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Studies on organochlorine pesticide residues in Hindon river surface water of Ghaziabad.

Introduction

Pesticides are chemicals or other agents used to destroy any organism that is considered a pest. Pesticides are used to increase the production of food and fiber and to promote public health. Among the pests attacking agricultural crops are insects, fungi, rodents, and birds. Weeds loosely defined, as any undesired plants are also agricultural pests. Persistent organic pollutants (POPs) persist in the environment for a long time; they are prone to long range transport; they can be carried through the upper levels of the atmosphere. There is a particular concern about the trace quantities of highly chlorinated compounds that are found in the environment; they can also enter the food chain mainly through the intake of animal fats. Some pesticides are selective. They act against limited group of organism because they affect some aspect of metabolism specific to a limited number of plants, animals, or microbes. Pesticides are broad-spectrum affecting a wide rage of organisms and more likely to pose a danger to non-target species.

The world health organization indicates that adverse effects of pesticides on human health are much as at least 20,000 deaths and million illnesses every year result from pesticide misuse. Persistent organochlorine compounds may be related to point sources eg; industrial discharges and domestic sewage, but more frequently, as in the case of pesticide pollution. If can also be attributed to precipitation agricultural runoff etc. Rand et al [1] studied that most of the applied pesticides are subject to many transport and conversion products. They do not remain at their target site but often enter aquatic environment via soil percolation air drift or surface run off affecting [2] abundance and diversity of non target species. M. concepcion Contreras Lopez [2] studied the organochlorine compds can be persistent environmental contaminates and may be accumulated through the food chain to the aquatic organisms. Viswnathan and Krishanamurti [3] introduced the factors that can increase toxicity of pesticides to aquatic biota at higher temperatures are higher solubility of toxicants in water, an augmented rate of uptake and blood flow & increased bioconcentration. It causes headache, nausea, vomiting, diarrhea, parenthesias of lips and tongue, coarsetremor, convulsions, respiratory failure

Davies, Dobbs, Meiler, Soon and Bergner [4-7] verify a theoretical model of persistent pollutant behaviour in aquatic environment from laboratory studies.

Heavy loading of industrial effluent discharge directly into the Karhera drain places an intolerable burden on the river's natural ability to assimilate pollutants. Key contaminants identified within the effluents of these industries include a very high loading of organic pollutants and frequently pathogens as a result of contaminated raw materials entering the plants. R. Babu Rajendran et al., [8] studied on distribution of PCBs, HCH and DDTs and their ecotoxicological implication in Bay of Bengal, India. Imran Ali et al., [9] reported that pesticides values exceeding in Hindon river water indicates that the river is polluted and water is not fit for drinking, recreation, washing purposes and other purposes. Nalini Sankaramakrishnan et al., [10] undertaken a survey in northern India, has shown the presence of high concentration of both organochlorine and organophosphorus pesticides in the surface and ground water samples.

Agricultural practices within the Hindon river catchment have an important effect on the quality to the river surface water run off from agriculture carries with it a no. of suspended pollutants particularly elevated suspended sediments due to soil erosion and agricultural chemicals. Such as pesticides and fertilizers. The Karhera Drain receives large volumes of untreated sewage and municipal wastes from all population centers within the catchments & polluting the Hindon river.

Study area

The study area included four sample locations near village Karhera in Ghaziabad. They were U/S of out fall of Karhera drain, Karhera drain, mixing point of Karhera drain & Hindon river, D/S of out fall of Karhera drain. To study the impact of industrial activity & agricultural activity water sample collected from U/S of out fall of Karhera drain, Karhera drain, mixing point of Karhera drain & Hindon river, D/S of out fall of Karhera drain.

Sample Collection

For the present studies & Karhera drain water samples were collected from the Hindon river, at different 4 locations (figure 1). These sample water was collected in the pre-washed glass containers closed with Teflon lined caps. After transpiration to the laboratory, samples were stored at -20[degrees]C and extraction was normally done within 48 h.

[FIGURE 1 OMITTED]

Analytical procedure

The pesticide residues were analyzed by gas chromatography (GC) using supported by electron capture detector. This detector allows the detection of contaminants at trace level concentrations in the lower ppb range in the presence of a multitude of compounds extracted from the matrix to which these detectors do not respond. The standard condition of GC-ECD for analysis is given in Table-1

Liquid-liquid extraction followed by gas chromatographic detection (USEPA,1980) [11] was used for the determination of pesticide residues. Reddy SP et al, anonymous NCIPM, Kathpal TS et al., [12-14] studied a multiresidue method the simultaneous estimation of pesticides belonging to organochlorine and Organophosphorus groups in water using gas liquid chromatograph (GLC) equipped with capillary column and electron capture detector (ECD).

In general, the EPA protocols with certain modifications were used for the analysis. Around 11 of the water sample was filtered using 0.45-[micro]m Whatman glass fiber filter paper, treated with 10g of sodium sulfate and extracted thrice with 75ml of methylene chloride. The combined extracts were filtered and concentrated in a vacuo rotary evaporator. The solution thus obtained was filtered with a pinch of sodium sulfate and made up to 5 ml with hexane. One microliter of the sample thus prepared was injected and analyzed. The detection limits (DL) for these compounds derived by use of a signal-to-noise ratio 1:3 are also presented in Table-2. The analytical quality-control scheme included periodic analyses of organochlorine standard mixtures and ultrapure water along with the samples. Using standard samples containing known amounts of pesticides, accuracy of the determinations was routinely checked. A hexane stock solution of organochlorine pesticide standard was prepared in a 10ml volumetric flask filled with hexane. Known amounts of the stock solution were added to 11 of ultrapure water in a volumetric flask and thoroughly mixed by inverting the flask three or four times to give standard water solutions. These standard solutions were stored similar to that of the samples and the recovery studies were carried out as that of the sample in Table-2 & chromatograph(1). The results obtained for the various surface water samples show high concentration of organochlorine pesticides.

Results and discussion

The results of analysis of the water samples have shown the presence of organochlorine pesticides. The compounds detected were HCH (the isomers [alpha]-, [beta]-, [gamma]-, HCH). Results of the sample analysis are summarized in tables-3& Chromatography) .Belfroid et al., [15] studied that many pesticides eventually end up in ground water and their transformation produces may remain for years.

Among the various pesticides analyzed only HCH, residues were found in the surface water samples from the River Hindon (Table-3). The highest concentration of 26.8 [micro]g/l was observed for HCH in Karhera drain. In accordance with European Economic Commission (EEC) Directive 80/778/EEC) [16] for drinking water, the total pesticide level should not exceed 0.5[micro]g/l and individual pesticide not greater than 0.1 [micro]g/l.

The high concentration of pesticides in the surface water could be attributed to the agricultural run off resulting from the extensive agricultural activity in the banks of these locations. The predominance of [alpha]-, [beta]-, [gamma]-, HCH residues in the water samples analyzed indicate the liberal application of these pesticides by the local farmers owing to its low cost. HCH, commonly called as Lindane, is still used most extensively for human vector control because of its insecticidal property and long-lasting effects. Mathur [17] studied that In India, even though its agricultural use is being phased out, the annual production of Lindane in 1996-1997 was 40 MT with a forecast of 50 MT in 1997-1998.Hans et al., & Sanghi and Tewari [18-19] have also shown the presence of very high concentrations of similar pesticides in fruits and vegetables produced in Ghaziabad.Lu [20] studied that Considering the dietary daily intake of a common man which includes fruit, vegetables, cereals, milk and water, the concentrations of the pesticides intake from these foodstuffs alone could be much higher than the acceptable daily intake.

Conclusions

This assessment clearly shown that the Karhera drain heavily contaminated with a wide range of pesticides and their breakdown products. Standards are exceeded for both World Health Organization and Bureau of Indian Standards requirements, by several order of magnitude. Nowhere within the Hindon River is the water free from levels of pesticides that are proven to be toxic to human health.

HCH (the isomers [alpha]-, [beta]-, [gamma]-, HCH) have been detected in the absence of DDT and its metabolite DDE indicated the growing awareness of its ill effects amongst the farmers. In most of the samples, the pesticide levels detected were much higher than EC drinking water quality standards. The presence of HCH in surface water could be attributed to the intense agricultural activity in the area of Karhera drain. It can be inferred that the environment may be considerably degraded by these compounds, providing additional impact to the biota and bringing a potential risk to human health.

Reference

[1] Rand G.M, Wells PG, Mclarty LS, 1995. In: Rand GM. editor. Introduction to aquatic toxicology. Washington: Taylor and Francis; 1995. p. 3-66.

[2] M. Concepcion Contreras Lopez. Determination of potentially Bioaccumulating complex mixtures of organochlorine compounds in waste water. Environment International 2003;28:751-759

[3] Viswnathan, P.N.And C.R. Krishnamurti 1989,effects of temperature and humidity & ecotoxicology of chemicals in P.Bourdeau, J.A.Haines, W.klein & C.R.Krishnamurti, eds, ecotoxicology & climate SCOPE 38.John Willey & Sons, Suffolk,U.K.,pp 139-154

[4] Davies, R.P. and A.J.Dobbs. 1984.The Prediction. The prediction of bioconcentration in fish .Water Res .18:1253-1262.

[5] Bergner, P.E. 1985 On relations between bioaccumulation & weight of organisms. Ecol. Model. 27: 207-220

[6] Meier, P.G., D.C.Fook & K.F.Lagler.1983 Organochlorine pesticide residues in rice paddies in Malaysia, 1981.Bull.Environ. Contam.Toxicol. 30:351-357

[7] Soon, L.G. &O.S. Hock.1987. Environmental problems of pesticide usage in Malaysian rice-fields--perception & future considerations. In J. Tait &B. Napompeth, eds.,

[8] Babu Rajendran R, T. Imagawa, H.Tao, R, Ramesh. distribution of PCBs, HCHs and DDTs and this ecotoxicological. Implications in Bay of Bengal, India, Environmental international 31; 2005; (503-512)

[9] Imran Ali et al., analysis of organochlorine pesticides in the Hindon river water, India Journal of Environmental protection science 2008; 2: 47-53. from coastal environment, south India. Chemosphere 1999;39:1669-706

[10] Sankararamakrishnan N, Sharma KA, Sanghi R. Organochlorine and Organophosphorus pesticides residues in ground water and surface water of Kanpur, Uttar Pradesh, India. Environmental international, 2005;31:113-120.

[11] USEPA (United States Environmental Protection Agency), In: Watts RR, editor, Analysis of pesticide residues in human and environmental samples--a compilation of methods selected for use in pesticide monitoring programs; 1980. EPA-600/80-038.

[12] Reddy SP and Suryamani M. Health effects of pesticide use among cotton farmers. Journal of research ANGRAU 2005;33:48-52.

[13] Anonymous (2006) NCIPM website http://www.ncipm.org source directorate of plant protection and Quarantine, Faridabad.

[14] Kathpal TS , Rani S, Kumari B and Prasad G. Magnitude of pesticidal contamination of sediment and water of Keoladea National Park Lake, Bharatpur.PesticRes J 2004;16: 75-77.

[15] Belfroid AC. Van Drumen M, Beck MA, Vangestal CAN, Van Hattum B. Relative risks of transformation products of pesticides for aquatic ecosystems. Sci Total Environ 1998;222:167-83.

[16] EEC council Directive 80/778/EEC. Official journal of European communities, vol.L.229; 1980 (Aug. 30th).p.11

[17] Mathur SC. Pesticides industry in India. Pestic inf 1993:19:7-15.

[18] Hans RK, Farooq M, Suresh Babu G, Srivastava SP, Joshi PC, Viswanathan PN. Agricultural produce in the dry bed of the River Ganga in Kanpur, India-a new source of pesticide contamination in human diets. Food Chem Toxicol 1999;37:847-52.

[19] Sanghi R, Tewari V. Monitoring of pesticide residues in summer fruits and vegetables from Kanpur, India. Bull Environ Contam Toxicol 2001; 67:587 93.

[20] Lu FC. A review of the acceptable daily intakes of pesticides assessed by the World Health Organization. Regul Toxicol Pharmacol 1995; 21:5-39.

* Lubna Najam (1), Nidhi Sharma (2), R.P. Tyagi (3) and D.S. Jadon (4)

(1) Department of Applied Science, Radha Govind Engineering College, Meerut

(2),(4) Department of Chemistry D.A.V (P.G) College, Muzaffarnagar

(3) Department of Chemistry M.M. (P. G.) College, Modinagar

* Corresponding Author Email: najam.lubna@gmail.com, lubna_mini@yahoo.com
Table 1: GC-ECD conditions.

Conditions Values

Injections volume 1[micro]l
Inlet pressure 7.00 psi
Injector temperature 300 [degrees]C
Detector temperature 300 [degrees]C
ECD makeup gas flow 40 ml/min
Oven programming 220-240 [degrees]C at 2[degrees]C/min;
 240-260 [degrees]C at 1.0 [degrees]C/min;
 260-280 [degrees]C at 5 [degrees]C/min
Total run time 34 min

Table 2: Retention time and detection limit of various
pesticide residues by GC-ECD multi residue technique.

Pesticides RT (min) Detection limit ([micro]g/l)

[alpha]-HCH 8.78 0.008
[beta]-HCH 9.29 0.020
[gamma]-HCH 9.99 0.008
Aldrin 12.86 0.008
4,4-DDE 18.91 0.008
DDT 29.29 0.012

Table 3: Results of the Pesticides analysis.

Pesticides H-U/S H-D H-M H-D/S

[alpha]-HCH 7.0 26.8 18.2 12.0
[beta]-HCH 7.1 23.0 17.7 10.7
[gamma]-HCH Nd 22.8 17.2 10.0
Aldrin Nd Nd Nd Nd
4,4-DDE Nd Nd Nd Nd
DDT Nd Nd Nd Nd
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Author:Najam, Lubna; Sharma, Nidhi; Tyagi, R.P.; Jadon, D.S.
Publication:International Journal of Applied Environmental Sciences
Geographic Code:9INDI
Date:Feb 1, 2010
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