (polluted) – >75 >500 >25000 – >50 >50Dicle River – – 277–703 18900–22504 17–47.2 64–154 50–135Dipsiz Creek – 19 – – – – 13Manchar Lake 13932–19483 14–27 144–193 10581–17712 3–6.8 16–26.6 15–29.7Balaton Lake – 66 160–760 – 17 4.4–55 0.7–36Atatürk Dam Lake – – 73–514 12587–19265 – 43–139.7 14–22.7Beysehir Lake – 11 57–1029 9237–15136 – – 5–10.47

Zn As Mo Cd Sn Ba Pb

March 08 134 ± 65.2 4.4 ± 0.71 0.74 ± 0.11 0.20 ± 0.01 2.15 ± 0.33 141 ± 7.98 14.89 ± 0.63April 1.6 ± 0.21 37 ± 3.05 8.61 ± 1.98 0.28 ± 0.48 1.83 ± 0.35 624 ± 61.44 17.07 ± 0.46May 1.2 ± 0.56 38 ± 3.52 6.99 ± 0.05 0.00 1.32 ± 0.37 567 ± 89.25 13.05 ± 1.43June 1.2 ± 0.28 42 ± 2.29 0.00 0.62 ± 0.60 4.87 ± 0.50 510 ± 80.31 51.18 ± 30.09July 96.5 ± 53.6 44 ± 2.73 0.00 0.34 ± 0.11 1.52 ± 0.32 167 ± 31.63 13.73 ± 0.65August 36.9 ± 6.91 42 ± 3.58 0.03 ± 0.05 0.14 ± 0.12 1.12 ± 0.37 136 ± 26.04 10.52 ± 1.01September 713 ± 772 40 ± 2.71 0.00 0.03 ± 0.02 0.00 103 ± 16 23.39 ± 4.46October 539 ± 735 44 ± 1.92 0.00 0.00 0.00 100 ± 19 22.04 ± 4.93November 650 ± 594 42 ± 4.83 0.00 0.00 0.00 94 ± 14.28 19.47 ± 0.80December 623 ± 437 49 ± 3.55 0.00 0.00 0.00 106 ± 16.01 20.62 ± 2.96February 09 594 ± 305 49 ± 1.86 0.00 0.00 0.00 108 ± 10 19.75 ± 0.44Kuzuviran 165 ± 212 39 ± 7.2 2 ± 3.5 0.08 ± 0.14 0.49 ± 0.44 129 ± 91 12 ± 6.7Deliler 130 ± 184 39 ± 3.3 2 ± 3.9 0.00 0.63 ± 0.54 202 ± 215 14 ± 3.1Soil 528 ± 462 53 ± 8.6 0.00 0.00 0.00 131 ± 45 26 ± 5.9PEC 458 5 128EPA (polluted) >200 – – >5 – – >60Dicle River 20–48 – – – – – –Dipsiz Creek 37 – – 0.8 – – 83Manchar Lake 53–154 11–17.7 – 4–9.7 – – 14–22.9Balaton Lake 13–150 – – 0.1–0.7 – – 2.4–160Atatürk Dam Lake 59–60 – – – – – –Beysehir Lake 10–58.05 – – 13.05 – – 32.65

Dicle River (Karadede and Ünlü 2007), Dipsiz Creek (Demirak et al. 2006), Manchar Lake (Arain et al. 2008), BalatonLake (Nguyen et al. 2005), Atatürk Dam Lake (Karadede and Ünlü 2000), Beysehir Lake (Altındag and Yigit 2005; Tekin2008), EPA (Perin et al. 1997), PEC (Macdonald et al. 2000)

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In the soil and sediment samples taken fromthe Deliler and Kuzuviran Creeks, it was shownthat high concentrations were found in themeasurements of the heavy metals aluminum(658–2594 μg/g), manganese (244–853 μg/g), iron(1102–4160 μg/g), and barium (65.8–451 μg/g).

When considering the concentration of heavymetals determined in soil samples taken from thevicinity of Yeniçaga Lake, they can be listed interms of higher to lower levels thus; Fe > Al >

Mn > Zn > Ba > Ni > Cr > As > Cu > Pb > Co:molybdenum, cadmium, and tin were not detectedin the soil samples. The same arrangement forheavy metals in sediments taken from stationsoperating in Yeniçaga Lake would appear as Fe >

Al > Mn > Zn > Ba > Ni > Cr > As > Cu >

Pb > Co > Mo > Sn > Cd, and concentrationlevels in the sediment taken from the streamsfeeding the lake would be; Fe > Al > Mn >

Zn > Ba > Ni > Cr > As > Cu > Pb > Co >

Mo > Sn > Cd. The similar rates of occurrence ofheavy metals in soil and lake and creek sedimentsshowed that the transportation of heavy metalsoccurs from surface drainage and sewage throughinto the lake. Despite not being present in thesoil, a large amount of the molybdenum, tin, andcadmium found in the sediment and creek wateris moved by way of the sewage and creeks into thelake (Tables 1 and 2).

While it is possible to find quite a lot of ma-terial about standards and regulations related tothe subject of acceptable values that should befound in surface and drinking water standards,sediment standards seemed to be very limited inthe literature. Among the limited sediment stan-dards to be found are some given EPA values(Perin et al. 1997), alongside the Probable EffectConcentrations (PEC) values given by Macdonaldet al. (2000). When viewed in terms of the stan-dards give in the EPA, chrome was found to be atcontamination levels during some months in thelake sediment and soil, manganese was found tobe at contamination levels in the sediment of trib-utaries outside Kuzuviran Creek, nickel was foundat contaminant levels in all sources, and zinc wasfound at contaminant levels in the soil and lakesediment. PEC values laid out in the literaturewere given as: cadmium 5 μg/g, chrome 111 μg/g,copper 149 μg/g, nickel 49 μg/g, lead 128 μg/g, and

zinc 459 μg/g (Macdonald et al. 2000). Accord-ingly to this information, the chrome, copper, andlead levels in Yeniçaga Lake, the creeks and soilin its environ were below the PEC values, nickelwas above the PEC level, and zinc in the soil andthe lake’s sediment were above PEC levels.

The measurements of heavy metal concentra-tions in the soil and sediments from sources thatfeed Yeniçaga Lake and the lake itself was com-pared with the findings obtained in different stud-ies (Table 2). According to these, aluminum, iron,and cadmium concentration of Yeniçaga Lake,and the sediment of its streams was lower thanthat found in polluted Manchar Lake (Arain et al.2008) but higher in terms of chromium, man-ganese, cobalt, nickel, copper, zinc, and arsenic.Concentrations of chromium, copper, and zinc inYeniçaga Lake were above the levels of DipsizCreek and Balaton Lake (Nguyen et al. 2005;Demirak et al. 2006), while levels of lead and cad-mium remained below. The concentration valuesof manganese, copper, and zinc found in the sed-iment of Yeniçaga Lake were found to be abovethose measured in the Ataturk Dam (Karadedeand Ünlü 2000), while iron value was found tobe below those measured in the Beysehir Lakeand Dicle River (Karadede and Ünlü 2007; Tekin2008).

The results obtained in plankton in YeniçagaLake showed that aluminum, iron, manganese,zinc, and barium accumulated in the plankton.The accumulation of concentrations of heavy met-als in the plankton listed from the highest to thelowest, respectively, were Al > Fe > Zn > Mn >

Ba > Pb > As > Cu > Cr > Ni > Co > Mo >

Sn > Cd. What is more, the lower averages oflead prevalent in the water and sediment dur-ing some months were seen to have a significantmean accumulation in the plankton. The mea-surements of accumulation found in the planktonat Yeniçaga Lake were between: aluminum 68–2759 μg/g, chrome 1.86–62 μg/g, manganese 30–620 μg/g, iron 87–2272 μg/ g, cobalt 0.44–8.55 μg/g,nickel 1.47–32.38 μg/g, copper 7.28–78.69 μg/g,zinc 0.81–2908 μg/g, arsenic 3.95–172 μg/g, barium16–721 μg/g, and lead 1.58–239 μg/g (Table 3).

The plankton accumulation of metals inYeniçaga Lake changed on a monthly basis, andin this respect, seasonal differences were observed

1386 Environ Monit Assess (2012) 184:1379–1389

Table 3 The concentration of heavy metals in plankton (μg/g d.w.) in Yeniçaga Lake compared with other studies

Al Cr Mn Fe Co Ni Cu

March 08 2759 ± 915 62 ± 95 434 ± 401 803 ± 501 3.27 ± 3.83 0.00 0.00April 68 ± 63 4.30 ± 4.85 57 ± 60 87 ± 102 0.65 ± 0.94 12.16 ± 21.06 23.27 ± 36.69May 213 ± 73 4.51 ± 0.66 620 ± 143 123 ± 26 0.89 ± 0.20 1.47 ± 2.55 12.04 ± 5.65June 252 ± 158 93 ± 112 350 ± 106 387 ± 288 1.48 ± 0.52 1.98 ± 3.43 24.68 ± 11.86July 257 ± 49 13 ± 4.11 183 ± 124 149 ± 40 3.17 ± 1.25 32.38 ± 10.5 41.64 ± 20.04August 151 ± 96 5.72 ± 3.34 107 ± 70 114 ± 54 0.84 ± 0.39 6.65 ± 2.82 13.37 ± 8.75September 2504 ± 1338 55 ± 72 140 ± 54 1153 ± 275 4.48 ± 0.22 0.00 0.00October 491 ± 103 5.88 ± 2.64 66 ± 47 742 ± 13 3.18 ± 0.35 0.00 15.42 ± 16.20November 2307 ± 1496 4.18 ± 7.24 314 ± 296 2272 ± 834 8.55 ± 1.70 0.00 78.69 ± 122December 1309 ± 71 10.5 ± 18.3 385 ± 636 1805 ± 1091 3.93 ± 4.86 0.00 7.28 ± 12.60February 09 1192 ± 313 1.86 ± 0.36 30 ± 13 281 ± 23 0.44 ± 0.04 0.00 6.51 ± 5.75Gediz River – 442 43 4 24 274 168Beysehir Lake – 49 – – – – –Burdur Lake – 6 – – – – –Balaton Lake – 0.14–20 17–350 – 0.3–4.3 1–16.0 4.2–170Guardimar River – – – – – – 138–375Mascardi Lake 35–160 810–4098 22.4–31.5

Zn As Mo Cd Sn Ba Pb

March 08 549 ± 331 0.00 0.00 2.24 ± 0.61 0.00 721 ± 380 0.00April 4.73 ± 8.08 3.95 ± 4.58 11.69 ± 13.72 0.20 ± 0.34 0.00 58.14 ± 14.04 6.66 ± 7.99May 0.81 ± 0.51 4.26 ± 0.57 7.58 ± 2.11 0.00 0.00 93.40 ± 11.72 1.58 ± 1.05June 7.41 ± 8.86 18.50 ± 15.4 0.00 3.70 ± 4.33 0.00 48.53 ± 22.40 216 ± 242July 75 ± 130 13.19 ± 4.78 0.00 0.36 ± 0.61 0.00 42.76 ± 11.54 12 ± 4.73August 59 ± 35 5.89 ± 3.13 0.00 0.27 ± 0.30 0.00 157 ± 106 4.34 ± 4.22September 2908 ± 933 83 ± 24.71 0.00 0.00 0.00 16 ± 14.08 86 ± 17.87October 1007 ± 559 53 ± 11.7 0.00 0.00 0.00 0.00 77 ± 48.81November 767 ± 398 113 ± 30.9 0.00 0.00 0.00 25.37 ± 43.93 239 ± 89.56December 1241 ± 683 172 ± 79 0.00 0.00 0.00 17.27 ± 29.92 42 ± 7.64February 09 204 ± 44 15 ± 3.36 0.00 0.00 0.00 0.00 7.13 ± 0.10Gediz River 210 – – 1478 – – 56Beysehir Lake – – – 53 – – 55Burdur Lake – – – 23 – – 29Balaton Lake 20–340 – – 0.17–2.3 – – 0.4–290Guardimar River 2921–9072 51–531 3–25.4 145–1006Mascardi Lake 14.7–15.7 116–126

Gediz River (Aksoy 2005), Beysehir Lake (Altındag and Yigit 2005), Balaton Lake (Nguyen et al. 2005), Burdur Lake (Yigitand Altındag 2002), Guirdmar River (Prat et al. 1999), Mascardi Lake (Markert et al. 1997)

(p < 0.05). In studies conducted in the literature,it has been demonstrated that the relationshipbetween heavy metal accumulation in plankton,and seasonal variation was significant in termsof the qualitative and quantitative characteristicsof the organism, metal type, season, the water’sphysicochemical characteristics, and the trophiclevels of aquatic systems (Marshall and Mellinger1980; Kerrison et al. 1998; Chen et al. 2000). Theheavy metals which showed the most seasonalchange in plankton in Yeniçaga Lake were found

to be iron, aluminum, zinc, manganese, lead, andcopper, respectively (Table 3). With the exceptionof the months mentioned for each metal, lowvalues were either found or detected in the plank-ton: March and June, cadmium; April, May, July,and August, nickel. In addition to the seasonalchanges in plankton, accumulation rates werealso found to differ between stations (p < 0.05)(Table 4). High levels of aluminum, manganese,iron, chromium, and nickel were usually detectedin the plankton at station 1 (B1). It can be said that

Environ Monit Assess (2012) 184:1379–1389 1387

Table 4 Statistical analyses results of water, sediment, and plankton of different stations

Al Cr Mn Fe Co Ni Cu

Water B1 34.4 ± 29.1a 2.2 ± 3.3a 74.7 ± 83.5a 44.2 ± 41.9a 0.41 ± 0.10a 3.31 ± 3.34a 0.02 ± 0.08a

B2 28.1 ± 23.9a 2.0 ± 1.6a 85.2 ± 100.9b 46.0 ± 34.3a 0.43 ± 0.08a 3.19 ± 2.99a 0.02 ± 0.07a

B3 23.7 ± 10.6b 2.4 ± 2.9a 74.5 ± 89.6a 47.0 ± 43.2a 0.38 ± 0.09a 3.67 ± 3.35a 0.19 ± 0.52b

Sediment B1 1746 ± 1263a 61.9 ± 18.3a 576 ± 154a 3023 ± 2811a 14.35 ± 2.40a 61.9 ± 25.0a 19.33 ± 7.07a

B2 2148 ± 1516b 87.4 ± 18.7c 734 ± 162b 4016 ± 2390b 20.69 ± 1.72b 107 ± 19.8b 32.53 ± 4.47b

B3 1922 ± 1418a 52.8 ± 16.7b 736 ± 221b 2981 ± 2240a 13.72 ± 1.07a 48.4 ± 21.1a 21.90 ± 5.78a

Plankton B1 1239 ± 1385a 43.6 ± 79.5a 378 ± 354a 825 ± 874a 3.96 ± 3.19a 9.00 ± 15.8a 19.81 ± 21.65a

B2 843 ± 852b 20.5 ± 41.8b 171 ± 228b 698 ± 841b 2.15 ± 2.14a 2.50 ± 7.25b 29.79 ± 63.43b

B3 1053 ± 1223a 6.7 ± 5.0c 184 ± 205b 637 ± 796b 2.31 ± 3.00a 3.38 ± 8.79b 11.17 ± 19.07c

Zn As Mo Cd Sn Ba Pb

Water B1 29.7 ± 49.3a 13.4 ± 9.7a 0.72 ± 1.7a 2.66 ± 8.4a 0.24 ± 0.68a 86.1 ± 34.3a 6.14 ± 15.2a

B2 33.0 ± 20.6a 14.5 ± 10.2a 0.79 ± 2.2a 9.60 ± 31.6b 0.28 ± 0.69a 85.1 ± 39.0a 3.60 ± 6.0b

B3 18.6 ± 25.8b 14.4 ± 9.9a 0.76 ± 2.14a 2.3 ± 7.5a 0.21 ± 0.69a 85.3 ± 34.7a 3.40 ± 6.4b

Sediment B1 319 ± 424a 37.2 ± 11.7a 1.43 ± 3.00a 0.20 ± 0.28a 1.41 ± 1.52a 222 ± 206a 20.8 ± 12.5a

B2 305 ± 466a 39.3 ± 12.5a 1.69 ± 3.68a 0.17 ± 0.35a 1.05 ± 1.33a 232 ± 202a 22.1 ± 19.1a

B3 300 ± 491a 41.8 ± 12.7a 1.34 ± 2.80a 0.06 ± 0.14b 1.30 ± 1.62a 269 ± 231b 18.7 ± 4.8a

Plankton B1 635 ± 1112a 51.6 ± 75.8a 2.97 ± 8.28a 1.15 ± 2.56a 3.30 ± 10.9a 157 ± 336a 78.0 ± 143a

B2 449 ± 654b 43.0 ± 54.9b 1.10 ± 2.87b 0.45 ± 1.03b 1.35 ± 4.48b 86.7 ± 179b 58.4 ± 76.5b

B3 776 ± 989a 36.8 ± 48.2b 1.17 ± 2.70b 0.23 ± 0.50b 0.40 ± 1.33c 77.8 ± 115c 51.8 ± 98.2b

The same letter in the column show no statistically different (p = 0.05)

the seasonal and spatial changes in heavy metalsdetected in the plankton in Yeniçaga Lake couldbe due to seasonal variations in the physical andchemical structure of water, the ratio of phyto-plankton/zooplankton found in the plankton, andthe effect of the properties of the metals.

Studies conducted in terms of the photosyn-thetic organisms due to the characteristics of traceelements suggest that in the instance of accu-mulation of manganese, iron, copper, and zinc,the average of phytoplankton is at higher rates(Markert et al. 1997). The study conducted atYeniçaga Lake showed that lake is of eutrophicstructure and that phytoplankton was dominant inthe percentage of plankton (Saygı and Demirkalp2004a, b; Saygı and Yigit 2010). In the planktonof Yeniçaga Lake, the level of lead accumulationwas noteworthy among the accumulations of alu-minum, iron, zinc, and manganese. It has beenshown in existing literature that even if there is alow concentration of trace metals, phytoplanktoncan easily accumulates trace elements from water(Förstner and Wittmann 1981). Prat et al. (1999)observed in a study conducted on GuardimarRiver that the highest level of accumulation foundin plankton was of the heavy metals zinc, copper,

lead, arsenic, and cadmium from mining and ananthropogenic origin.

The findings of the present study concerningthe accumulation of heavy metal in the planktonof Yeniçaga Lake are compared with the findingsof other research in the literature in Table 3. Thecopper, zinc, cadmium, and lead levels found inplankton in Yeniçaga Lake were low comparedwith the values due to mining activities and an-thropogenic contamination found in GuardimarRiver (Prat et al. 1999). The levels of manganese,iron, and zinc measured in plankton in YeniçagaLake were found to be higher than those found inthe Gediz River (Aksoy 2005), while chromium,cobalt, cadmium, nickel, and copper were lower.In plankton in Yeniçaga Lake, manganese andarsenic measurements were higher than those ofLake Mascardi (Markert et al. 1997), while iron,copper, and lead were detected at lower rates. Itwas also found that plankton in Yeniçaga Lakehad lower chromium levels that those in BeysehirLake (Altındag and Yigit 2005) but higher thanthose in Burdur Lake (Yigit and Altındag 2002),while cadmium levels were lower than those foundin both Beysehir and Burdur Lakes, a higher levelof lead was found than in either of these lakes.

1388 Environ Monit Assess (2012) 184:1379–1389

Conclusion

Upon analysis of the heavy metals found in thesoil, with the exception of molybdenum, tin, andcadmium, the means of the metals found in the soilwere found to be at exactly the same rates withthe sediment taken from Yeniçaga Lake and thesurrounding creeks. While molybdenum, tin, andcadmium were not detected in the soil during theanalysis, it was identified in the streams and lakesediment, in spite of at very low rates. The similarresults obtained during the analysis of soil andsediment suggests that the accumulation of heavymetals in the sediment is a natural process. Metalsaccumulated in the lake are naturally mixed fromthe soil. However, the presence of heavy metalsin the analysis of artesian well water and sewagearound the lake reveals that the transportation ofheavy metals occurs from the groundwater to thelake. Although not found in the soil, molybdenum,tin, and cadmium were found in the artesian wellwater and sewage. For this reason, it is impossibleto say that the origin of metals is from soil, ground-water, or of domestic origin.

Acknowledgement This research was a part of theproject financed by the Scientific and Technical ResearchCouncil of Turkey (TUBITAK): “Determination of HeavyMetal Accumulation in the Food Chain of Yeniçaga Lake(Bolu)” ÇAYDAG-107Y180.

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