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Metals in the sediment and liver offour fish species from different trophiclevels in Tisza River, SerbiaSnežana Štrbaca, Aleksandra Šajnovićb, Ljiljana Budakova, Nebojša

Vasićc, Milica Kašanin-Grubina, Predrag Simonovićd & Branimir

Jovančićevićea Faculty of Environmental Protection, Educons University, SremskaKamenica, Serbiab Center of Chemistry, Institute of Chemistry, Technology andMetallurgy, University of Belgrade, Belgrade, Serbiac Faculty of Mining and Geology, University of Belgrade, Belgrade,Serbiad Faculty of Biology, University of Belgrade, Belgrade, Serbiae Faculty of Chemistry, University of Belgrade, Belgrade, SerbiaPublished online: 02 Oct 2013.

To cite this article: Snežana Štrbac, Aleksandra Šajnović, Ljiljana Budakov, Nebojša Vasić, MilicaKašanin-Grubin, Predrag Simonović & Branimir Jovančićević , Chemistry and Ecology (2013): Metalsin the sediment and liver of four fish species from different trophic levels in Tisza River, Serbia,Chemistry and Ecology, DOI: 10.1080/02757540.2013.841893

To link to this article: http://dx.doi.org/10.1080/02757540.2013.841893

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Chemistry and Ecology, 2013http://dx.doi.org/10.1080/02757540.2013.841893

Metals in the sediment and liver of four fish species fromdifferent trophic levels in Tisza River, Serbia

Snežana Štrbaca∗, Aleksandra Šajnovicb, Ljiljana Budakova, Nebojša Vasicc,Milica Kašanin-Grubina, Predrag Simonovicd and Branimir Jovancicevice

aFaculty of Environmental Protection, Educons University, Sremska Kamenica, Serbia; bCenter ofChemistry, Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Belgrade, Serbia;

cFaculty of Mining and Geology, University of Belgrade, Belgrade, Serbia; dFaculty of Biology, Universityof Belgrade, Belgrade, Serbia; eFaculty of Chemistry, University of Belgrade, Belgrade, Serbia

(Received 23 February 2013; final version received 3 September 2013)

In aquatic environments metals originate from various natural and anthropogenic sources. The degreeof contamination in fish tissues depends on the pollutant, fish species, their mode of feeding, samplingsite and trophic level. This study presents concentrations of Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb,Se, Sr and Zn in sediment and liver of four ecologically different fish species: piscivorous northern pike(Esox lucius L.), benthivorous sterlet (Acipenser ruthenus L.) and silver bream (Brama brama L.), andomnivorous common carp (Cyprinus carpio L.). Fish were caught at four sites along the stretch of theRiver Tisza in Serbia during October 2010. The concentrations of metals have been assessed using theinductively coupled plasma – optical emission spectrometry. Results revealed that metals with the highestvalues in sediment and fish samples were Al and Fe, respectively and sometimes concentrations of Zn arein the same order of magnitude as Fe concentrations. The highest concentration of metals was recorded inomnivorous common carp.

Keywords: bioaccumulation; biomonitoring; metals; sediment; River Tisza

1. Introduction

Contamination of aquatic ecosystems with metals has seriously increased worldwide attention.[1,2] Over the last few decades there has been growing interest in determining metal levels in theaquatic environment and attention has been drawn to the measurement of contamination levels inpublic food supplies, particularly fish.

Fish are one of the most indicative factors in freshwater systems for the estimation of metalspollution and risk potential of human consumption.[3,4] Furthermore, fish are often at the topof the food chain and may accumulate large amounts of metals.[5] Metals enter fish throughfood particles, gills, water and skin. Once in the body they enter the bloodstream and are carriedeither to a storage point or to the liver for transformation or storage.[6] The liver is the mainsite of accumulation, biotransformation and excretion of pollutants in fish.[7] Variations in thebioaccumulation of metals in various fish tissues are conditioned by a large number of factors:nutrition type, trophic status, source of each specific metal, remoteness of organisms from the

∗Corresponding author. Email: strbacsn@eunet.rs

© 2013 Taylor & Francis

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communication sources, presence of other ions,[8] food access,[9] occurrence of metallothioneinand other proteins responsible for detoxification in fish tissues,[10] water temperature, transport ofmetals through the membrane, rate of fish metabolic activity, different mechanisms of adsorption,regulation, depositing and excretion of metals, species, age and size of fish, exposure time,[11]as well as position and organ function.[12] Reports on bioaccumulation of heavy metals andtrace elements in different organs of fish were previously reported by Khaled [13] and VišnjicJeftic et al.[14] Numerous studies analysed metal accumulation in the muscle as it is the mainfish part consumed by humans.[15–17] However, gills and liver are a much better contaminationindicator than the fish muscle. Gills are the primary organ by which the metals are adopted fromthe water and they thereby reflect the concentration of metals in the water in which the fishlive.[18] On the other hand, ability of the liver to accumulate metals is a result of the activities ofthe metàllothionein, a protein which bonds metals and reduces their toxicity.[14,19]

Fish species at different trophic levels are exposed to different levels of contamination. Hence,this research was focused on four selected ecologically different fish species which are an impor-tant food supply: carnivorous northern pike (Esox lucius L.), benthivorous sterlet (Acipenserruthenus L.), silver bream (Brama brama L.), and omnivorous common carp (Cyprinus carpioL.). Sterlet is a rheophilic, benthivorous fish, mostly feeding on insect larvae, small molluscs,articulated worms and other invertebrates. Common carp is omnivorous, feeding on the bottomfauna, plant material and small fish in great age and size. Silver bream is a benthivorous fish whichfeeds on worms, molluscs, insect larvae and shrimps,[20] and northern pike is a visual predatorthat occasionally feed on frogs and crayfish, as well.

The aim of this study is to assess the impact of concentration of metals and their potentialrisk to human health by determining the metal accumulation in sediment and in the liver of fourfreshwater fish species. Special attention in this paper will be devoted to the accumulation ofheavy metals. Furthermore, the purpose of this study is to determine the source of heavy metals,i.e. anthropogenic vs. lithogenic. Tisza River has been chosen because fish from this river is animportant food supply not only for people living along the watershed but for the whole region.

In this study the extent of heavy metals concentrations in sediments was evaluated by Enrich-ment Factor (EF),[21] potential ecological risk levels of heavy metals by the Potential EcologicalRisk Index Method.[22] Furthermore, Bio-concentration factor (BCF) was used to evaluatebio-accumulation of metals in fish.[23]

The obtained concentrations of heavy metals in the sediment of the Tizsa River were comparedwith Serbian Regulation of limit values pollutant substances into surface water, groundwaterand sediments and the deadlines for their attaining (SRLVsS),[24] and with the internationalguideline values for freshwater sediments.[25] The obtained concentrations of metals in fish liverwere compared with Serbian Regulation of levels of pesticides, metals and metalloids and othertoxic substances, chemotherapeutics, anabolics and other substances which can be found in food(SRLVsF).[26]

2. Material and methods

2.1. Study area

Tisza River in Serbia was chosen as a study area. The basin of the River Tisza is one of the largestnatural river systems in southeastern Europe, and it is located almost exactly in the geographicalcentre of Europe. The River originates in the Zakarpatian Mountains in western Ukraine andflows into the Danube by Slankamen in Serbia (Figure 1). With respect to its length of 966 km,the River Tisza forms the largest tributary of the Danube River. The anthropogenic activity causesthe permanent pollution of Tisza River from communal, industrial and agricultural activities. In

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Figure 1. Study area. Four sites of fish samples marked with: 3rd km, 58th km, 72nd km and 153rd km river flow.Twenty-five sites of sediment samples marked with numbers: 1–25.

Serbia sources of pollutions are the waste-waters from factories and municipal sewage discharges.In the past, the Tisza River has witnessed a large number of pollution accidents, of which the mostwell know is the spill of water and sludge with the high cyanide and heavy metals concentrationfrom the flotation tailing of the gold mine in Baira Mare, Romania in February 2000. Accordingto official Romanian data, about 100,000 m3 of water and sludge were spilled into the River Laposand further on into the River Tisza, finally draining into the Danube River. At the time this wasconsidered an ecological catastrophe of international proportions unprecedented in Europe so far,both owing to great load of pollutants into the River Tisza ecosystem and especially owing togreat kill of fish that seemed to happen. Despite this fact the toxic effect of cyanide salts werediminished by the low water temperature, high level of dissolved oxygen and high water-tablelevel. Great flow velocity passed the pollution wave quickly through the middle of the main riverchannel only slightly affecting the fish community in the Tisza River.[27]

This study was performed at four sites on Tisza River in Serbia. The first fish sampling site(Figure 1) was on the border with Hungary where the Tisza River enters onto Serbian territory atthe 153rd km of the river flow. The second and third sampling points were situated at 58th kmand 72nd km river flow. The forth sampling point was at 3rd km river flow near confluence of theTisza River on the Danube. All marks refer to the upstream distance from the confluence with theDanube (Figure 1).

Sediment samples were collected from 25 locations along the Tisza River on the territory of theRepublic of Serbia (Figure 1). On Figure 1 sediment sampling locations are indicated by numbers1–25.

2.2. Sample collection

A total number of 160 fish individuals (10 specimens of four fish species from each samplingsite) were caught by professional fishermen during October 2010. Immediately after catchingfish were carefully conserved on ice and transported to the laboratory where they were stored

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at −20◦C. Before the dissection, samples were thawed at room temperature and their total wetweight, total body (TL), fork (FL) and standard (SL) length and height (H) were measured. Toavoid contamination of samples, dissection was performed on polypropylene base with stainlesssteel scissors, scalpels and forceps. Dissected livers were packed in clean dry polyethylene bagsand stored at −20◦C.

Surface sediment samples were collected using a plastic corer. After sampling sediments werepacked in polyethylene bags and transported to the laboratory. In the laboratory sediment sampleswere wet-sieved through a 63 μm sieve and air-dried. The samples were then split into smalleraliquots by coning and quartering.

2.3. Sample preparation

One gram of each fish sample was digested in the microwave digester (ETHOS 1, AdvancedMicrowave Digestion System, MILESTONE, Italy) using 8 mL of 65% HNO3 and 4 mL of 30%H2O2 (Carlo Erba, Italy) of analytical reagent grade. The samples were allowed to ramp to200◦C for 15 min, digest at 200◦C for 20 min, and cool down for 10 min. After cooling to aroom temperature, digested samples were diluted with distilled water to a total volume of 25 mL.All the plastics and glassware were washed in nitric acid for 15 min and rinsed with distilledwater before use. Analysis was performed by inductively coupled plasma optical spectrometry(ICP/OES, Thermo Scientific iCAP 6500 Duo Instrument, Thermo Fisher Scientific, Cambridge,UK), and comprised assessment of concentrations of 14 metals (Al, As, Cd, Co, Cr, Cu, Fe, Hg,Mn, Ni, Pb, Se, Sr, and Zn). The following wavelength lines of the ICP-OES analysis were used:Al 167.079 nm, As 189.042 nm, Cd 228.802 nm, Co 237.862 nm, Cr 267.716 nm, Cu 224.700 nm,Fe 240.488 nm, Hg 184.930 nm, Mn 257.610 nm, Ni 231.604 nm, Pb 220.353 nm, Se 206.279 nm,Sr 421.552 nm, Zn 202.548 nm. All heavy metals concentrations were expressed in μg/g.

Sediments underwent two stages of preparation consisting of drying and screening. Sedimentswere dried at 60◦C to minimise loss of volatile elements (e.g. Hg). Samples were then handled,dried and screened in an area dedicated for these media to avoid contamination from more min-eralised rock and core samples. Screening consists typically of two stages comprising extractionof the desired elements into a solution and element determination by instrumental analysis of thesolution. Extraction was total to measure the total abundance of the elements from all minerals inthe sample. Analysis was performed by ICP-MS.

2.4. Statistical analysis

Correlation of metal content between sediment and fish liver was tested by Pearson r coefficient.To investigate significant differences between fish sample, one-way ANOVA with post hoc testanalyses based on the Games-Howell test was applied. Data showed mostly normal distributionor close to normal distribution and therefore no transformation were performed for statisticalanalyses. Statistical confidence was set at α = 0.05. A statistical analysis of data was performedusing software SPSS version 15.0 (SPSS Inc. Chicago, USA).

2.4.1. Determination of limit vales

Despite its source heavy metal concentration varies in sediment samples with the % of organicmatter (OM) and clay. Therefore, limit values should not be presented as a single value but shouldbe calculated for each sample. This is also a part of the Serbian regulation.

In assessing sediment quality limit values for the sediment were corrected according to the mea-sured % of OM and clay. Corrected thresholds were compared with the measured concentrations

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Table 1. Limit values for standard sediment with 25% clayand 10% OM.[24]

Substance LV MLC RV

Metals (in μg/g DW)Arsenic 29.00 42.00 55.00Cadmium 0.80 6.40 12.00Chromium 100.00 240.00 380.00Copper 36.00 110.00 190.00Mercury 0.30 1.60 10.00Lead 85.00 310.00 530.00Nickel 35.00 44.00 210.00Zinc 140.00 430.00 72.00

Notes: LV, limit values; MLC, maximum legal concentration; RV,remediation values.

Table 2. Constants depending on the type of metal.[24]

Constants

Substance A B V

Metals (in μg/g DW)Arsenic 15.00 0.40 0.40Cadmium 0.40 0.007 0.21Chromium 50.00 2.00 0Copper 15.00 0.60 0.60Mercury 0.20 0.0034 0.0017Lead 50.00 1.00 1Nickel 10.00 1.00 0Zinc 50.00 3.00 1.50

of heavy metals in the investigated sediment. To correct limits of heavy metal concentrationdepending on the % of clay and OM in the investigated sediment following correction formulawas used [24]:

GVK = GVST∗(A + B∗% clay + V∗% OM/A + B∗25 + V∗10) (1)

where: GVK – corrected threshold for a sediment when the % of clay and OM are considered;GVST – limit values for standard sediment with 25% clay and 10% OM (Table 1); % clay –mineral fractions <2 μm in the examined sediment expressed in percentage of the dry weight;% OM – measured OM content in the investigated sediment expressed in percentage of the dryweight and A, B i V – constants depending on the type of metal (Table 2).[24]

2.5. Bio-concentration factor (BCF)

Bio-concentration factor (BCF) was used to evaluate bio-concentration of metal elements inorganisms.[23] This factor can also be used for field investigation of data. Bio-concentrationfactor is calculated using the next equation:

BCF = Corg/Cw (2)

where Corg is the concentration of the metal element in the organisms and Cw is the concentrationof the metal element in environment A bioconcentration factor greater than 1 is indicative of a

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hydrophobic or lipophilic chemical. It is an indicator of how probable a chemical is to bioaccu-mulation. These chemicals have high lipid affinities and will concentrate in tissues with high lipidcontent.[23]

2.6. Enrichment factor

The enrichment factor (EF) can be utilised to differentiate between the heavy metals originatingfrom human activities and those from natural origin. In this way the degree of anthropogenicinfluence can be assessed. A technique that has often been applied is normalisation of a testedelement against a reference one. A reference element is often a conservative one, such as the mostcommonly analysed elements: Al, Fe, Me, Mn, Sc, Ti etc. Commonly, normalisation of the metalsto a conservative and natural element such as Al is used as an index to evaluate anthropogenicinfluences to the sediments.

According to Ergin et al.,[21] the heavy metal EF is defined as follows:

EF = (M/Al)samples/(M/Al)background area (3)

EF values were interpreted as suggested by Birch [28] where EF < 1 indicates no enrichment;<3 is minor; 3–5 is moderate; 5–10 is moderately severe; 10–25 is severe; 25–50 is very severe;and >50 is extremely severe.

2.7. Potential ecological risk

The potential ecological risk index (RI) was introduced to assess the degree of heavy metalpollution in sediments, according to the toxicity of heavy metal pollution in sediments and theresponse of the environment.[22]

RI =∑

Eir (4)

Eir = T i

r Cif (5)

Cif = Ci

o/Cin (6)

where RI is calculated as the sum of all risk factors for heavy metals in sediments, Eir is the

monomial potential ecological risk factor, T ir is the toxic-response factor for a given substance,

which accounts for a given substance, which accounts for the toxic requirement and the sensitivityrequirement (Table 3). Ci

f is the contamination factor, Cio is the concentration of metals in sediment,

and Cin is a reference value for metals (Table 3).

The potential ecological risk for single regulator (Eir) follows a ranking with: low risk (Ei

r < 40),moderate (40 ≤ Ei

r < 80), considerable (80 ≤ Eir < 160), high (160 ≤ Ei

r < 320) and very high(Ei

r ≥ 320). RI is the total heavy metal potential ecological risk index and represents the sensitivityof various biological communities to toxic substances and follows the terminology: low ecologicalrisk for all factors (RI < 150), moderate (150 ≤ RI < 300), considerable (300 ≤ RI < 600) andvery high (RI ≥ 600).[29]

Table 3. Reference values (Cin) and toxicity coefficients (Ti

r ) of heavy metals in sediments.

Heavy metals As Cd Cr Cu Hg Ni Pb Zn

Cin (μg/g) 9.50 0.30 123.20 28.30 0.10 57.00 19.80 84.00

Tir 10 30 2 5 40 5 5 1

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3. Results and discussion

3.1. Metals in the Tisza River sediment

Contents of metals (in μg/g of dry mass) in the sediment of the Tisza River bed are given in Table 4.In Table 5 are presented Serbian limit values and maximum legal concentrations for heavy metals(As, Cd, Cr, Cu, Hg, Pb, Ni and Zn) in sediment for each sediment sample, depending on the% of OM and clay as discussed above. The concentrations of Cd, Cr, Cu, Ni and Zn in TiszaRiver sediments and their limit values and maximum legal concentrations which are defined withSRLVsS are shown in Figure 2.

The declining trend of metal concentrations in the sediment is the following: Al > Fe >

Mn > Zn > Sr > Cr > Cu > Ni > Pb > Co > As > Cd > Se > Hg.Al followed by Fe had thehighest accumulation values for all sites. This is expected asAl and Fe are the most common weath-ering products. Which correspond to a classical weathering product in research areas where thesediments are mainly composed of Al and Fe.

The sediment samples for all sites contained elevated concentrations of Cd, Cr, Cu, Ni and Znwith regard to SRLVsS. Concentrations of Cd, Cr, Cu and Zn are below maximum allowed legalconcentration, except Ni which concentrations are above maximum legal concentration (Figure 2).Research area has a strong agriculture activity and the main metal sources are impurities fromfertilisers, pesticides and sewage sludge.

The obtained results were compared with international guideline values for freshwater sedi-ments reported previously by MacDonald et al.[25] (Tables 6 and 7). Specifically, the previouslypublished SQGs (Sediment Quality Guidelines) for the protection of sediment-dwelling organismsin freshwater ecosystems were grouped into two categories according to their original narra-tive intent, including threshold effect concentration (TECs) and probable effect concentration(PECs). The TECs were intended to identify contaminant concentrations below which harmfuleffects on sediment-dwelling organisms were not expected. TECs include threshold effect levels[TELs; 30,31], effect range low values [ERLs; 32], lowest effect levels [LELs; 33], minimal effectthresholds [METs; 34], and sediment quality advisory levels [SQALs; 35] (Table 6). The PECswere intended to identify contaminant concentrations above which harmful effects on sediment-dwelling organisms were expected to occur frequently. PECs include probable effect levels [PELs;30,31], effect range median values [ERMs; 32]; severe effect levels [SELs; 33], and toxic effectthresholds [TETs; 34] (Table 7). In comparison with international guideline values for freshwatersediments all heavy metals in sediments from Tisza River show values which are above thresholdeffect concentration TECs but below probable effect concentration PECs, except Cr and Ni whichvalues are above probable effect concentration PECs.

3.2. Potential ecological risk

Potential ecological risk index was applied for assessing the status of sediment heavy metalenrichment and the extent of potential ecological risk. Using Equations (4–6) and parameterslisted in Table 3, the potential ecological risk indices Ei

r and RI for each site were obtainedand are listed in Table 8. Potential ecological risk for single regulator indexes (Ei

r) for the TiszaRiver sediments at all sites show low potential ecological risk for all analysed metals, exceptHg that had moderate and considerable risk and Cd that had high potential ecological risk forall sites. The total heavy metal potential ecological risk index (RI) leads to the conclusion thatsediment samples had moderate and considerable ecological risk. Moderate (150 ≤ RI < 300)and considerable (300 ≤ RI < 600) heavy metals potential risk in the Tisza River reveals themoderate and considerable danger of heavy metals to resident aquatic organisms of this river. TheRI values were clearly related to the degree of anthropogenic disturbance.

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Table 4. Metal concentrations (Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, Sr, Zn) in sediments (in μg/g of dry mass).

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

1 80,947.00 15.10 2.00 18.20 123.20 77.60 44,832.70 0.26 851.90 50.00 44.60 0.50 140.70 299.002 80,418.00 17.60 2.60 20.20 130.00 77.00 46,441.30 0.36 619.60 45.80 48.90 0.50 144.10 307.003 85,765.00 16.40 2.40 20.80 130.00 86.10 48,469.60 0.25 464.70 51.30 51.80 0.50 143.10 315.004 79,994.00 17.40 2.40 18.30 130.00 81.30 44,832.70 0.23 1394.00 47.00 50.00 0.50 131.60 364.005 80,947.00 17.30 2.80 18.20 130.00 80.20 45,042.50 0.27 1548.90 46.40 51.90 0.50 145.40 335.006 76,976.00 14.80 1.60 16.50 130.00 67.80 42,244.80 0.17 1471.50 44.10 43.60 1.00 138.30 287.007 80,629.00 15.00 1.60 18.70 123.20 67.70 44,692.80 0.18 1626.30 47.20 42.00 0.50 150.00 253.008 77,188.00 14.10 2.00 18.00 123.20 67.90 41,965.10 0.30 1394.00 45.50 42.70 0.50 136.10 301.009 79,200.00 17.40 2.60 17.20 136.80 84.00 43,923.40 0.20 1161.70 45.90 56.00 0.50 137.40 349.0010 81,318.00 15.30 1.90 17.30 116.30 74.30 44,762.70 0.22 1394.00 49.30 44.40 0.50 148.80 282.0011 79,571.00 18.50 2.50 18.70 136.80 88.90 44,692.80 0.26 1316.60 49.60 50.40 0.50 137.80 346.0012 80,629.00 14.30 2.50 17.50 130.00 76.50 44,413.00 0.31 1239.10 46.00 46.80 0.50 138.70 303.0013 81,741.00 19.00 2.10 18.00 130.00 82.00 46,721.10 0.28 1471.50 48.10 48.50 0.80 131.20 336.0014 86,824.00 18.70 1.40 18.40 123.20 82.90 48,119.90 0.21 1471.50 51.70 45.80 0.50 143.90 287.0015 75,600.00 17.10 2.10 17.20 123.20 75.30 40,496.30 0.30 1394.00 50.50 50.90 0.50 132.40 337.0016 79,200.00 17.00 1.90 16.60 130.00 61.60 43,433.80 0.18 1548.90 47.50 43.90 0.50 135.90 281.0017 80,629.00 14.30 2.50 17.50 130.00 76.50 44,413.00 0.31 1239.10 46.00 46.80 0.50 138.70 303.0018 81,635.00 17.40 1.50 17.00 123.20 68.00 46,371.40 0.18 1394.00 47.40 44.50 0.50 134.40 284.0019 78,459.00 17.80 2.20 17.10 123.20 76.00 41,895.10 0.25 1626.30 47.10 49.70 0.50 131.90 349.0020 83,382.00 16.90 1.80 17.20 130.00 72.90 45,881.80 0.14 464.70 50.20 47.30 0.50 144.90 279.0021 83,806.00 17.40 1.90 17.90 130.00 73.70 45,392.20 0.26 1394.00 53.70 51.20 0.50 117.20 354.0022 84,441.00 16.80 1.70 18.10 123.20 78.10 47,420.50 0.20 1394.00 50.40 44.60 0.50 145.60 273.0023 82,535.00 16.30 20 18.50 116.30 78.00 45,392.20 0.19 1548.90 51.60 47.40 0.50 131.00 311.0024 85,235.00 16.30 1.50 19.90 123.20 78.20 46,930.90 0.20 1239.10 51.80 45.50 0.50 141.80 287.0025 78,935.00 14.10 2.60 15.80 130.00 67.30 43,224.00 0.22 1548.90 43.00 47.40 0.50 127.50 284.00

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Table 5. Serbian limit values and maximum legal concentrations for heavy metals (As, Cd, Cr, Cu, Hg, Ni, Pb and Zn) (in μg/g of dry mass) in sediment for each sediment sample,depending on the % of OM and clay which are defined in the Serbian Regulation of limit values pollutant substances into surface water, groundwater and sediments, and the deadlinesfor their attaining.

As Cd Cr Cu Hg Ni Pb ZnSedimentSamples LV MLC LV MLC LV MLC LV MLC LV MLC LV MLC LV MLC LV MLC

1 26.58 38.49 0.88 7.02 103.54 248.50 33.23 101.54 0.29 1.57 36.77 46.23 78.94 287.89 133.56 410.232 25.11 36.36 0.84 6.70 96.60 231.84 30.94 94.55 0.28 1.50 33.30 41.86 75.26 274.49 122.85 377.313 28.39 41.12 0.92 7.35 112.90 270.96 35.90 109.70 0.31 1.65 41.45 52.11 83.48 304.46 147.40 452.724 23.43 33.94 0.80 6.38 88.20 211.68 28.44 86.90 0.27 1.43 29.10 36.58 71.08 259.23 110.27 338.695 23.80 34.46 0.81 6.46 89.88 215.71 29.02 88.66 0.27 1.44 29.94 37.64 71.99 262.56 112.90 346.766 20.96 30.35 0.73 5.83 76.70 184.08 24.56 75.03 0.25 1.32 23.35 29.35 64.90 236.68 92.37 283.717 22.40 32.44 0.77 6.17 83.18 199.63 26.86 82.08 0.26 1.38 26.59 33.43 68.50 249.82 102.63 315.238 22.15 32.08 0.76 6.11 82.04 196.90 26.47 80.88 0.26 1.37 26.02 32.71 67.88 247.55 100.85 309.749 22.23 32.19 0.77 6.13 82.42 197.81 26.58 81.23 0.26 1.37 26.21 32.95 68.07 248.24 101.42 311.4910 25.23 36.54 0.84 6.73 97.14 233.14 31.15 95.17 0.28 1.51 33.57 42.20 75.58 275.63 123.72 379.9911 24.00 34.76 0.81 6.48 91.16 218.78 29.26 89.42 0.27 1.45 30.58 38.44 72.50 264.40 114.61 352.0312 22.67 32.83 0.78 6.24 84.26 202.22 27.32 83.47 0.26 1.39 27.13 34.11 69.17 252.26 104.45 320.8013 24.18 35.02 0.81 6.51 92.18 221.23 29.52 90.19 0.27 1.46 31.09 39.08 72.95 266.07 116.07 356.4914 22.97 33.26 0.79 6.30 85.68 205.63 27.78 84.89 0.26 1.40 27.84 35.00 69.92 254.99 106.64 327.5215 24.78 35.89 0.83 6.63 95.10 228.24 30.43 92.97 0.28 1.49 32.55 40.92 74.45 271.51 120.49 370.0916 24.83 35.96 0.83 6.64 95.32 228.77 30.52 93.25 0.28 1.49 32.66 41.06 74.58 272.00 120.86 371.2217 20.00 28.96 0.69 5.51 73.58 176.59 22.77 69.58 0.24 1.28 21.79 27.39 62.49 227.90 86.42 265.4318 24.01 34.77 0.81 6.48 91.28 219.07 29.27 89.43 0.27 1.45 30.64 38.52 72.52 264.50 114.74 352.4319 20.43 29.59 0.72 5.78 73.38 176.11 23.90 73.04 0.24 1.29 21.69 27.27 63.58 231.88 87.90 269.9920 27.17 39.35 0.89 7.09 107.06 256.94 34.02 103.95 0.30 1.60 38.53 48.44 80.43 293.34 138.44 425.2221 29.05 42.08 0.93 7.44 116.74 280.18 36.79 112.41 0.32 1.68 43.37 54.52 85.14 310.50 152.76 469.1922 25.71 37.24 0.85 6.79 99.94 239.86 31.79 97.13 0.29 1.53 34.97 43.96 76.78 280.00 127.62 391.9723 27.64 40.02 0.90 7.21 109.06 261.74 34.78 106.26 0.30 1.62 39.53 49.69 81.59 297.56 141.68 435.1524 28.85 41.78 0.93 7.45 115.00 276.00 36.62 111.90 0.31 1.67 42.50 53.43 84.62 308.62 150.68 462.8125 25.31 36.66 0.84 6.74 97.64 234.34 31.26 95.51 0.28 1.51 33.82 42.52 75.79 276.40 124.41 382.12

Notes: LV, limit values; MLC, maximum legal concentration.

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Figure 2. Distribution of Cd, Cr, Cu, Ni and Zn (in μg/g of dry mass) in sediment samples. LV – limit values andMLC – maximum legal concentration defined with Serbian Regulation of limit values pollutant substances into surfacewater, groundwater and sediments and the deadlines for their attaining.

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Chemistry and Ecology 11

Table 6. Sediment quality guidelines for metals in freshwater ecosystems that reflect TECs (i.e., belowwhich harmful effects are unlikely to be observed).[24]

Threshold Effect Concentrations

Substance TEL LEL MET ERL TEL-HA28 SQAL Consensus-Based TEC

Metals (in mg/kg DW)Arsenic 5.9 6 7 33 11 NG 9.79Cadmium 0.596 0.6 0.9 5 0.58 NG 0.99Chromium 37.3 26 55 80 36 NG 43.4Copper 35.7 16 28 70 28 NG 31.6Lead 35 31 42 35 37 NG 35.8Mercury 0.174 0.2 0.2 0.15 NG NG 0.18Nickel 18 16 35 30 20 NG 22.7Zinc 123 120 150 120 98 NG 121

Notes: TEL, Threshold effect level; dry weight (Smith et al. [30]); LEL, Lowest effect level, dry weight (Persaud et al.[33]); MET, Minimal effect threshold; dry weight (EC and MENVIQ [34]); ERL, Effect range low; dry weight (Longand Morgan [32]); TEL-HA28, Threshold effect level for Hyalella azteca; 28 day test; dry weight (US EPA [31]); SQAL,Sediment quality advisory levels; dry weight at 1% OC (US EPA [35]); NG, No guideline.

Table 7. Sediment quality guidelines for metals in freshwater ecosystems that reflect PECs (i.e.,above which harmful effects are likely to be observed).[24]

Substance PEL SEL TET ERM PEL-HA28 Consensus-Based PEC SQAL

Metals (in mg/kg DW)Arsenic 17 33 17 85 48 33.0Cadmium 3.53 10 3 9 3.2 4.98Chromium 90 110 100 145 120 111Copper 197 110 86 390 100 149Lead 91.3 250 170 110 82 128Mercury 0.486 2 1 1.3 NG 1.06Nickel 36 75 61 50 33 48.6Zinc 315 820 540 270 540 459

Notes: PEL, Probable effect level; dry weight (Smith et al. [30]); SEL, Severe effect level, dry weight (Persaud et al.[33]); TET, Toxic effect threshold; dry weight (EC and MENVIQ [34]); ERM, Effect range median; dry weight(Long and Morgan [32]); PEL-HA28, Probable effect level for Hyalella azteca; 28-day test; dry weight (US EPA[31]); NG, No guideline.

3.3. Enrichment factor (EF)

To determine whether levels of heavy metals in Tisza River sediments and its surrounding envi-ronment were of anthropogenic origins Enrichment Factor (EF) was calculated. In this study Alwas used as a conservative tracer to differentiate natural from anthropogenic components. Surfacesediments from Tisza River have minor enrichment factor (EF < 3) for As, Cu, Ni, Co, Pb, Sr, Crand Se, minor and moderate for Hg, moderate (EF 3–5) for Zn and moderately severe enrichmentfactor (EF 10–25) for Cd (Table 9). The values of Zn and Cd were clearly related to the degree ofanthropogenic disturbance.

3.4. Metals concentration in fish liver

A total of 160 fish were chosen for metal concentration analysis from the four sampling points(Figure 1). Sampled specimens were represented by four different fish species. The collected fishbelong to three groups according to feeding habits carnivorous northern pike (Esox lucius L.),benthivorous sterlet (Acipenser ruthenus L.), silver bream (Brama brama L.), and omnivorouscommon carp (Cyprinus carpio L.).

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Table 8. Heavy metal potential ecological risk indexes of the Tisza River system.

As Cd Cr Cu Hg Ni Pb ZnSedimentsamples Ei

r Eir Ei

r Eir Ei

r Eir Ei

r Eir RI

1 15.89 200.00 2.00 13.71 104.00 4.39 11.26 3.56 354.812 18.53 260.00 2.11 13.60 144.00 4.02 12.35 3.65 458.263 17.26 240.00 2.11 15.21 100.00 4.50 13.08 3.75 395.914 18.32 240.00 2.11 14.36 92.00 4.12 12.63 4.33 387.875 18.21 280.00 2.11 14.17 108.00 4.07 13.11 3.99 443.666 15.58 160.00 2.11 11.98 68.00 3.87 11.01 3.42 275.977 15.79 160.00 2.00 11.96 72.00 4.14 10.61 3.01 279.518 14.84 200.00 2.00 12.00 120.00 3.99 10.78 3.58 367.199 18.32 260.00 2.22 14.84 80.00 4.03 14.14 4.15 397.7010 16.11 190.00 1.89 13.13 88.00 4.32 11.21 3.36 328.0211 19.47 250.00 2.22 15.71 104.00 4.35 12.73 4.12 412.6012 15.05 250.00 2.11 13.52 124.00 4.04 11.82 3.61 424.1513 20.00 210.00 2.11 14.49 112.00 4.22 12.25 4.00 379.0714 19.68 160.00 2.00 14.65 84.00 4.54 11.57 3.42 279.8615 18.00 210.00 2.00 13.30 120.00 4.43 12.85 4.01 384.5916 17.89 190.00 2.11 10.88 72.00 4.17 11.09 3.35 311.4917 18.32 150.00 2.00 12.01 72.00 4.16 11.24 3.38 273.1118 18.74 220.00 2.00 13.43 100.00 4.13 12.55 4.15 375.0019 17.79 180.00 2.11 12.88 56.00 4.40 11.94 3.32 288.4420 18.32 190.00 2.11 13.02 104.00 4.71 12.93 4.21 349.3021 17.68 170.00 2.00 13.80 80.00 4.42 11.26 3.25 302.4122 17.16 200.00 1.89 13.78 76.00 4.53 11.97 3.70 329.0323 17.16 150.00 2.00 13.82 80.00 4.54 11.49 3.42 282.4324 18.40 190.00 2.00 13.02 72.00 4.43 12.73 4.15 275.9725 17.13 160.00 2.11 10.88 124.00 4.40 11.26 3.36 458.26

Table 9. Heavy metal Enrichment Factor in Tisza River sediments.

As Cd Cr Cu Hg Ni Pb ZnSedimentsamples EF EF EF EF EF EF EF EF

1 1.60 6.70 0.95 2.75 2.61 1.11 2.26 3.582 1.87 8.76 1.01 2.75 3.64 1.02 2.50 3.703 1.64 7.59 0.95 2.88 2.37 1.07 2.48 3.564 1.86 8.13 1.02 2.92 2.34 1.05 2.57 4.415 1.83 9.38 1.00 2.85 2.71 1.03 2.63 4.016 1.65 5.63 1.06 2.53 1.80 1.03 2.33 3.617 1.59 5.38 0.96 2.41 1.82 1.05 2.14 3.048 1.56 7.02 1.00 2.53 3.16 1.06 2.27 3.789 1.88 8.90 1.08 3.05 2.05 1.04 2.90 4.2710 1.61 6.33 0.89 2.63 2.20 1.09 2.24 3.3611 1.99 8.52 1.08 3.21 2.66 1.12 2.60 4.2112 1.52 8.40 1.01 2.73 3.13 1.02 2.38 3.6413 1.99 6.96 0.99 2.88 2.79 1.06 2.44 3.9814 1.84 4.37 0.89 2.74 1.97 1.07 2.17 3.2015 1.94 7.53 1.02 2.86 3.23 1.20 2.77 4.3216 1.84 6.50 1.03 2.23 1.85 1.08 2.28 3.4317 1.82 4.98 0.94 2.39 1.79 1.04 2.24 3.3718 1.94 7.60 0.98 2.78 2.59 1.08 2.60 4.3119 1.73 5.85 0.98 2.51 1.37 1.08 2.33 3.2420 1.78 6.15 0.97 2.53 2.52 1.15 2.51 4.0921 1.70 5.46 0.91 2.66 1.93 1.07 2.17 3.1322 1.69 6.57 0.88 2.72 1.87 1.12 2.36 3.6523 1.94 7.53 1.02 2.86 3.23 1.20 2.77 4.3224 1.64 4.77 0.90 2.64 1.91 1.09 2.19 3.2625 1.53 8.93 1.03 2.45 2.27 0.98 2.47 3.48

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Chemistry and Ecology 13

Table 10. Results of one-way ANOVA – Tests of bioaccumulation of metals atdifferent localities of sampling.

Sum of Squares Df Mean Square F Sig.

Between Groups 22.445 3 7.482 0.105 .957∗Within Groups 3974.302 56 70.970Total 3996.748 59

∗The mean difference is significant at the 0.05 level.

Table 11. Results of One-way ANOVA – Tests of bioaccumulation of metals indifferent fish species.

Sum of Squares Df Mean Square F Sig.

Between Groups 1339.517 3 446.506 9.410 .0001∗Within Groups 2657.230 56 47.451Total 3996.748 59

∗The mean difference is significant at the 0.05 level.

The results did not indicate any differences between the measured metal concentrations fromthe four sampling points (Figure 1). Statistical analysis showed that the differences between metalconcentrations by sampling site were not significant which was confirmed by results of one-wayANOVA (p > 0.05) (Table 10).

The difference in bioaccumulation between particular fish species was significant (p < 0.05)and the Games-Howell post hoc test revealed the significantly greater content of metals in commoncarp than in silver bream, sterlet and northern pike (Table 11). This study confirms the hypothesisthat predatory fish are not the best indicator species, as previously proposed by Rincon-Leon et al.[36] These authors studied the importance of eating habits in the estimation of environmentalcontamination through indicator species and concluded that omnivorous species such as C. carpio,as biological indicator of contamination, allows for estimation with a greater confidence level thanthe piscivourous species. Yousafzai et al. [37] showed that omnivore fish accumulate 65.2% moremetal than carnivore fish.

Content of metals (in μg/g wet weight) in the liver four ecologically different fish species fromdifferent localities from Tisza River are given in Table 12. The mean concentration of the testedelements for common carp followed the sequence: Zn > Fe > Al > Cu > Mn > Cd > Pb >

Se > Sr > As > Cr > Ni > Co > Hg; for northern pike: Fe > Zn > Cu > Mn > Sr > Se >

Al > Cr > Pb > Hg > Cd > As > Co > Ni; for silver bream: Fe > Zn > Al > Cu > Sr >

Mn > Se > Pb > Cr > Cd > As > Co > Ni > Hg; and for sterlet: Fe > Al > Zn > Cu >

Mn > Se > Pb > As > Cd > Sr > Cr > Ni > Hg > Co. In total average concentrations of Al(31.86 μg/g) mostly accumulated in liver of the sterlet. BCF of Al in all fish species was the low-est (Table 13). Metals in sediments originating from the decomposition of rocks, such as Al andFe are usually connected in the form of chemical compounds that are not easily bio-available forthe wildlife. Data related to the bioaccumulation of As in the river are spares. Aquatic organismsadopt As either directly from the water or through the food chain. As accumulates in primaryproducers (plants and algae), but its concentration does not increase in the invertebrates and fish.In total average values As (0.64 μg/g) accumulated the most in sterlet. But these values are belowthe maximum legal concentration of As (2 μg/g) which prescribed SRLVsF (Figure 3). Cd is nota part of natural biochemical processes and is extremely hazardous toxic heavy metal that can beassimilated, stored and concentrated by organisms through the food chain.[38] In total averageCd concentrations (0.78 μg/g) accumulated the most in common carp. The liver of common carpshows the highest BCF for Cd but it is still less than one (Table 13). Concentrations of Cd in

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Table 12. Concentrations of Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, Sr and Zn in liver (in μg/g wet weight) of B. brama, A. ruthenus, C. carpio and E. luceus from differentlocalities.

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

3rd km river flowB. brama 4.07 ± 0.03 0.09 ± 0.02 0.07 ± 0.01 0.03 ± 0.01 0.09 ± 0.01 8.99 ± 0.08 53.91 ± 0.34 n.d. 1.56 ± 0.01 0.02 ± 0.01 0.12 ± 0.03 1.20 ± 0.284 0.24 ± 0.01 20.11 ± 0.11A. ruthenus 43.47 ± 0.06 0.94 ± 0.02 0.58 ± 0.01 0.02 ± 0.02 0.26 ± 0.01 8.29 ± 2.96 70.13 ± 0.15 0.09 ± 0.01 1.64 ± 0.01 0.17 ± 0.01 1.89 ± 0.05 1.37 ± 0.05 0.31 ± 0.01 30.23 ± 0.09C. carpio 45.56 ± 0.06 0.12 ± 0.01 1.25 ± 0.01 0.03 ± 0.02 0.22 ± 0.01 11.20 ± 0.10 179.56 ± 1.14 n.d. 2.23 ± 0.01 0.08 ± 0.02 0.90 ± 0.03 0.22 ± 0.21 0.32 ± 0.04 173.68 ± 0.46E. luceus 0.48 ± 0.01 n.d. 0.02 ± 0.02 0.02 ± 0.02 0.09 ± 0.01 6.87 ± 0.03 162.38 ± 0.63 0.03 ± 0.01 1.15 ± 0.01 n.d. 0.11 ± 0.07 0.89 ± 0.14 0.14 ± 0.01 30.06 ± 0.1358th km river flowB. brama 0.75 ± 0.01 0.07 ± 0.05 0.18 ± 0.04 0.04 ± 0.03 0.10 ± 0.01 24.11 ± 0.02 47.31 ± 0.24 n.d. 1.55 ± 0.01 0.02 ± 0.02 0.29 ± 0.02 1.54 ± 0.19 0.15 ± 0.01 25.04 ± 0.01A. ruthenus 1.52 ± 0.72 0.33 ± 0.13 0.44 ± 0.23 n.d. n.d. n.d. n.d. n.d. n.d. 0.04 ± 0.02 0.03 ± 0.09 0.99 ± 0.25 n.d. 11.07 ± 6.05C. carpio 12.70 ± 0.06 0.04 ± 0.04 0.75 ± 0.04 0.03 ± 0.02 0.12 ± 0.02 30.12 ± 0.11 130.28 ± 1.34 n.d. 1.53 ± 0.01 0.02 ± 0.02 1.11 ± 0.03 0.03 ± 0.13 0.19 ± 0.01 150.49 ± 0.67E. luceus 0.20 ± 0.02 0.04 ± 0.04 0.01 ± 0.01 0.01 ± 0.01 0.12 ± 0.01 2.57 ± 0.05 31.70 ± 0.19 n.d. 0.24 ± 0.01 0.01 ± 0.01 0.23 ± 0.05 0.21 ± 0.17 2.26 ± 0.01 13.77 ± 0.0572nd km river flowB. brama 81.82 ± 0.23 0.03 ± 0.04 0.02 ± 0.04 n.d. 0.31 ± 0.01 1.29 ± 0.05 114.64 ± 0.86 n.d. 5.35 ± 0.03 0.10 ± 0.02 0.03 ± 0.01 0.62 ± 0.02 11.26 ± 1.63 14.23 ± 0.02A. ruthenus 66.19 ± 1.24 0.29 ± 0.03 0.07 ± 0.05 n.d. 0.34 ± 0.04 n.d. 85.66 ± 7.49 0.01 ± 0.01 2.74 ± 0.24 0.12 ± 0.01 0.18 ± 0.02 0.76 ± 0.23 0.57 ± 0.06 16.50 ± 0.34C. carpio 5.26 ± 0.02 0.09 ± 0.02 0.38 ± 0.01 0.02 ± 0.03 0.10 ± 0.01 10.56 ± 0.04 76.00 ± 0.52 0.01 ± 0.02 1.89 ± 0.01 0.01 ± 0.01 n.d. 0.58 ± 0.09 0.17 ± 0.10 114.21 ± 0.19E. luceus 0.14 ± 0.01 0.01 ± 0.03 0.02 ± 0.03 0.02 ± 0.02 0.08 ± 0.02 6.13 ± 0.03 109.90 ± 0.91 0.09 ± 0.01 1.36 ± 0.01 n.d. n.d. 0.66 ± 0.25 0.13 ± 0.01 33.22 ± 0.03153rd km river flowB. brama 0.47 ± 0.02 0.06 ± 0.01 0.15 ± 0.01 0.05 ± 0.03 0.10 ± 0.01 20.91 ± 0.14 59.40 ± 0.31 0.01 ± 0.01 1.61 ± 0.01 0.01 ± 0.02 0.34 ± 0.01 1.41 ± 0.31 0.27 ± 0.02 28.53 ± 0.22A. ruthenus 16.25 ± 0.02 0.99 ± 0.02 0.79 ± 0.01 0.10 ± 0.03 0.250 ± 0.01 10.89 ± 0.08 71.76 ± 0.18 0.08 ± 0.02 2.18 ± 0.01 0.14 ± 0.01 0.55 ± 0.08 1.48 ± 0.16 0.30 ± 0.02 31.26 ± 0.03C. carpio 6.47 ± 0.06 0.30 ± 0.02 0.73 ± 0.01 0.07 ± 0.02 0.11 ± 0.03 11.43 ± 0.08 193.66 ± 0.67 0.01 ± 0.01 2.17 ± 0.01 0.03 ± 0.01 n.d. 0.35 ± 0.18 0.3 ± 0.01 181.67 ± 0.53E. luceus 0.15 ± 0.01 0.01 ± 0.01 0.02 ± 0.02 0.02 ± 0.01 0.09 ± 0.01 9.11 ± 0.03 139.59 ± 0.89 0.03 ± 0.01 1.64 ± 0.01 n.d. n.d. 0.80 ± 0.15 0.13 ± 0.02 28.22 ± 0.04

Note: n.d., undetectable. The values in the table represent mean value ± SD in total analysed specimens.

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Chemistry and Ecology 15

Table 13. BCF of Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, Sr and Zn in liver (in μg/g wet weight) of B. brama,A. ruthenus, C. carpio and E. luceus from different localities.

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

3rd km river flowB. brama 0.00 0.01 0.03 0.00 0.00 0.12 0.00 0.00 0.00 0.00 0.00 2.40 0.00 0.07A. ruthenus 0.00 0.05 0.22 0.00 0.00 0.11 0.00 0.25 0.00 0.00 0.04 2.74 0.00 0.10C. carpio 0.00 0.01 0.48 0.00 0.00 0.15 0.00 0.00 0.00 0.00 0.02 0.44 0.00 0.57E. luceus 0.00 0.00 0.01 0.00 0.00 0.09 0.00 0.08 0.00 0.00 0.00 1.78 0.00 0.1058th km river flowB. brama 0.00 0.00 0.06 0.00 0.00 0.30 0.00 0.00 0.00 0.00 0.01 3.08 0.00 0.07A. ruthenus 0.00 0.02 0.16 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.98 0.00 0.03C. carpio 0.00 0.00 0.27 0.00 0.00 0.38 0.00 0.00 0.00 0.00 0.02 0.06 0.00 0.45E. luceus 0.00 0.00 0.00 0.00 0.00 0.03 0.00 0.00 0.00 0.00 0.00 0.42 0.02 0.0472nd km river flowB. brama 0.00 0.00 0.01 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.62 0.08 0.04A. ruthenus 0.00 0.01 0.04 0.00 0.00 0.00 0.00 0.05 0.00 0.00 0.00 0.76 0.00 0.05C. carpio 0.00 0.00 0.23 0.00 0.00 0.15 0.00 0.05 0.00 0.00 0.00 0.58 0.00 0.39E. luceus 0.00 0.00 0.01 0.00 0.00 0.09 0.00 0.52 0.00 0.00 0.00 0.66 0.00 0.11153rd km river flowB. brama 0.00 0.00 0.07 0.00 0.00 0.27 0.00 0.03 0.00 0.00 0.00 2.82 0.00 0.08A. ruthenus 0.00 0.05 0.37 0.00 0.00 0.14 0.00 0.26 0.00 0.00 0.01 2.96 0.00 0.09C. carpio 0.00 0.01 0.34 0.00 0.00 0.15 0.00 0.03 0.00 0.00 0.00 0.7 0.00 0.53E. luceus 0.00 0.00 0.00 0.00 0.00 0.12 0.00 0.1 0.00 0.00 0.00 1.6 0.00 0.08

the liver of common carp and sterlet are above maximum legal concentration (0.1 μg/g) whichprescribed SRLVsF (Figure 3). Concentration of Co determined in the fish liver is a most probablya reflection of the functions of this tissues in Co metabolism. This metal belongs to the group ofessential elements and is a component of the B12 vitamin. In total average values Co (0.04 μg/g),accumulated the most in common carp. There are several different kinds of Cr that differ in theireffects on organisms. Cr enters the air, water and sediment in the chromium(III) and chromium(VI)form through natural processes and human activities. In water Cr absorb on sediment and becomeimmobile. Cr is not known to accumulate in the bodies of fish, but high concentrations, owing tothe disposal of metal products in surface waters, can damage the gills of fish that swim near thepoint of disposal. Cr is a non-essential element. In total average values (0.21 μg/g) accumulatedthe most in sterlet. Cu is an essential element because of its important role in biological systems.In total average values Cu (15.83 μg/g) accumulated the most in common carp. Low levels foundin the present study are in agreement with its homeostatic control.[39] The common carp livershows the highest BCF for Cu but it is still less than one (Table 13). In total average values Fe(144.88 μg/g) accumulated the most in common carp. Similar to Al, Fe has a low BCF becausein the sediment it originates from the decomposition of rocks, and it is not easily bio-availablefor aquatic ecosystem wildlife. Hg is a highly toxic element that is found both naturally and as anintroduced contaminant in the environment. The toxic effects of Hg depend on its chemical formand the route of exposure. Methylmercury (CH3Hg) is the most toxic form. It affects the immunesystem, alters genetic and enzyme systems, and damages the nervous system. CH3Hg is particu-larly damaging to developing embryos, which are five to ten times more sensitive than adults. Intotal average values Hg (0.05 μg/g) accumulated the most in sterlet. Concentrations of Hg in thefish liver are below maximum legal concentration levels (0.5 μg/g) which prescribed SRLVsF(Figure 3). Mn is an essential element for both animals and plants and is possibly homeostaticallycontrolled and relatively non-toxic to aquatic biota and is seldom a problem in freshwater. In totalaverage values Mn (2.52 μg/g) accumulated the most in silver bream. The larger part of all Nicompounds that are released to the environment will adsorb to sediment particles and becomeimmobile. In acidic ground however, Ni is bound to become more mobile and it will often rinse

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Figure 3. Concentrations of As, Cd, Hg and Pb (in μg/g wet weight) in liver common carp, northern pike, silverbream and sterlet and Serbian Regulation of levels of pesticides, metals and metalloids and other toxic substances,chemotherapeutics, anabolics and other substances which can be found in food.

out to the groundwater. There is not much information available on the effects of Ni on organ-isms. For animals Ni is an essential foodstuff in small amounts. But, is not only favourable as anessential element; it can also be dangerous when the maximum tolerable amounts are exceeded. Intotal average values Ni (0.12 μg/g) accumulated mostly in sterlet. Pb is a toxic metal that can beassimilated, stored and concentrated by organism trough the food chain. In total average valuesPb (0.66 μg/g) accumulated the most in sterlet. Concentrations of Pb in the liver of commoncarp and sterlet are above maximum legal concentration (0.4 μg/g) which prescribed SRLVsF(Figure 3). The obtained values for Se in the livers of the starlet and silver bream are higherthan those in the sediment. In total average values Se (1.19 μg/g) accumulated the most in silverbream. Se is the only metal that shows a negative linear correlation between the concentration inthe liver of starlet and silver bream and sediments. The livers of sterlet and silver bream show thehighest BCF for Se (Table 13). Sr in its elemental form occurs naturally in many compartmentsof the environment, including rocks, soil, water, and air. Strontium compounds can move throughthe environment fairly easily, because many of the compounds are water–soluble. Because of thenature of Sr, some of it can end up in fish, livestock and other animals. In total average values Sr(2.98 μg/g) accumulated the most in silver bream. Zn is a very common substance that occursnaturally. Occurs naturally in air, water and sediment, but Zn concentrations are rising unnaturally,owing to addition of Zn through human activities. Zn is essential for fish. In total average values(155.01 μg/g) accumulated the most in common carp.

Values for Pearson’s Correlation Coefficient between the contents of metals in the sediment andliver at particular localities were similar for all four fish species. All metals which we investigatedrevealed positive correlation between their contents in the liver and in the sediment for all fishspecies at all localities (r < 0, 5), except Se. Se is the only metal that shows a negative linearcorrelation between the metal concentration in the liver of starlet and silver bream and sediments

4. Conclusions

On the basis of the research conducted at the Tisza River the following conclusions can be drawn:

(a) The sediment samples for all sites contained elevated concentrations of Cd, Cr, Cu, Ni andZn. Concentrations of Cd, Cr, Cu and Zn are below maximum legal concentration, except

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Chemistry and Ecology 17

Ni which values are above maximum legal concentration based on the Serbian Regulationof limit values pollutant substances into surface water, groundwater and sediments, and thedeadlines for their attaining;

(b) Surface sediments from Tisza River showed for As, Cu, Ni, Co, Pb, Sr, Cr and Se minorenrichment factor, for Hg minor and moderate, for Zn moderate and for Cd moderately severeenrichment factor. The concentrations of Zn and Cd were clearly related to the anthropogenicdisturbance;

(c) Potential ecological risk for single regulator indexes for the Tisza River sediments at all sitesshow low potential ecological risk for almost all analysed metals. Mercury had moderate andconsiderable potential ecological risk and Cd had high potential ecological risk for all sites.The total heavy metal potential ecological risk index leads to the conclusion that sedimentsamples had moderate and considerable ecological risk. Moderate and considerable heavymetals potential risk in the Tisza River reveals the moderate and considerable danger ofmetals to resident aquatic organisms of Tisza River;

(d) This study showed that omnivore and benthivore fishes accumulated more metal than carnivorefishes;

(e) Concentrations of Pb and Cd in the liver of common carp and sterlet are above maximumlegal concentration which prescribed Serbian Regulation of levels of pesticides, metals andmetalloids and other toxic substances, chemotherapeutics, anabolics and other substanceswhich can be found in food.

Acknowledgements

Research was supported by Grants 173025, 176006 and 176019 of the Ministry of Education and Science of the Republicof Serbia.

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