endosulfan has not contaminated yamuna river scientific report

12
Pesticide residues in river Yamuna and its canals in Haryana and Delhi, India C. P. Kaushik & H. R. Sharma & S. Jain & J. Dawra & A. Kaushik Received: 14 February 2007 / Accepted: 19 September 2007 / Published online: 28 November 2007 # Springer Science + Business Media B.V. 2007 Abstract Yamuna, a prominent river of India covers an extensive area of 345,843 km 2 from Yamunotri glacier through six Indian states. Residues of organ- ochlorine pesticides (OCPs) namely, isomers of HCH and endosulfan, DDT and its metabolites, aldrin, diel- drin, were analysed in water of river Yamuna along its 346 km stretch passing through HaryanaDelhiHaryana and the canals originating from it. β-HCH, p.p-DDT, p.p-DDE and p.p-DDD had maximum traceability in test samples (95100%) followed by +- HCH, α-HCH and o.p-DDD (6084%) and o.p- DDT, δ-HCH and o.p-DDE (730%) while aldrin, dieldrin, α and β endosulfan remained below detec- tion limits (BDL). The concentration of ΣHCH and ΣDDT at different sites of the river ranged between 12.76593.49 ng/l (with a mean of 310.25 ng/l) and 66.17722.94 ng/l (with a mean of 387.9 ng/l), respectively. In canals the values were found between 12.38571.98 ng/l and 109.121572.22 ng/l for ΣHCH and ΣDDT, respectively. Water of Gurgaon canal and Western Yamuna canal contained maximum and minimum concentration, respectively both of ΣHCH and ΣDDT residues. Sources of these pesti- cides and suggested measures to check pesticide pol- lution of this major Indian river, keeping in view its vital link with life, are discussed in this paper. Keywords Organochlorine . Pesticide residues . River . Yamuna . Canals Introduction Organochlorine pesticides like HCH and DDT are ubiq- uitously found in all the components of the environ- ment. Oceans are the ultimate sink for these pesticides which receive major rivers terminating into them. Pes- ticide dynamics in the environment reveals occurrence and movement of pesticide residues from soil by vola- tilization (Kaushik 1989 and 1991), from air (Kaushik et al. 1987) by wet precipitation (Agarwal et al. 1987; Kumari et al. 2007a), and aerial fall-out (Kaushik et al. 1991) into soil and water bodies. These pesticides also reach water bodies by drift during spraying, soil erosion, agricultural run off, leaching, municipal and industrial wastes (Young and Heesen 1974; Goldberg 1976; Harper et al. 1977; Rihan et al. 1978; Musick 1979). The surface transport of pesticides and their run- off to the river depends on factors like slope, texture and porosity of soil, intensity of rainfall, erosivity of rain- water, erodibility of soil, water table and solubility and polarity of pesticides. Since water of rivers and canals is used for drinking purposes in India, it becomes imperative to study the extent and magnitude of these restricted or banned pesticides in these water bodies. Environ Monit Assess (2008) 144:329340 DOI 10.1007/s10661-007-9996-4 DO09996; No of Pages C. P. Kaushik (*) : H. R. Sharma : S. Jain : J. Dawra : A. Kaushik Department of Environmental Science and Engineering, Guru Jambheshwar University of Science and Technology, Hisar 125 001 Haryana, India e-mail: [email protected]

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Yamuna, a prominent river of India covers an extensive area from Yamunotri glacier through six Indian states. Residues of endosulfan were analyzed in water of river Yamuna along its stretch passing through. The studies concluded that endosulfan remained below detection limits. Hence, the report clearly states the absence of endosulfan accumulation in water.

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Page 1: Endosulfan has not contaminated yamuna river  scientific report

Pesticide residues in river Yamuna and its canalsin Haryana and Delhi, India

C. P. Kaushik & H. R. Sharma &

S. Jain & J. Dawra & A. Kaushik

Received: 14 February 2007 /Accepted: 19 September 2007 /Published online: 28 November 2007# Springer Science + Business Media B.V. 2007

Abstract Yamuna, a prominent river of India coversan extensive area of 345,843 km2 from Yamunotriglacier through six Indian states. Residues of organ-ochlorine pesticides (OCPs) namely, isomers of HCHand endosulfan, DDT and its metabolites, aldrin, diel-drin, were analysed in water of river Yamuna along its346 km stretch passing through Haryana–Delhi–Haryana and the canals originating from it. β-HCH,p.p′-DDT, p.p′-DDE and p.p′-DDD had maximumtraceability in test samples (95–100%) followed by +-HCH, α-HCH and o.p′-DDD (60–84%) and o.p′-DDT, δ-HCH and o.p′-DDE (7–30%) while aldrin,dieldrin, α and β endosulfan remained below detec-tion limits (BDL). The concentration of ΣHCH andΣDDT at different sites of the river ranged between12.76–593.49 ng/l (with a mean of 310.25 ng/l) and66.17–722.94 ng/l (with a mean of 387.9 ng/l),respectively. In canals the values were found between12.38–571.98 ng/l and 109.12–1572.22 ng/l forΣHCH and ΣDDT, respectively. Water of Gurgaoncanal and Western Yamuna canal contained maximumand minimum concentration, respectively both ofΣHCH and ΣDDT residues. Sources of these pesti-cides and suggested measures to check pesticide pol-

lution of this major Indian river, keeping in view itsvital link with life, are discussed in this paper.

Keywords Organochlorine . Pesticide residues .

River . Yamuna . Canals

Introduction

Organochlorine pesticides like HCH and DDTare ubiq-uitously found in all the components of the environ-ment. Oceans are the ultimate sink for these pesticideswhich receive major rivers terminating into them. Pes-ticide dynamics in the environment reveals occurrenceand movement of pesticide residues from soil by vola-tilization (Kaushik 1989 and 1991), from air (Kaushiket al. 1987) by wet precipitation (Agarwal et al. 1987;Kumari et al. 2007a), and aerial fall-out (Kaushik et al.1991) into soil and water bodies. These pesticides alsoreach water bodies by drift during spraying, soilerosion, agricultural run off, leaching, municipal andindustrial wastes (Young and Heesen 1974; Goldberg1976; Harper et al. 1977; Rihan et al. 1978; Musick1979). The surface transport of pesticides and their run-off to the river depends on factors like slope, texture andporosity of soil, intensity of rainfall, erosivity of rain-water, erodibility of soil, water table and solubility andpolarity of pesticides. Since water of rivers and canalsis used for drinking purposes in India, it becomesimperative to study the extent and magnitude of theserestricted or banned pesticides in these water bodies.

Environ Monit Assess (2008) 144:329–340DOI 10.1007/s10661-007-9996-4

DO09996; No of Pages

C. P. Kaushik (*) :H. R. Sharma : S. Jain : J. Dawra :A. KaushikDepartment of Environmental Science and Engineering,Guru Jambheshwar University of Science and Technology,Hisar 125 001 Haryana, Indiae-mail: [email protected]

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Haryana state which is predominantly an agricultur-al state in India extends between 27°39′N to 30°55′NLatitude and 74°27′ to 77°36′E longitude and covers atotal geographical area of 4,42,100 ha forming about1.35% of the total area of the country. The state with apopulation of 21.08 million (Census of India 2001),occupies an interesting position, as its north-easternpart acts as Delhi upstream of Yamuna while its southeastern part as Delhi down stream. River Yamuna oneof the major rivers of India with a total stretch of345,843 km2, passes through Haryana state along itseastern border. River along with its canals is mainlyresponsible for supply of water to the majority of thedistricts of the state and the National Capital, Delhifor drinking as well as irrigation purposes. Out of atotal drinking water supply of 2,700 million litres perday (mld), the Wazirabad waterworks supplies945 mld and Haiderpur waterworks supplies 900 mldof water to national capital of Delhi. The raw water forthese water works is drawn from the Yamuna River andthe Western Yamuna canal, respectively.

The presence of OCPs in water of river Yamunaat selected sampling sites only has been reported(Agarwal et al. 1986; Thakkar and Sarin 1987). Thepresent study was carried out, as no systematic data isavailable on these pesticide residues in major stretchof 346 km of the river, and its canals flowing throughthe state of Haryana, predominantly an agriculturalstate using significant quantities of pesticides.

Materials and methods

River Yamuna originates from Yamunotri glacier nearBandarpunch (31°13′N 78°26′E) in the Mussorrierange of lower Himalayas at a height of 6,387 mabove mean sea level in the Uttarkashi district ofUttarakhand. The river flows 1,367 km from here toits confluence with the river Ganga at Allahabad inthe state of Uttar Pradesh. In the total 345,843 km2 oftotal catchment area of river Yamuna, Haryana statehas a share of 6.10%.

The Western Yamuna Canal (WYC) originatesfrom the river Yamuna at Tajewala barrage nearHathnikund in Haryana about 200 km upstream ofDelhi. It flows through the agricultural and industrialbelts of Yamunanagar, Karnal, Panipat and Sonepatjust parallel to the river Yamuna before entering Delhi.The WYC branches off at Munak head into two

branches i.e. Sunder Branch (SB) and WYC main.Sunder Branch is mainly used for irrigating Hansi andTosham areas of Hisar and Bhiwani districts ofHaryana State whereas the WYC main reaches Delhiat Haiderpur waterworks. The Agra canal (AC)emerges from River Yamuna at Okhla barrage in Delhiand passes through Faridabad, Ballabgarh, Palwal,Hodal regions of Southern Haryana before enteringinto the state of Uttar Pradesh. The Gurgaon canal(GC) bifurcates from Agra canal at Meethapur inHaryana and flows parallel to Agra canal. It passesthrough Faridabad, Gurgaon, Sohna and Hodal andleaves Haryana at Punhana.

Water sampling and analysis

Sampling of water of river Yamuna from Hathnikund toHassanpur, WYC from Tajewala barrage to Haiderpurtreatment plant, SB from Safido head to NH-10 bridge,Agra canal from Okhla to Hassanpur and Gurgon canalfrom Meethapur to Ujjina was done in February, 1999.A total of 44 samples, in triplicate, were collected. Sitespecifications for the river and canals have been shownin Table 1 and position of the river and canals isdepicted in the map (Fig. 1). The sampling sites havebeen chosen keeping in view the possibility of gettingaccumulated residues in aquatic environment bothfrom agricultural run-off as well as from urban –industrial area. Water samples were collected in thepre-cleaned, oven dried, hexane rinsed, amber colouredbottles of 1 L capacity and were sealed with screw capslined with aluminium foil.

Experimental

The samples were extracted with hexane by usingconventional liquid–liquid extraction (LLE) methodimmediately after bringing to the laboratory. This is acommon method frequently used for the determina-tion of organic pollutants in water (Tan 1992). Onelitre water sample was extracted with 40 ml of dis-tilled hexane and 2 g of anhydrous sodium sulphate in1 L capacity separately funnel and shaken well for 4–5 min. The upper hexane layer was collected in a flatbottom flask and the remaining portion was extractedtwice with 30 ml of hexane by gently mixing the sam-ple with teflon coated magnet on a magnetic stirrer.Total 100 ml hexane was pooled and demoisturised bypassing over Na2SO4 (anhydrous) and concentrated to

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Table 1 Sampling locations of River Yamuna (Y), Western Yamuna Canal (WYC), Sunder Branch (SB), Agra Canal (AC) andGurgaon Canal (GC) in Haryana

Sampling station Distance from origin (km) Land use in adjoining area

River YamunaY-1 Hathnikund 01 Rocky and agriculturalY-2 Kalanor 41 Industrial and residentialY-3 Kundaghat 62 Industrial and residentialY-4 Manglora Bridge 107 Agricultural and industrialY-5 Kairana 150 Agricultural and industrialY-6 Khojkipur 164 Agricultural and industrialY-7 Mimarpur Ghat 184 Agricultural and industrialY-8 Garh Bridge 200 Agricultural and industrialY-9 Bhairabakipur 208 Agricultural and industrialY-10 Palla Ghat 214 Agricultural and industrialY-11 Wazirabad 225 Industrial and residentialY-12 Okhla 247 Industrial and residentialY-13 Dadasiya 268 Industrial and agriculturalY-14 Hassanpur 310 AgriculturalWestern Yamuna CanalWYC-01 Tajewala head 2 Rocky, agricultural, residentialWYC-02 Yamunanagar 40 Industrial area; Yamunanagar Complex

(distillery, sugar, starch, utensils, paper mill)WYC-03 Karnal 125 AgriculturalWYC-04 Munak AgriculturalWYC-05 Haiderpur Treatment plant 236 Industrial zone, Haiderpur water worksSunder BranchSB-01 Safido head 0 AgriculturalSB-02 Ada Urlana 21 AgriculturalSB-03 Saifabad 35 AgriculturalSB-04 Mall Savana head 46 AgriculturalSB-05 Bodipul (Nandgarh) RD33 56 AgriculturalSB-06 Gatauli 67 AgriculturalSB-07 100 m away from Gatauli 67 Agricultural (mixing of ground water)SB-08 Karela 78 AgriculturalSB-09 Bass 87 AgriculturalSB-10 National highway bridge, Mundhal 100 AgriculturalAgra CanalAC-01 Okhla head 0 Abundant foaming, eutrophication in standing waterAC-02 Faridabad 37 bridge 6 Industrial and residentialAC-03 Old Faridabad bridge 11 ResidentialAC-04 Chandwai bridge 28 AgriculturalAC-05 Mandkola village 41 AgriculturalAC-06 Janoli 46 AgriculturalAC-07 Ghodi 54 AgriculturalAC-08 Hassanpur 73 AgriculturalGurgaon CanalGC-01 Meethapur 0 Residential, waste dumping from Badarpur Industrial areaGC-02 Mowai 5 Residential, dumping of waste through pipelineGC-03 Banoli 23 ResidentialGC-04 Pratapgrah 26 Residential, industrial and agriculturalGC-05 Bijopur 37 AgriculturalGC-06 Mindkola 45 AgriculturalGC-07 Ujjina 53 Agricultural

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about 5–6 ml in a rotary evaporator (Buchhi type) at50–60 °C. The extract was cleaned by deactivatedalumina (basic) column chromatography with 100 mlof hexane and concentrated to 2 ml for analysis on agas liquid chromatograph (GLC).

Hexane and acetone used as solvents were ofpesticide residue analysis grade and were distilled inall glass distillation apparatus prior to use. Calibrationof the instrument was done before the sample anal-ysis, using the standards of the pesticides obtainedfrom Labour Dr. Ehrenstorfer, D-8900 Augsburg.Qualitative and quantitative analyses were made bycomparing the retention time and peak area of thesamples, respectively with those of the calibratedreference standards.

Analysis of pesticide residues was carried out on aChemito series 2865, microprocessor controlled gaschromatograph, equipped with electron capture detec-tor, having Nickel (63) foil as the electron source. Thecolumn specifications and operating conditions were:

Column: 2 m glass, 0.25 in. I.D., packed with1.5% OV-17/1.95% QF-1 on Gas Chrom Q, 100–120 mesh.Temperatures: Column 200 °C (6 min), 215 °C(5 min) and 230 °C (5 min). Detector 280 °C,Injector 220 °CCarrier Gas: Nitrogen at a flow rate of 50 ml/min.

Confirmation of the identity of the organochlorineresidues was done on Hewlett Packard series 5890 IIgas chromatograph with the following operatingconditions:

Column: BP5 Capillary 30 m, 0.25 mm I.D.Temperatures: Column 135 °C (20 min), 155 °C(15 min), 210 °C (10 min) and 250 °C (5 min),Detector 300 °C, Injector 250 °CCarrier Gas: Nitrogen at a flow rate of 1 ml/min.

The identities were further confirmed by chemical de-hydrochlorination and subsequent gas chromatography.

Results and discussion

All the samples were analyzed in triplicate. Retentiontimes, mean % recoveries and minimum detectionlimits for various pesticides are mentioned in Table 2.

In river Yamuna, WYC, SB, AC and GC the rangeof temperature was 10.5–24 °C, 15.0–26.2 °C, 14.6–16.8 °C, 20.8–25.9 °C and 18.0–21.0 °C, respectivelywhile pH varied from 6.9–7.8, 7.8–8.6, 7.0–7.5, 6.0–6.9 and 7.14–7.99, respectively and the electricalconductivity ranged from 0.2–1.1, 0.10–0.30, 0.3,0.6–0.8 and 0.65–1.82 dS m−1 respectively. The waterquality of river Yamuna at the studied sites hasalready been discussed elsewhere by Ravindra et al.(2003) and the presence of heavy metals in thesewater bodies by Kaushik et al. (2001, 2003). Thelevels (range and arithmetic mean±SD values) ofpesticides detected in water samples of river Yamunaand its canals are discussed here. All the sampleswere analyzed in triplicates. Residues of HCH andDDT were found in all the water samples from riverand canals while aldrin and dieldrin remained belowdetection limit (BDL) (Table 3). The mean concentra-tion of HCH and DDT at different sites is depicted inTable 3 and Figs. 2 and 3. The maximum mean HCHwas found in Gurgaon canal (338.21 ng/l) followed byriver Yamuna (310.25 ng/l), SB (184.58 ng/l), AC(161.26 ng/l) and WYC (76.75 ng/l). The relativeabundance of HCH isomers in river Yamuna and itscanals has been given in Figs. 2 and 3.

In river Yamuna the concentration of HCH rangedbetween 12.76–593.49 ng/l with an average value of

Fig. 1 Course of river Yamuna and the sampling locations(Inset: map of Haryana)

Table 2 Retention times, mean % recoveries and minimumdetection limits of organochlorine pesticide standards by LLEwith hexane as extracting solvent

OCPs Retention time(min) on glasscolumn

% recoveries Minimumdetectionlimit (ng)

α-HCH 3.83 90 0.5+-HCH 4.77 87 0.4β-HCH 5.60 92 0.6δ-HCH 6.40 85 0.8Aldrin 7.35 88 0.04o.p′-DDE; 10.40 83 0.7α-endosulfan 11.50 88 0.3p.p′-DDE 12.30 86 0.4Dieldrin 13.11 87 0.14o.p′-DDT 15.11 82 0.7o.p′-DDD 15.79 80 0.4p.p′-DDD 16.15 86 0.5β-endosulfan 16.67 87 0.4p.p′-DDT 17.25 83 0.7

R

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310.25 ng/l. The minimum and maximum concen-trations were observed at Bhairabakipur and Kalanorsites of the river. To determine the pollution load ofthe river in Haryana and Delhi states, the concentra-tion of OCPs was studied under three sections of riveri.e. Section-I of Haryana state and Delhi upstream(Y-01 to Y-10), Section-II of Delhi State (Y-11 andY-12) and Section-III (Y-13 and Y-14) again of Haryanastate and Delhi down stream. The mean concentrationof ΣHCH in upstream, Delhi and down stream ofriver Yamuna were 248.89, 468.40 and 458.88 ng/l,respectively. The high concentration of ΣHCH in Delhisection in the present study and in different lakes/reservoirs of Delhi (CPCB 2000) and in their benthicmacroinvertebrates (Sharma et al. 2000) has been dueto the usage of these pesticides in mosquito control(CPCB 2000).

In WYC the minimum concentration of ΣHCH i.e.38.23 ng/l was found in Tajewala head (WYC-01) just

2 Km away from its origin and the maximum con-centration of 134.59 ng/l at Munak (WYC-04) havingagricultural fields. The concentration of HCH prior tothe origin of WYC at Y-1 was 298.54 ng/l which showsthat the intake water is a source of pesticide pollution. InSB the minimum and maximum concentrations of HCHwere observed in Karela (SB-08) and Bodipul (SB-05)sites, respectively. The SB originates from WYC atMunak (WYC-04) having ΣHCH concentration of134.58 ng/l and in 60% of the sampling sites of SB,the concentration of ΣHCH exceeded the values that ofits intake water, indicating other sources of HCHpollution. In Agra canal the concentration of ΣHCHranged from 12.38 to 298.41 ng/l. At all the sampling

Table 3 HCH and DDT residues (range, mean±SD, ng/l) in water of Yamuna River and its canals

Sr. no. Pesticide Yamuna(n=14)

WYC(n=5)

Sunder Branch(n=10)

Agra Canal(n=8)

Gurgaon canal(n=6)

All canals(n=29)

1. α-HCH BDL*–166.8963.57±59.39

BDL–13.683.85±6.00

BDL–134.7330.03±40.65

BDL–39.916.97±13.10

BDL–16.812.80±6.87

BDL–134.7316.28±26.87

2. +-HCH BDL–207.71113.87±70.88

11.78–47.7825.86±15.85

BDL–218.9981.42±77.47

BDL–81.5048.86±33.57

19.06–246.64145.61±96.15

BDL–246.6476.11±74.25

3. β-HCH 12.27–242.29117.46±70.68

19.09–70.9045.60±20.44

13.05–162.7771.17±59.99

11.91–164.6892.32±59.53

22.60–316.98184.91±118.64

11.91–316.9896.13±83.59

4. δ-HCH BDL–58.8112.02±18.93

BDL BDL BDL BDL BDL

5. ΣHCH 12.76–593.49310.25±191.57

38.23–134.5976.75±38.60

35.01–455.86184.58±135.89

12.38–298.41161.26±108.01

42.23–571.98338.21±219.04

12.38–571.98191.34±157.14

6. o.p′-DDT BDL–20.491.46±5.97

BDL BDL–11.542.06±4.40

BDL BDL BDL–11.540.47±2.22

7. p.p′-DDT 25.38–470.67170.89±134.40

78.70–123.19103.11±18.18

33.77–183.07101.45±45.63

164.54–743.41421.19±163.97

307.54–1423.44843.02±462.72

33.77–1423.44343.36±363.47

8. o.p′-DDE BDL–6.670.90±1.99

BDL–1.540.35±0.67

BDL–1.380.32±0.51

BDL–1.660.20±0.59

BDL–2.000.56±0.89

BDL–2.000.34±0.63

9. p.p′-DDE 22.86–402.18183.91±105.02

29.44–86.2257.30±23.77

12.791–123.8765.13±34.91

31.84–375.00193.50±120.52

124.29–233.13179.48±43.03

12.79–375.00124.88±91.02

10. o.p′-DDD BDL–17.994.12±4.99

1.56–6.143.97±1.99

BDL–9.003.56±3.41

BDL 2.14–4.923.37±0.97

BDL–9.002.61±2.69

11. p.p′-DDD BDL–57.2019.14±15.36

3.0–29.3111.64±10.71

5.67–69.0816.44±18.88

5.16–50.2323.28±14.79

BDL–159.5283.13±72.71

BDL–159.5231.29±43.24

12. ΣDDT 66.17–722.94387.90±181.18

113.57–222.21178.03±40.83

109.12–291.35197.10±61.31

308.11–1141.83643.43±261.56

680.25–1572.211114.51±383.26

109.12–1572.22506.74±427.56

* BDL – Below detection limit, Mean of three replicates.

Fig. 2 Relative abundance of DDT and its metabolites (a),isomers of HCH (b), and total DDT and total HCH (c) in waterof river Yamuna

b

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sites, concentration of ΣHCH remained lower than thatof intake water of AC i.e. river Yamuna at Okhla (Y-12)had ΣHCH of 572.10 ng/l. As discussed above thealready contaminated water of river Yamuna of Delhisection was one of the main sources ofΣHCH pollution

for ACwater. Except some sites of AC, a declining trendin ΣHCH concentration was observed. The concentra-tion of ΣHCH in Gurgaon canal was minimum at 42.23ng/l at Meethapur (GC-01) and maximum at 571.98 ng/l at Bijopur (GC-05). In the studied Yamuna river and

Fig. 3 Relative abundanceof DDT and its metabolites(a), isomers of HCH (b),and total DDT and totalHCH (c) in water of canalsof river Yamuna

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all canals the maximum mean concentration ofΣHCH was in this canal which showed furtherincreasing trend from upstream to downstream sitesindicating additional pollution sources of Gurgaoncanal.

All the studied water samples were within maxi-mum permissible limit (MPL) of 3,000 ng/l forΣHCH residues in drinking water (WHO 1971).However, on comparing with that of the EuropeanCommission (1998) only 37% were within MPL of100 ng/l. The mean concentration of ΣHCH in riverYamuna (310.25 ng/l) was less as compared to thatobserved in some other Indian rivers i.e. river Krishnaand Godavari during 1993 (Reddy et al. 1997), riverGandak during 1995–1996 (Srivastava et al. 1996).The ΣHCH concentration in river Ganga during1991–1992 (Agnihotri et al. 1994) was comparableto the levels found in the present study. However,when compared with that of world rivers the meanconcentration of ΣHCH in Yamuna River was stillhigh as compared with that of river Liaohe in Chinaduring 1998 (Zhang et al. 2000), Yongding River inChina during 2000 (Wang et al. 2003) and Tana Riverin Kenya (Lalah et al. 2003).

In the present study the mean concentration ofΣHCH in all the studied canals (191.34 ng/l) wasquite low when compared with ΣHCH concentrationin canals studied in 1991 and 1999 from AndhraPradesh and Tamil Nadu states of India, respectively(Reddy et al. 1997; Krishnamurthi 1999). However,when the concentration of ΣHCH in western Yamunacanal was compared with that of our earlier investi-gation the present levels were found to be higher.

Among HCH isomers, β-HCH was found in allwater samples and had concentration more than α-HCH and +-HCH in more than 80% samples. In riverwater the concentration of β-HCH ranged between12.27–242.29 ng/l with a mean value of 117.46 ng/lwhile in four canals the range was found between11.91–316.98 ng/l with an average concentration of96.13 ng/l. The presence of β-HCH as the main iso-mer contributing to ΣHCH in the studied river andcanals indicates an old source of pollution due to thisisomer’s least reactiveness and most persistence amongHCH isomers (Wang et al. 2003).

Until ban on the use of HCH was imposed in 1997,two forms of HCH, technical HCH (a mixture of α,β, +, and δ HCH in the proportion of 55–80, 5–14,8–15 and 2–16%, respectively) and lindane (only +

HCH) were used. Although restricted use of lindane isallowed in India, industries engaged in export of +

HCH generate α, β and δ as by-product and discardthis waste in the open (Prakash et al. 2004). Even incountries where the use of insecticide HCH has beendiscontinued for a number of years, the problem ofresidues of all isomers of HCH remains because of thehigh persistence and inter-conversion of these isomersin soil (Steinwandter and Schluter 1978). The pes-ticide residues which lie in the soil due to earlierapplications become a source of pesticide pollution ofriver water during agricultural run-off. The occurrenceof relatively higher proportions of β and + HCH ascompared to α and δ is due to the fact that β HCH isrecalcitrant and the use (though restricted) of + HCHstill continues. Moreover, the loss of various isomersdue to volatilization depending upon their vapour pres-sure (Kaushik 1989) from the time of application andrun-off to join water bodies and differential solubilityexplains variation in distribution and abundance inrelation to the proportion of their occurrence in the inthe river/canal water. Kumari et al. (2007b) havereported HCH concentration up to 0.051 μg/g in thepaddy wheat-paddy cotton and sugarcane field soils.Prakash et al. (2004) have reported total HCH (α, β ,+ and δ) residues of up to 212.20 μg/kg in the surfacesoils of Delhi and adjoining areas of Haryana andUttar Pradesh. They have reported still high concen-tration of total HCH i.e. 637.00 mg/kg in soil sampleof Indian Pesticide Limited (IPL), Lucknow. Thesepesticides contaminate drinking water, the fact whichhad caused considerable concern as various laborato-ries detected pesticide residues in different brands ofmineral water with the total HCH concentration of24.10 μg/l (Prakash et al. 2004), and the highestconcentration of lindane i.e. 0.0042 mg/l in variousbrands of soft drinks (Centre for Science and Envi-ronment 2003).

Water samples were also analysed for aldrin,dieldrin, α- and β-endosulfan. These pesticides re-mained below the detection limit. Endosulfan sulfatecould not be analysed. Singh (2001) also could notdetect endosulfan sulfate in any soil or groundwatersample from Agra City. Sankararamakrishnan et al.(2005) reported absence of endosulfan residues inGanga River water and groundwater from agriculturaland industrial areas of Kanpur, Uttar Pradesh, India,which may be attributed to limited application of thispesticide in this region.

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The mean concentration of ΣDDT in studied riverand canals was observed in the order: Guargon canal >Agra canal > Yamuna > Sunder branch and WesternYamuna canal. Except 19% samples, the concentrationof ΣDDT was more than ΣHCH in all the watersamples analysed. HCH and DDT remain in soil forquite sometime. The high value of DDT reported inwater is either from its residues in the environment orits current use in mosquito control/public health pro-grammes in the catchment areas. However, highervapour pressures of HCHs than DDTs facilitate rela-tively rapid atmospheric dissipation in the tropics,leaving fewer residues in soils and water (Kaushik1991; Kannan et al. 1995).

In river Yamuna the maximum and minimum valueof ΣDDT was found at Kalanor (702.94 ng/l) andOkhla barrage (66.17 ng/l), respectively. However, inthree segments of river Yamuna the most pollutedstretch, Delhi (Section II) had minimum concentrationof ΣDDT in water, the maximum being in down-stream stretch of the river. The organic matter adsorbsthese pesticides and other pollutants and settles downin form of sludge (CPCB 2000). In this section theestimated BOD load of 682.70 MT/day, was contrib-uted by domestic (449.85 MT/day), by industrial(127.32 MT/day) and other sources (105.53 MT/day)(CPCB 2000). Low concentration of heavy metalsand organochlorine pesticides were earlier observedin water of this stretch by Kaushik et al. (2001) andSharma et al. (2003), respectively while the accumu-lated highest levels of OCPs in this section of river inbenthic macroinvertebrates was observed by (Sharmaet al. 2000).

The present study was conducted during February,1999, a period having no or scanty rains. Althoughnot much load of agricultural run-off/dilution by rainis experienced and the sediments were also notanalysed for pesticide residues, it was thought worth-while to conduct the study in order to assess pesticideresidue concentration during this period of time as thewater is used for drinking purposes throughout theyear. In fact, extensive regular monitoring should bedone to evaluate the extent of pesticide pollution ofthis major river and its canals.

In WYC the minimum concentration of ΣDDT(113.57 ng/l) was observed in water of Tajewala Head(WYC-01) and maximum (222.21 ng/l) at Munak(WYC-04). Lower levels of DDT were found at allthe sampling sites of WYC when compared with its

sources of origin source (Y-1) indicating the originitself as a source of pollution. In SB the minimumand maximum values of ΣDDT were found in MallSavana Head (SB-04) and Karela (SB-08), respec-tively. The first four sampling (SB-01 to 04) sitesshowed a declining while others (SB-05 to 09) anincreasing trend. The high concentration of p.p′-DDTin these sites reflects the current use of DDT in thecorresponding areas.

In Agra canal the concentration of ΣDDT rangedbetween 308.11–1141.83 ng/l at Hassanpur (AC-08)and Faridabad 37 bridge (AC-02) with a mean con-centration of 643.43 ng/l. The canal water containedvery high concentration of ΣDDT when compared toits source of origin (Y-12), indicating use of DDT in thearea. In 1996–1997 concentration of ΣDDT rangedbetween BDL-511.80 ng/l in the canal water at 26 kmdownstream of Delhi (CPCB 2000).

Gurgaon canal had the highest concentration ofΣDDT among all the studied canals and the river,had further its minimum and maximum values of680.25 ng/l to 1,572.22 ng/l observed at Pratapgarh(GC-04) and Bijopur (GC-05), respectively. As ob-served earlier in case of SB and Agra canal, Gurgaoncanal also has high concentrations of ΣDDT from itssource of origin. The consumption of technical gradepesticide in India during the study period (1998–1999)was 57,240 MT (of which 60%, 34,628 MT, wereinsecticides) and in Haryana it was about 5,030 MT(Agnihotri 2000).

The relative abundance of DDTand its metabolites inriver Yamuna and its canals has been given in Figs. 2and 3. The mean concentration of ΣDDT in riverYamuna (387.90 ng/l) was quite low as compared tovalues reported in river Krishna in 1993 (Reddy et al.1997) but remained high in comparison to river Ganga(Agnihotri et al. 1994) and river Godavari (Reddy et al.1997). However, the concentration of ΣDDT (66.17–722.94 ng/l) in river Yamuna was found to be lesswhen compared with earlier studies on the river during1976–1978 (Agarwal et al. 1986) and 1996–1997(CPCB 2000). Similarly, the mean concentration ofΣDDT in water of canals was 506.74 ng/l which waslow when compared with other canals in differentstates of India (Reddy et al. 1997; Krishnamurthi 1999).

The p.p′-DDT undergoes slow degradation to p.p′-DDE and p.p′-DDD in natural environment by chem-ical and biological processes (Wedemeyer 1967;Baxtor 1990). The ratio of (p.p′-DDE+p.p′-DDD)/

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p.p′-DDT provides an indication of the extent of re-cent release of DDT into the environment, with theratio increasing over time as the DDT degraded. Inriver Yamuna the ratio was between 0.15–13.07 andat only four sites the ratio was less than one. Incanals, except in five samples the ratio was less thanone. From the ratio and nature/types of metaboliteswe can say that in river Yamuna it was the earlier useof DDT in the catchment areas, as a possible sourceof pollution. In canals the illegal use of these pes-ticides by the users and release from contaminatedsoils were the main sources of pollution.

Conclusions and control measures

From the present study it can be concluded that riverYamuna and its canals are contaminated with HCH andDDT residues. In river water HCH was more while incanals more DDT residues were observed. All thestudied water samples were within the maximum per-missible limit (MPL) of 3,000 ng/l for ΣHCH residueswhile 03 samples had crossed the MPL of 1,000 ng/l ofΣDDT in drinking water (WHO 1971). However, oncomparing with European Commission (1998) only37% were within MPL of 100 ng/l of ΣHCH whileall the samples crossed 100 ng/l of ΣDDT. Conse-quent upon banning/restriction on the use of persis-tent organochlorine compounds in India, the levelsof their residues have been coming down in riverand canals also.

Treatment of water should be done before use asin many samples the concentration of the studiedpesticides exceeded the permissible limits. There isa need for awareness among farmers so that illegaluse can be controlled. Strict action against sellers ofbanned or spurious pesticides and adoption of inte-grated pest management practices could be the pos-sible ways to overcome/bring down the present levelsin future. The illegal use of DDT in cattle sheds andvegetable fields was observed in the command areasof both Gurgaon canal and Agra canal which shouldbe monitored for corrective measures.

Acknowledgements The authors wish to thank EnvironmentDepartment, Govt. of Haryana for providing financial assis-tance in the form of major research project ‘Water quality ofmajor rivers and canals in Haryana’ under which the samplingfor the present study was also done. Assistance provided by Er.Anil Haritash in various forms is also thankfully acknowledged.

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