No endosulfan residues in fishes

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No endosulfan residues in fishes

  1. 1. Bull Environ Contam Toxicol (2008) 80:154–157DOI 10.1007/s00128-007-9335-zDetermination of Organochlorine Pesticide Residues inFreshwater Fish Species in Punjab, IndiaManpreet Kaur Æ Jagdish K. Sharma Æ Jatinder P. Gill Æ Rabinder Singh Aulakh ÆJasbir S. Bedi Æ Balbir S. JoiaReceived: 1 June 2007 / Accepted: 10 December 2007 / Published online: 9 January 2008Ó Springer Science+Business Media, LLC 2008Abstract The levels of organochlorine pesticides resi- could persist in soil and water for several years and sub-dues were determined in five freshwater fish species in sequently get accumulated in aquatic organisms (AbdallahPunjab State, India. These species were selected in view of et al. 1990). In India, the indiscriminate and injudicious usetheir importance to local human fish consumer. DDTs were of OCPs have led to the contamination of water bodies nearthe predominant organochlorine contaminants in all species to lands, rivers and estuarine bodies (Sarkar and Guptawith pp DDT and pp DDE as the main pollutants. Other 1988; Singh et al. 2005) resulting in high concentration inorganochlorines, such as HCH isomers and dieldrin were aquatic life especially fish, prawns, otters, shrimps etc.also found at lower levels in fish species. The a-HCH was (Murray and Beck 1990; Sreenivasa and Rao 2000; Sarkarthe dominant isomer of HCH in all fish species followed by and Gupta 1998). The consumption of biota from con-c-, b- and d-HCH. The residues of aldrin, chlordane, hep- taminated aquatic body is considered to be an importanttachlor and endosulphan were not detected in any fish route of exposure to OCPs (Johansen et al. 1996) insample. The levels of organochlorines detected in present humans resulting in variety of health hazards particularlystudy were below the tolerance limits recommended at endocrine dysfunction, births defects, breast cancer, lowerNational and International standards. sperm count, testicular cancer (Brody and Rudel 2003; Ahmed et al. 1996; Garry et al. 2004; Soto et al. 1998).Keywords Fish Á India Á Organochlorine Á Residues Fish are valuable source of high-grade protein and occupy an important position in the socio-economic con- ditions of South Asian countries. India is the third largestThe usage of Organochlorine pesticides (OCPs) is indis- producer of fish and second in inland fish production (Ferozpensable in the agricultural production technology and and Panikkar 2006) with annual production of 7.75 millioncontrol of vector borne diseases in the developing coun- tones. Keeping in view of public health significance oftries. The lipophilic nature, hydrophobicity and low pesticide residues, safety of consumers and legal restric-chemical and biological degradation rates of OCPs have tions on export the present study was proposed to monitorled to their widespread accumulation in food chain (John the OCPs levels in edible fish species in Punjab.et al. 2001; Bedi et al. 2005; Aulakh et al. 2006) andsubsequent magnification of concentrations in human, afinal link in the food chain (Surendernath et al. 2000). The Materials and Methodspesticides applied on land eventually find their way to theaquatic environment, thus contaminating it and the OCPs Punjab is northwestern state of India which has great potential for integration of inland fish farming with agri- culture. Randomly nine sampling sites were chosen in stateM. Kaur Á J. K. Sharma Á J. P. Gill Á R. S. Aulakh (&) Á and five species of fish were selected and depending uponJ. S. Bedi Á B. S. Joia their availability three samples of each species were col-Department of Veterinary Public Health, Gadvasu, Ludhiana,Punjab 141004, India lected (weighing 400–500 g) which constitute a totale-mail: rsaulakh@rediffmail.com sampling of 90 fish samples. The samples were transported123
  2. 2. Bull Environ Contam Toxicol (2008) 80:154–157 155 0.001 (33.3) 0.001 (14.2)to laboratory under chilled conditions and were stored at - 0.001 (25) Dieldrin20°C till processing. 0.003 BDL BDL Anhydrous sodium sulphate and silica gel extra pure – –(60–120 mesh) for column chromatography were obtained 0.013 (100) 0.014 (100) 0.012 (100) 0.011 (100) 0.011 (100)from Merck. The adsorbents were washed thrice withhexane and activated at 160°C overnight. The solvents RDDT 0.061(Merck) were glass distilled before use and they did notyield any interfering gas chromatographic peak when 0.005 (100) 0.004 (100) 0.003 (100) 0.003 (100) 0.003 (100)concentrated from 10 mL to 100 lL. All individual stan- ppDDEdards of pesticides a-, b-, c-, d-HCH, aldrin, dieldrin, 0.018chlordane, a-endosulphan, b-endosulphan, endosulphansulphate, heptachlor, op DDT, op DDE, pp DDT, pp DDE 0.003 (88.9) 0.003 (87.5) 0.002 (71.4) 0.001 (25) 0.001 (50)and pp DDD were obtained from Dr. Ehrenstofer Labo- ppDDD 0.010ratories (Augsburg, Germany). The extraction and clean up of fish samples were carriedout by the method as described by Abdallah et al. (1990) 0.004 (77.8) 0.004 (62.5) 0.003 (57.2) 0.005 (100) 0.003 (75)with slight modifications. Briefly, for extraction high-speed ppDDT 0.019blending was done by using petroleum ether. The clean upof the samples was performed by silica gel chromatogra- 0.001 (33.3) 0.003 (75.0) 0.004 (85.7)phy and the final elution was carried out by using 6% 0.004 (100) 0.002 (50)diethyl ether in petroleum ether. The eluate was concen- opDDT 0.014trated under vacuum to suitable volume and stored inlabelled glass stoppered vials. The quantitative analysis of 0.005 (100) 0.007 (100) 0.006 (100) 0.005 (100) 0.006 (100)organochlorines was done by gas liquid chromatography Table 1 Average residue levels (mg/kg) of OCPs in different edible freshwater fish species in Punjab RHCHequipped with electron capture detector and a 2 m 0.029(length) 9 3 mm id. Glass column packed with 1.5% OV-17 + 1.95% OV-210 on chromosorb WHP 80–100 mesh. 0.001 (22.2) 0.002 (100)Temperature of injection port, column and detector were d-HCH250, 230 and 260°C, respectively, with N2 gas flow at rate 0.003 BDL BDL BDLof 3.0 kg/cm2 Psig. The limit of detectability was – – –0.0005 mg/kg for c-HCH and 0.001 mg/kg for DDT 0.003 (87.5) 0.002 (100) 0.003 (100) 0.002 (100) 0.002 (50)metabolites. Confirmation of results were done on an c-HCHalternate glass column (1.1 m 9 3 mm) packed with OV- 0.012210 coated on 100–120 mesh chromosorb WHP. 0.001 (25) b-HCH 0.001 BDL BDL BDL BDLResults and Discussion – – – – Figure in parentheses indicates frequency of detection 0.002 (77.8) 0.003 (75.0) 0.003 (100) 0.003 (100) 0.002 (100)Recoveries of HCH isomers, DDT metabolites, dieldrin, a-HCHendosulphan and heptachlor spiked at levels of 0.5 and 0.0131.0 mg/kg were ranged from 84% to 94%. The averagelevels of organochlorine residues and their frequency of samples No. ofdetection in different fish species are presented in Table 1. 27 24 21 12 06 90The maximum levels of total HCH (0.007 mg/kg) andDDT (0.014 mg/kg) were detected in common carp. The Silver carp Hypophthalmichthys Common carp Cyprinus carpio BDL-below detectable limitspresent study indicates that 100% contamination of fish Ctenopharyngodon idellaspecies by one or metabolites of HCH or DDT. Dieldrinresidues were detected in rohu, grass carp and catla only. Rohu Labeo rohitaThe residues of aldrin, chlordane, endosulphan and hep- Catla Catla catlatachlor were not detected in any fish sample. As far as the Fish species Grass carp molitrixtotal pesticide residue burden is considered in differentspecies, common carp had maximum levels of OCPs as Total0.021 mg/kg followed by rohu (0.019), grass carp (0.019), 123
  3. 3. 156 Bull Environ Contam Toxicol (2008) 80:154–157catla (0.017) and silver carp (0.017). Among the orga- Table 2 Comparison of total OCPs residue levels in fish of presentnochlorines, DDT contributed more as compared to HCH study with national and international standardsand dieldrin. The proportion of DDT in rohu, common Pesticide Present National* International*carp, grass carp, catla and silver carp were 68.4%, 66.6%, study (mg/kg) (mg/kg)63.1%, 68.7% and 61.1%, respectively. (mg/kg) In some earlier studies in India, Battu et al. (1984) Aldrin/dieldrin 0.003 0.02 0.11 ± 0.09detected OCPs in fresh water fish in Ludhiana, residues of DDT (either DDE, DDT, 0.061 1.0 7.0both DDT and HCH were present in all the samples and DDD or combination)maximum levels of DDT were found to be 3.02 mg/kg, a-HCH 0.013 0.25 –while Kannan et al. (1992) reported mean levels of HCH b-HCH 0.001 0.25 –and DDT as 0.002 and 0.015 mg/kg, respectively, in fish. c-HCH 0.012 0.25 0.2 ± 0.1Amaraneni and Pillala (2001) analysed fish samples in d-HCH 0.003 0.25 –Andra Pardesh, India and the maximum concentration of a- *Mohindru (2005), c-HCH and pp DDT were found to be 123.8, 98.70 and157.4 mg/kg, respectively. Anupma et al. (2001) detectedresidue levels of DDT in fish samples from Ganga River, reported the contamination of fish species with pesticideIndia with range of 0.0726–1.666 mg/kg. residues. In Pakistan, Saqqib et al. (2005) detected DDE, In present study, among various isomers of HCH, a- aldrin and dieldrin residues in fish tissues while JabberHCH was predominant followed by c-HCH, while b-HCH et al. (2001) in Bangladesh reported the levels of DDT,was detected only in common carp. Amaraneni and Pillala aldrin, dieldrin, lindane and heptachlor in different organs(2001) reported a-HCH as the predominant isomer of HCH of fish.with maximum concentration of 123.8 lg/g followed by c- The results obtained in this study were compared withHCH (98.7 lg/g). Pandit et al. (2001) also reported the a- the recommended tolerance limits of the Ministry ofHCH to be more dominant isomer of HCH in fish. Among Health, Government of India and FAO/WHO for theDDT metabolites pp DDT and pp DDE were at highest organochlorine residues which showed that concentrationslevels followed by op DDT and pp DDD. Kannan et al. were below the limits (Table 2). More importantly, in(1992) reported pp DDE as main contaminant metabolite of comparison to earlier reports in India the present levels ofDDT followed by pp DDD and pp DDT; similarly Jiang the contaminants are substantially lower which indicate theet al. (2005) detected pp DDE as predominant metabolite gradual phase out of these compounds, but keeping in mindwhile Amaraneni and Pillala (2001) reported higher levels the long term health hazards of pesticide residues it isof pp DDT among DDT metabolites. advisable to regularize the monitoring of pesticide con- India banned DDT for agricultural purposes in 1989, but taminants in fish as these are highly lipophilic and persist incontinues to use between 5,000–10,000 kg/year for malaria nature and moreover fish has tremendous capacity to con-control. Technical HCH, once the most heavily used pes- centrate them.ticide in India with annual consumption exceeding6 9 107 kg was banned in 1997, but lindane (c-HCH) hasbeen used as a replacement since that time (Santilo et al. References1997). In present study a-HCH was detected in all fish Abdallah MA, Hassan IM (1990) Survey of residues of organochlo-species despite the ban which indicates the current or rine pesticides in some marketable Egyptian fish. J Assoc Analrecent use of HCH technical mixture. The presence of op Chem Int 73:502–508DDT and pp DDT in fish species also indicates its recent Ahmed S, Ajmal MS, Nomani AA (1996) Organochlorines andexposure and pp DDE and pp DDD indicates the outcome polycyclic hydrocarbons in the sediments of Ganga river, India. Bull Environ Contam Toxicol 57:794–802of metabolic process in body of fish (Kannan et al. 1997). Amaraneni SR, Pillala RR (2001) Concentration of pesticide residuesMoreover the a-HCH and pp DDE have the highest bio- in tissues of fish from Kolleru Lake in India. Environ Toxicolmagnifications potential as compared to other isomers/ 16:550–556metabolites of HCH and DDT (Manirakiza et al. 2002). In Anupma K, Sinha RK, Krishna Gopal Kumar Gopal K (2001) Quantitative estimation of DDT residues in some freshwater fishChina, DDT was banned 20 years ago, inspite of this of river Ganga at Patna, Bihar. Environ Ecol 19:396–399organochlorine pesticides were detected in soil, water, fish Aulakh RS, Gill JP, Bedi JS, Sharma JK, Joia BS Ockerman HWand sediment samples. DDT residues in fish ranged from (2006) Organochlorine pesticide residues in poultry feed,3.7 to 23.5 lg/kg and HCH ranged from 3.7 to 132 lg/kg. chicken muscle and eggs at a poultry farm in Punjab, India. J Science Food Agric 86(5):741–744These results demonstrate an accumulation through food Battu RS, Gupta SC, Chawla RP, Kalra RL (1984) Residues of DDTchain, from soil–water–sediment–microbes–crop–fish etc. and BHC in market samples of meat of various animals. Indian J(Feng et al. 2003). Some other South-Asian countries also Ecol 2:177–182123
  4. 4. Bull Environ Contam Toxicol (2008) 80:154–157 157Bedi JS, Gill JPS, Aulakh RS, Joia BS, Sharma JK (2005) Asian and Oceanic countries. Rev Environ Contam Toxicol Contamination levels of DDT and HCH residues in different 152:1–55 caprine tissues in Punjab, India. Indian J Anim Sci 75(1):11–13 Manirakiza P, Akimbamijo O, Covaci A, Adediran SA, Cisse I, FallBrody JG, Rudel RA (2003) Environmental pollutants and breast ST, Schepens P (2002) Persistent chlorinated pesticides in fish cancer. Environ Health Perspect 111:1007–1019 and cattle fat and their implications for human serum concen-Feng K, Yu BY, Ge DM, Wong MH, Wang XC, Cao ZH (2003) trations from the Sene-Gambian region. J Environ Monit 4:609– Organochlorine pesticides (DDT and HCH) residues in the Taihu 617 Lake region and its movement in soil water system. Chemo- Mohindru SM (2005) Food contaminants-origins, propagation and sphere 50:683–687 analysis. Analysis of pesticides/insecticides in/on foods. APHFeroz MK, Panikkar P (2006). Indian fisheries scenario. a Peep into Publishing Corporation, New Delhi, India, pp 93 constraints/needs for its future development. Fishing Chimes Murray HE, Beck JN (1990) Concentration of selected chlorinated 26(9):13–20 pesticides in shrimp collected from the Calcasieu river/lakeGarry VF (2004) Pesticide and children. Toxicol Appl Pharmacol complex, Louisina. Bull Environ Contam Toxicol 44:768–804 198:152–163 Pandit GG, Rao AMM, Jha SK, Krishnamoorthy TM, Kale SP, RaghuJabber SA, Khan YS, Rahman MS (2001) Levels of organochlorine K, Murthy NBK (2001) Monitoring of organochlorine pesticide pesticide residues in some organs of the Ganges perch, Lates residues in the Indian marine environment. Chemosphere calcarifer, from the Ganges–Brahmaputra–Meghna estuary, 44:301–305 Bangladesh. Mar Pollut Bull 42(12):1291–1296 Santilo D, Johnston P, Stringer R (1997) A catalogue of grossJiang QT, Lee TK, Chen K, Wong HL, Zheng JS, Giesy JP, Lo KK, contamination. Organochlorine production and exposure in Yamashita N, Lam PK (2005) Human health risk assessment of India. Pesticide News 36:4–6 organochlorines associated with fish consumption in a costal city Saqqib TA, Nagvpo SN, Sidiqui PA, Azmi MA (2005) Detection of of China. Environ Pollut 136(1):155–165 pesticide residues in muscles, liver and fat of 3 species of LobeoJohansen HR, Alexander J, Ronland OJ, Planting S, Lovik M, Gaarder found in Kalri and Haliji lakes. J Environ Biol 26(2):433–438 PI, Gdyma W, Bjerve NS, Becher G (1996) PCDDs, PCDFs and Sarkar A, Gupta RS (1988) DDT residues in sediments from Bay of PCBs in human blood in relation to consumption of crabs from a Bengal. Bull Environ Contam Toxicol 41:664–669 contaminated Fjord area in Norway. Environ Health Perspect Singh KP, Malik A, Mohan D, Takroo R (2005) Distribution of 7:756–764 persistent organochlorine pesticide residues in Gomti River,John PJ, Bakore N, Bhatnagar P (2001) Assessment of organochlorine India. Bull Environ Contam Toxicol 74(1):146–154 pesticide residues levels in dairy milk and buffalo milk from Sreenivasa RA, Rao RP (2001) Kolleru lake water pollution by Jaipur city, Rajasthan, India. Environ Int 20(4):231–236 pesticides. Indian J Environ Health 42:169–175Kannan K, Tanabe S, Ramesh A, Subramanian A, Tatsukawa R Soto AM, Michaelson CL, Preehti NV, Weill BC, Sonnenschein C, (1992) Persistent organochlorine residues in foodstuffs from Serrano F, Olea N (1998) Assays to measure estrogen and India and their implication on human dietary exposure. J Agric androgen agonists and antagonists. Adv Exp Med Biol 444:9–23 Food Chem 40:518–524 Surendernath B, Usha MA, Unikrishnan (2000) OrganochlorineKannan K, Tanabe S, Giesy JP, Tastukawa R (1997) Organochlorine pesticides residues contents of human milk and dairy milk. Ind pesticides and polychlorinated biphenyis in foodstuffs from J Nutr Dietet 37:188–194 123

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