Fractionation studies and bioaccumulation of sediment-bound heavy metals in Kolleru lake by edible fish

Environment International 29 (2003) 1001 – 1008 www.elsevier.com/locate/envint

Fractionation studies and bioaccumulation of sediment-bound heavy metals in Kolleru lake by edible fish K. Chandra Sekhar a,*, N.S. Chary a, C.T. Kamala a, D.S. Suman Raj b, A. Sreenivasa Rao c a

Analytical Chemistry and Environmental Sciences, Indian Institute of Chemical Technology (IICT), Hyderabad 500 028 (A.P), India b Centre for Environment, IPGSR, Jawaharlal Nehru Technological University (JNTU), Hyderabad 500 028 (A.P), India c Department of Applied Environmental Chemistry, College of Engineering, Gandhi Institute of Technology and Management (GITAM), Vishakapatnam- 530 045 (A.P), India Received 21 January 2003; accepted 18 March 2003

Abstract Kolleru lake is the largest fresh water lake in the districts of East and West Godavari of Andhra Pradesh, India. Many anthropogenic sources contribute to the heavy metal pollution in the lake and the bioaccumulation of heavy metals in fish helps in assessing the aquatic pollution. Total contents and fractionation of selected heavy metals, viz., Zn, Cu, Cd, Pb, Cr, Ni and Co were measured in sediment sample and three edible fish. The investigation aimed at revealing differences in the accumulation pattern of heavy metals in fish inhabiting sediments characterized by varying metal bioavailability. The metal concentrations were found to be greater than the background concentrations of sediments indicating the anthropogenic origin of metals. Good recovery values were obtained for metal contents in sediments and fish. Large fractions of Zn, Cd and Cu were associated with mobile fraction of sediment and showed greater bioaccumulation in fish whereas Ni and Co were least mobilisable. The results clearly indicate that the fish of Kolleru lake are contaminated with metals and not advisable for human consumption. D 2003 Elsevier Science Ltd. All rights reserved. Keywords: Heavy metals; Fractionation; Bioavailable; Sediments

1. Introduction Bottom sediments are known to act as a sink for heavy metals introduced to the lake waters from both natural and anthropogenic sources (Pempkowiase et al., 1999). Industrial effluents, agricultural runoffs, transport, burning of fossil fuels, animal and human excretions and geologic weathering and domestic waste contribute to the heavy metals in the water bodies (Moore and Ramana Moorthy, 1984; Adnano, 1986). When environmental conditions change (pH, sediment redox potential, etc.) sediments can act as source of metals (Forstner, 1989a,b; Izquierdo et al., 1997; Zoumis et al., 2001; Morillo et al., 2002). Geochemical studies of lagoonal sediments and water are very less in India. There are only few studies attempting to establish the concentration of heavy metals in the sediments of Chilka lake (Asthana, 1976), Pulicat lake (Padma and Periakali, 1999), Dal lake * Corresponding author. E-mail addresses: [email protected], [email protected] (K. Chandra Sekhar). 0160-4120/$ - see front matter D 2003 Elsevier Science Ltd. All rights reserved. doi:10.1016/S0160-4120(03)00094-1

(Shah et al., 1988) and Hussainsagar lake (Sreenivas et al., 2001). There is no reported data on the concentration of heavy metals in the Kolleru lake sediments except for one by one of the authors (Sreenivasa Rao and Ramamohan Rao, 2001a). Kolleru lake is the largest natural fresh water lake of Andhra Pradesh in India and located between latitudes 16j32V and 16j47VN and longitudes 81j05V and 81j27VE. The lake is connected to the sea through the Upputeru river, a distance of 60 km. The catchment area of the lake is 4763 km2 and is occupied by agricultural fields and aquatic ponds (Anjaneyulu and Durga Prasad, 2003). Agricultural runoffs, agricultural effluents and domestic effluents directly enter into the lake through drains, channels and rivers (Amaraneni and Pillala, 2001). In addition, industries like dairy farms, tanneries, paper mills, sugar plants and distilleries located in the vicinity of the lake discharge effluents into the lake (Sreenivasa Rao and Ramamohan Rao, 2001b) (Fig. 1). Agriculture, aquaculture and fishing are the primary activities of the people living in the Kolleru lake basin. It is now widely accepted that the role of aquatic sediments as a sink for metal pollutants cannot be fully assessed by

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Fig. 1. Location of sediment samples from Kolleru lake.

measuring the total metal concentration (Christine et al, 1994). In addition, determination of total element does not give accurate estimate of the likely environmental impact (Christine et al, 1994). Hence, contaminant speciation and its effects on bioavailability are critical to understanding ecotoxicity (Shine, 2001). Metal speciation occurring in the sediments is in turn expected to influence metal bioavailability, and thereby metal content in biota, in particular in the soft tissues of fish and mussels (Pempkowiase et al., 1999; Yap et al., 2002). Since availability critically depends upon the chemical form in which a metal is present in the sediment, considerable interest exists in trace element speciation (Christine et al, 1994). In the present study sequential extraction scheme proposed by Tessier et al. (1979) has been applied successfully to evaluate the properties of metals bound to different phases of sediment matrix. This procedure allows us to obtain the distribution of metals in the following fractions: (a) loosely adsorbed to the surface of sediment particles; (b) bound to carbonates; (c) bound to iron and manganese oxides/hydroxides; (d) complexed by organic matter; and (e) incorporated into clay mineral lattices (Fergusson, 1990; Forstner, 1989a,b). Metal fraction (a) is considered to be the most bioavailable (Forstner, 1989a,b). The differences of metal contents determined in biota were explained on the basis of varying bioavailability. Since metal content in the tissues of fish is species-dependent, three species of edible fish, viz., Channa striata, Catla catla and Oreochromis mossambicus were retrieved from the lake for the present study. No information is available on the relationship between different geochemical fractions of metals in sediments

and metal levels in edible fish of Kolleru lake. This study was carried out with the aim of assessing the metal bioaccumulation in the soft tissue and muscle of edible fish and the possible risk associated with the consumption of these fish by humans.

2. Experimental 2.1. Methods and materials 2.1.1. Reagents All chemicals used were of analytical reagent grade. All solutions were prepared in deionized water. Calibration standards of each metal were prepared by appropriate dilution of the stock solutions of 1000 ppm J.T. Baker/E Merck standards. Physico-chemical characterization was carried out for all the 16 sediments of Kolleru lake using standard methods and are presented in Table 1. An Elico digital model LI-120 pH meter equipped with a combined glass electrode was used in pH measurement and adjustment. An R8C laboratory centrifuge, manufactured by Remi equipments (Mumbai, India), was used in rapid separation of the solid phase from the extractant liquid. 2.2. Measurement of metal contents Concentrations of Zn, Cd, Cu, Pb, Cr, Ni and Co were measured in all samples of sediments and fish obtained by

K. Chandra Sekhar et al. / Environment International 29 (2003) 1001–1008 Table 1 Physico-Chemical characteristics of the sediments of Kolleru lake Sites L1 L2 L3 L4 L5 L6 L7 L8 L9 L10 L11 L12 L13 L14 L15 L16

pH 6.89 7.01 7.11 6.92 6.96 6.99 7.14 7.21 6.89 7.08 7.10 7.0 6.99 6.96 7.22 7.10

Specific gravity

Bulk density (g/cm3)

%Organic carbon

CEC (C mol kg

0.661 0.592 0.590 0.601 0.620 0.589 0.608 0.611 0.5911 0.618 0.631 0.618 0.602 0.590 0.591 0.601

1.22 1.10 1.19 1.21 1.81 1.26 1.29 1.21 1.19 1.10 1.18 1.22 1.26 1.3 1.81 1.21

16.1 15.9 16.7 13.4 17.0 15.8 13.1 12.9 12.8 14.0 13.9 12.7 14.2 13.7 14.1 14.0

34.7 39.2 40.1 26.7 44.1 53.4 50.1 36.7 29.4 28.0 43.4 39.7 33.6 40.4 43.2 39.9

1

)

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values reported are an average of nine readings consisting of three samples using three different instrumental techniques, and recovery values in the range of 94 – 105% were taken, otherwise the experiment was repeated. 2.3. Sampling of sediments and fish

Ultramass 700 ICP-MS (Varian, Australia). Mathematical equations which were built into the software (Jarvis et al., 1992) were used for interference correction. In the absence of sediment standards in our lab for carrying out fractionation studies CANMET soil standards SO-1, SO-3 and SO-4 were used for calibration purposes and for accuracy of the analysis. For QC/QA checks interlaboratory testing was performed by ICP-OES (Jobin Yvon24, at C-MET, Hyderabad) and AAS (SpectrAA-500 Varian, at NGRI Hyderabad) for analyzing all the samples (sediment fractions and fish) including total metal concentrations. The

The sediment samples were collected in triplicates from Kolleru lake in three seasons of the year. A small rowing boat was utilized for collection of the sediment samples. Sediment was collected with sediment collector with an acid-washed plastic scoop and returned to the laboratory in polyethylene bags and frozen until analysis. Some of the fish were collected using a gill net at almost the same locations where the sediments were collected. Fish were then removed from the net, wrapped in plastic bags and frozen until analysis. For the analysis, fish from each age and same weight obtained were selected and dissected in gills, liver and muscles. Sixteen sampling sites (Fig. 1) were selected from the lake and the total heavy metal contents in the sediment are shown in Table 2. 2.4. Sediment characterization Sediment samples were oven-dried (80 jC, 12 h), homogenized in an agate mortar, sieved (2 mm) and stored. Various parameters are studied in characterizing the sediment using standard methods (EAWAG, 1978). Organic carbon content was estimated using standard procedure suggested by Charles and Simmons (1986).

Table 2 Total metal content in 16 locations of Kolleru lake in mg/Kg dry weight Location

Zn

Cu

Cd

Pb

Cr

Ni

Co

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Background values in Kolleru lake Background values of metals in sediments (India) Permissible limits

440 F 20 496 F 23 591 F 31 606 F 40 618 F 41 671 F 43 495 F 30 582 F 34 535 F 29 622 F 42 518 F 27 356 F 18 392 F 14 415 F 18 384 F 13 440 F 21 380 F 12

299 F 27 270 F 15 320 F 20 490 F 30 572 F 38 350 F 24 430 F 28 481 F 28 488 F 29 307 F 19 432 F 18 374 F 16 480 F 28 466 F 25 440 F 21 359 F 18 205 F 10

0.23 F 0.02 0.27 F 0.05 0.28 F 0.07 0.25 F 0.04 0.19 F 0.03 0.15 F 0.01 0.18 F 0.02 0.14 F 0.01 0.21 F 0.02 0.27 F 0.04 0.18 F 0.02 BDL 0.24 F 0.03 0.25 F 0.04 BDL BDL 0.20 F 0.06

5.0 F 0.8 5.6 F 0.86 3.61 F 0.61 4.41 F 0.77 4.50 F 0.76 3.8 F 0.69 2.88 F 0.57 3.43 F 0.65 3.88 F 0.68 5.10 F 0.83 2.54 F 0.54 4.86 F 0.99 2.94 F 0.58 3.87 F 0.67 4.51 F 0.86 4.91 F 0.99 3.4 F 0.71

47 F 7.6 44 F 8.5 50 F 8.9 52 F 9.2 56 F 10.6 54 F 9.5 49 F 8.8 48 F 8.6 51 F 8.9 52 F 9.11 53 F 9.3 54 F 9.50 52 F 9.22 46 F 7.6 63 F 7.1 66 F 12.1 40 F 6.0

0.27 F 0.11 0.18 F 0.09 0.27 F 0.11 0.31 F 0.12 0.41 F 0.14 0.60 F 0.14 0.84 F 0.18 0.67 F 0.17 1.48 F 0.14 1.60 F 0.16 1.58 F 0.15 1.84 F 0.18 1.76 F 0.17 2.16 F 0.20 2.05 F 0.15 2.21 F 0.21 0.39 F 0.1

3.0 F 0.45 2.4 F 0.40 2.5 F 0.44 2.8 F 0.39 3.1 F 0.36 3.4 F 0.48 3.7 F 0.51 4.4 F 0.56 2.4 F 0.44 3.1 F 0.40 2.5 F 0.38 3.4 F 0.48 3.8 F 0.52 2.4 F 0.66 2.0 F 0.36 2.7 F 0.39 3.1 F 0.7

96

56

0.41

18

73

26

13

160

34

0.9

15

22

20

18

All values are mean of nine values F S.D. BDL = below detection limit.

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Fig. 2. Flow chart of sediment handling and analysis.

2.5. Extraction of total metals Aliquots of 1.00 g of oven-dried (80 jC, 12 h) and homogenized sample that passed through a 2-mm mesh, nylon sieve were wet digested with a mixture of HClO4/HF (1:5) in a platinum crucible at 140 jC for 4 h (Pempkowiase et al., 1999). After acid evaporation to dryness, the residue was dissolved in 10 ml of 0.1 M HNO3. Soft tissues of fish were wet digested in glass vessel with 6 ml of concentrated HNO3, followed by 4 ml of concentrated HClO4. After acid evaporation to dryness, the residue was dissolved in 5 ml of 0.1 M HNO3 (Agnieszka et al., 1996). 2.6. Sequential extraction of metals from sediments A five-step extraction procedure proposed by Tessier et al. (1979) was used in the sequential extraction of metals from sediment samples. The procedure of sediment handling and analysis is given in Fig. 2.

3. Results and discussion The metal contents in sediments and the background values of Kolleru lake (Sreenivasa Rao and Ramamohan

Rao, 2001a), background values from some studies on the metal contaminants of sediments in India (Dutta and Subrahmanian, 1998; Baruah et al., 1996; Sahu and Bhosale, 1991) and permissible limits (Moss and Costanzo, 1998) for metals in sediments are shown in Table 2 for comparison. The pH of the sediments did not vary much and was near to neutral. The cation exchange capacity (CEC) ranged from 26.6 to 53.4 C mol kg 1. Organic carbon was in the range of 12– 17% and metal retention was found to be high in the locations with high %organic carbon (L1 – L3, L5 and L6). The distribution of heavy metals in the sediment is not uniform over the whole part of the lake. The variation in the concentration may be due to differences in the sources of the heavy metals and prevailing physico chemical conditions and complex reactions such as adsorption, flocculation and redox condition taking place in the sediments. In general, the concentration of organic bound fractions of metals in the sediments is high where there is high organic matter (L1 – L3, L5 and L6). Therefore, the organic fraction released in the oxidisable step is not considered very mobile or available because it is thought to be associated with stable, high molecular weight humic substances that release small amount of metals slowly (Singh et al., 1998). Fractionation of Co, Ni, Cr, Pb, Cu, Cd and Zn in the sediment samples using Tessier scheme is presented in Fig. 3. The sum of

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Fig. 3. Extractable contents of metals in sediments using Tessier sequential extraction scheme.

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metal extracted in each sequential extraction scheme was compared with the total digestion procedure for recovery studies (Table 2). Studies show that the geochemical properties of sediment are critical in affecting the metal bioavailability (Luoma and Campbell, 1987; Wang and Fisher, 1999; Culshaw et al., 2002). Pempkowiase et al. (1999) studied the speciation of heavy metals in sediments and their bioaccumulation by mussel Mytilus edulis. Chong and Wong (2000) found that sedimentary particles were potentially important sources of heavy metals uptake by Perna viridis from Hong Kong waters due to sediment resuspension as a result of tidal currents. Vijver et al. (2003) reported metal uptake from soils and soil sediment mixture by larvae of Tenebrio molitor (Coleoptera). Partitioning patterns for Zn, Cd, Cu, Pb, Cr, Ni and Co in sediment samples indicated that all metals were mainly associated with the oxidizable (organic matter bound) fraction and residual fraction, which allows us to predict the mobility of metals in sediments and thereby their entry into human food chain. According to these results, Zn, Cd, Cu and Pb are more associated with mobilisable fraction (exchangeable and carbonate bound). In other words, these metals are more available to aquatic life. Heavy metals of anthropogenic origin are generally introduced into the environment as inorganic complexes or hydrated ions, which are easily adsorbed on surfaces of sediment particles through relatively weak physical and

chemical bonds (Forstner, 1989a,b; Horowitz, 1985). Thus, heavy metals of anthropogenic origin are found predominantly as labile extractable fraction in sediments (Pempkowiase et al., 1999). The association of metals to the organic matter (Step IV) can be explained by the well-known high affinity of these metals, especially Cu, Zn, and Pb, to humic substances which are a fraction of natural organic matter (Pempkowiase et al., 1999; Forstner, 1989a,b). In contrast to other metals, Ni, Co and Cr were the least mobilisable since more than 70% of these metals were in the nonmobile fraction, which means they are less available to the aquatic fauna and have less chances of entering into the human food chain. Similar fractionation studies were carried out using BCR extraction scheme, which showed a similar trend, and these results were presented elsewhere (Chandra Sekhar et al., 2002). Based on these fractionation studies of the metals in sediments and their mobility and bioavailability, the elements under study can be arranged as follows (from more bioavailable to less bioavailable). Zn < Cd < Cu < Pb < Cr < Ni < Co 3.1. Heavy metal content in fish The knowledge of the chemical forms of the metal in sediments determine their transport and mobility in aquatic media. These metals can also act as a source of contami-

Table 3 Bioaccumulation of metals in the fish of Kolleru lake Permitted limits of heavy metals in fish in India (Ag/g, dry wt.) FAO, 1983

Heavy metals

50

Zn

NA

Cd

10

Cu

4

Pb

2

Cr

10

Ni

NA

Co

BDL = below detection limit. NA = not available.

Content of metals (Ag/g, dry weight) F standard deviation

Gills (n = 25) Liver (n = 25) Muscle (n = 25) Gills (n = 25) Liver (n = 25) Muscle (n = 25) Gills (n = 25) Liver (n = 25) Muscle (n = 25) Gills (n = 25) Liver (n = 25) Muscle (n = 25) Gills (n = 25) Liver (n = 25) Muscle (n = 25) Gills (n = 25) Liver (n = 25) Muscle (n = 25) Gills (n = 25) Liver (n = 25) Muscle (n = 25)

Channa striata

Catla catla

Oreochromis mossambicus

114 F 20 89 F 14 43 F 8.2 0.41 F 0.20 0.26 F 0.10 0.19 F 0.08 96 F 14.6 70 F 11.1 38 F 9.3 4.90 F 3.01 3.7 F 2.04 2.11 F 1.07 21 F 8.9 18 F 6.1 10 F 3.9 1.01 F 0.10 0.66 F 0.08 0.24 F 0.05 0.99 F 0.15 0.53 F 0.10 0.21 F 0.08

100 F 16 80 F 12 41 F 8.1 0.37 F 0.18 0.22 F 0.09 0.11 F 0.04 89 F 12.7 66 F 10.1 33 F 8.1 3.77 F 2.11 2.98 F 1.74 1.84 F 0.86 30 F 9.7 19 F 6.7 11 F 3.7 0.92 F 0.09 0.52 F 0.04 0.22 F 0.02 0.87 F 0.11 0.33 F 0.08 BDL

96 F 11 72 F 10 37 F 7.6 0.38 F 0.16 0.20 F 0.07 0.12 F 0.06 91 F 12.8 59 F 9.7 28 F 7.7 4.21 F 0.88 3.0 F 0.64 1.90 F 0.57 26 F 8.6 17 F 6.6 10 F 4.1 0.89 F 0.08 0.50 F 0.04 0.18 F 0.02 0.80 F 0.09 0.27 F 0.03 BDL

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nation when significant changes of pH, redox potential, salinity, particulate matter or microbial activity occur in the environment. These changes can increase the mobility and transport of the metals in the aquatic media and make them bioavailable (Rubio and Rauret, 1996). Sin et al. (2001) reported that sediment-contained metals ingested by the suspended filter feeder P. viridis became bioavaialable as sources of metal for mussels. The relationship between metal levels in the living biota and those in the sediment were reported only in few cases (Ismail and Asmah, 1999; Ismail and Rosniza, 1997). Benthic invertebrates were found to be an important link in the transfer of metals to higher trophic levels because of their close association with sediments and their ability to accumulate metals (Galay Burgos and Rainbow, 2001). Furthermore, they are often a major component in the diet of many fish (Summers, 1980). The entry of metals into food chain is a considerable hazard because of their high toxicity. Cadmium was found to be associated with more labile fraction by many researchers (Surija and Branica, 1995; Licheng and Guijiu, 1996). Lead is among the metals that was found to be least mobile and is present mainly in the residual fraction in amounts over 90% in most of the studies (Morillo et al., 2002; Routh and Ikramuddin, 1996). Significant increases of all metals, except Ni, were observed in the mussel Crenomytilus grayanus at concentrations of easily leachable metals in ambient sediments higher than 2, 100 and 800 Ag/g for Cd, Cu and Zn, respectively (Shulkin et al., 2003). Agriculture, aquaculture and fishing are the primary activities of the people living in the Kolleru lake basin (Rao et al., 1987; Ramasastry et al., 1988). The annual fish catch from the lake is 2362 metric tonnes (Amaraneni, 1997). To know the bioconcentration of heavy metals, three species of edible fish which are the dominating species of the lake and which are mainly consumed were taken for the present study. C. striata, C. catla and O. mossambicus were collected and estimated for the metal content in gills, liver and muscle. Table 3 shows the heavy metal concentration in three different fish of Kolleru lake and the permissible limits proposed by FAO (1983) for India. The concentrations of Zn, Cu and Pb were found to be very high, which is in good agreement with the sequential extraction schemes as these metals were mainly associated with the labile fractions of the sediments. The concentrations of metals were found to be higher in gills followed by liver and muscle of fish.

4. Conclusion The quality of the Kolleru lake water is degraded due to the industrial and agricultural activities in its vicinity (Amaraneni, 1997; Amaraneni and Pillala, 2000a,b). The people living in the Kolleru lake region are exposed to the heavy metals by consuming the contaminated lake fish (Khasim and Panduranga Rao, 2003). Although the total content of heavy

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metals in the sediments is much higher, the bioavailable quantity of few heavy metals is low which may tend to increase if no measures are taken to check the anthropogenic contamination of lake waters. The quantity of Zn, Cu and Pb is very high in total as well as in nonresidual fractions, which leads to their bioaccumulation in fish of Kolleru lake. The relatively large content of Zn, Cu, Pb and Cr in fish may be attributed to the association of these metals to the bioavailable fraction. Even though the amount of Cd associated with labile fraction is high the concentration of Cd in fish is low. This is due to the relatively low concentration of Cd in the sediments. The results indicate that the Kolleru lake fish are contaminated with metals and not advisable for human consumption.

Acknowledgements Authors are grateful to Dr. K.V. Raghavan, Director, Indian Institute of Chemical Technology, and Dr. M.Vairamani, Head, Analytical Chemistry and Centre for Mass Spectroscopy, for their encouragement and for providing all the facilities in carrying out this work. The authors are thankful to Dr. V. Balaram, Deputy Director, National Geophysical Research Institute (NGRI), for providing FAAS facility and SRMs for our study. We would like to acknowledge Dr. M.R.P. Reddy, Scientist, Centre for Materials for Electronic Testing (C-MET), for providing ICP-OES facility.

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