Environ Monit Assess (2008) 144:329–340 DOI 10.1007/s10661-007-9996-4
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 km2 from Yamunotri glacier through six Indian states. Residues of organochlorine pesticides (OCPs) namely, isomers of HCH and endosulfan, DDT and its metabolites, aldrin, dieldrin, were analysed in water of river Yamuna along its 346 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 maximum traceability 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 detection limits (BDL). The concentration of ΣHCH and ΣDDT at different sites of the river ranged between 12.76–593.49 ng/l (with a mean of 310.25 ng/l) and 66.17–722.94 ng/l (with a mean of 387.9 ng/l), respectively. In canals the values were found between 12.38–571.98 ng/l and 109.12–1572.22 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 pesticides and suggested measures to check pesticide polC. 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: cpkaushik@rediffmail.com
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 ubiquitously found in all the components of the environment. Oceans are the ultimate sink for these pesticides which receive major rivers terminating into them. Pesticide dynamics in the environment reveals occurrence and movement of pesticide residues from soil by volatilization (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 runoff to the river depends on factors like slope, texture and porosity of soil, intensity of rainfall, erosivity of rainwater, 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.
DO09996; No of Pages
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Haryana state which is predominantly an agricultural state in India extends between 27°39′N to 30°55′N Latitude and 74°27′ to 77°36′E longitude and covers a total geographical area of 4,42,100 ha forming about 1.35% of the total area of the country. The state with a population of 21.08 million (Census of India 2001), occupies an interesting position, as its north-eastern part acts as Delhi upstream of Yamuna while its south eastern part as Delhi down stream. River Yamuna one of the major rivers of India with a total stretch of 345,843 km2, passes through Haryana state along its eastern border. River along with its canals is mainly responsible for supply of water to the majority of the districts of the state and the National Capital, Delhi for drinking as well as irrigation purposes. Out of a total drinking water supply of 2,700 million litres per day (mld), the Wazirabad waterworks supplies 945 mld and Haiderpur waterworks supplies 900 mld of water to national capital of Delhi. The raw water for these water works is drawn from the Yamuna River and the Western Yamuna canal, respectively. The presence of OCPs in water of river Yamuna at selected sampling sites only has been reported (Agarwal et al. 1986; Thakkar and Sarin 1987). The present study was carried out, as no systematic data is available on these pesticide residues in major stretch of 346 km of the river, and its canals flowing through the state of Haryana, predominantly an agricultural state using significant quantities of pesticides.
Materials and methods River Yamuna originates from Yamunotri glacier near Bandarpunch (31°13′N 78°26′E) in the Mussorrie range of lower Himalayas at a height of 6,387 m above mean sea level in the Uttarkashi district of Uttarakhand. The river flows 1,367 km from here to its confluence with the river Ganga at Allahabad in the state of Uttar Pradesh. In the total 345,843 km2 of total catchment area of river Yamuna, Haryana state has a share of 6.10%. The Western Yamuna Canal (WYC) originates from the river Yamuna at Tajewala barrage near Hathnikund in Haryana about 200 km upstream of Delhi. It flows through the agricultural and industrial belts of Yamunanagar, Karnal, Panipat and Sonepat just parallel to the river Yamuna before entering Delhi. The WYC branches off at Munak head into two
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branches i.e. Sunder Branch (SB) and WYC main. Sunder Branch is mainly used for irrigating Hansi and Tosham areas of Hisar and Bhiwani districts of Haryana State whereas the WYC main reaches Delhi at Haiderpur waterworks. The Agra canal (AC) emerges from River Yamuna at Okhla barrage in Delhi and passes through Faridabad, Ballabgarh, Palwal, Hodal regions of Southern Haryana before entering into the state of Uttar Pradesh. The Gurgaon canal (GC) bifurcates from Agra canal at Meethapur in Haryana and flows parallel to Agra canal. It passes through Faridabad, Gurgaon, Sohna and Hodal and leaves Haryana at Punhana. Water sampling and analysis Sampling of water of river Yamuna from Hathnikund to Hassanpur, WYC from Tajewala barrage to Haiderpur treatment plant, SB from Safido head to NH-10 bridge, Agra canal from Okhla to Hassanpur and Gurgon canal from Meethapur to Ujjina was done in February, 1999. A total of 44 samples, in triplicate, were collected. Site specifications for the river and canals have been shown in Table 1 and position of the river and canals is depicted in the map (Fig. 1). The sampling sites have been chosen keeping in view the possibility of getting accumulated residues in aquatic environment both from agricultural run-off as well as from urban – industrial area. Water samples were collected in the pre-cleaned, oven dried, hexane rinsed, amber coloured bottles of 1 L capacity and were sealed with screw caps lined with aluminium foil. Experimental The samples were extracted with hexane by using conventional liquid–liquid extraction (LLE) method immediately after bringing to the laboratory. This is a common method frequently used for the determination of organic pollutants in water (Tan 1992). One litre water sample was extracted with 40 ml of distilled hexane and 2 g of anhydrous sodium sulphate in 1 L capacity separately funnel and shaken well for 4– 5 min. The upper hexane layer was collected in a flat bottom flask and the remaining portion was extracted twice with 30 ml of hexane by gently mixing the sample with teflon coated magnet on a magnetic stirrer. Total 100 ml hexane was pooled and demoisturised by passing 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) and Gurgaon Canal (GC) in Haryana Sampling station River Yamuna Y-1 Hathnikund Y-2 Kalanor Y-3 Kundaghat Y-4 Manglora Bridge Y-5 Kairana Y-6 Khojkipur Y-7 Mimarpur Ghat Y-8 Garh Bridge Y-9 Bhairabakipur Y-10 Palla Ghat Y-11 Wazirabad Y-12 Okhla Y-13 Dadasiya Y-14 Hassanpur Western Yamuna Canal WYC-01 Tajewala head WYC-02 Yamunanagar WYC-03 Karnal WYC-04 Munak WYC-05 Haiderpur Treatment plant Sunder Branch SB-01 Safido head SB-02 Ada Urlana SB-03 Saifabad SB-04 Mall Savana head SB-05 Bodipul (Nandgarh) RD33 SB-06 Gatauli SB-07 100 m away from Gatauli SB-08 Karela SB-09 Bass SB-10 National highway bridge, Mundhal Agra Canal AC-01 Okhla head AC-02 Faridabad 37 bridge AC-03 Old Faridabad bridge AC-04 Chandwai bridge AC-05 Mandkola village AC-06 Janoli AC-07 Ghodi AC-08 Hassanpur Gurgaon Canal GC-01 Meethapur GC-02 Mowai GC-03 Banoli GC-04 Pratapgrah GC-05 Bijopur GC-06 Mindkola GC-07 Ujjina
Distance from origin (km)
Land use in adjoining area
01 41 62 107 150 164 184 200 208 214 225 247 268 310
Rocky and agricultural Industrial and residential Industrial and residential Agricultural and industrial Agricultural and industrial Agricultural and industrial Agricultural and industrial Agricultural and industrial Agricultural and industrial Agricultural and industrial Industrial and residential Industrial and residential Industrial and agricultural Agricultural
2 40
236
Rocky, agricultural, residential Industrial area; Yamunanagar Complex (distillery, sugar, starch, utensils, paper mill) Agricultural Agricultural Industrial zone, Haiderpur water works
0 21 35 46 56 67 67 78 87 100
Agricultural Agricultural Agricultural Agricultural Agricultural Agricultural Agricultural (mixing of ground water) Agricultural Agricultural Agricultural
0 6 11 28 41 46 54 73
Abundant foaming, eutrophication in standing water Industrial and residential Residential Agricultural Agricultural Agricultural Agricultural Agricultural
0 5 23 26 37 45 53
Residential, waste dumping from Badarpur Industrial area Residential, dumping of waste through pipeline Residential Residential, industrial and agricultural Agricultural Agricultural Agricultural
125
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R
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Fig. 1 Course of river Yamuna and the sampling locations (Inset: map of Haryana)
Table 2 Retention times, mean % recoveries and minimum detection limits of organochlorine pesticide standards by LLE with hexane as extracting solvent
about 5–6 ml in a rotary evaporator (Buchhi type) at 50–60 °C. The extract was cleaned by deactivated alumina (basic) column chromatography with 100 ml of hexane and concentrated to 2 ml for analysis on a gas liquid chromatograph (GLC). Hexane and acetone used as solvents were of pesticide residue analysis grade and were distilled in all glass distillation apparatus prior to use. Calibration of the instrument was done before the sample analysis, using the standards of the pesticides obtained from Labour Dr. Ehrenstorfer, D-8900 Augsburg. Qualitative and quantitative analyses were made by comparing the retention time and peak area of the samples, respectively with those of the calibrated reference standards. Analysis of pesticide residues was carried out on a Chemito series 2865, microprocessor controlled gas chromatograph, equipped with electron capture detector, having Nickel (63) foil as the electron source. The column specifications and operating conditions were:
OCPs
Retention time (min) on glass column
% recoveries
Minimum detection limit (ng)
α-HCH +-HCH β-HCH δ-HCH Aldrin o.p′-DDE; α-endosulfan p.p′-DDE Dieldrin o.p′-DDT o.p′-DDD p.p′-DDD β-endosulfan p.p′-DDT
3.83 4.77 5.60 6.40 7.35 10.40 11.50 12.30 13.11 15.11 15.79 16.15 16.67 17.25
90 87 92 85 88 83 88 86 87 82 80 86 87 83
0.5 0.4 0.6 0.8 0.04 0.7 0.3 0.4 0.14 0.7 0.4 0.5 0.4 0.7
Column: 2 m glass, 0.25 in. I.D., packed with 1.5% 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 °C Carrier Gas: Nitrogen at a flow rate of 50 ml/min. Confirmation of the identity of the organochlorine residues was done on Hewlett Packard series 5890 II gas chromatograph with the following operating conditions: 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 °C Carrier Gas: Nitrogen at a flow rate of 1 ml/min. The identities were further confirmed by chemical dehydrochlorination and subsequent gas chromatography. Results and discussion All the samples were analyzed in triplicate. Retention times, mean % recoveries and minimum detection limits for various pesticides are mentioned in Table 2.
In river Yamuna, WYC, SB, AC and GC the range of 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, respectively while 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 electrical conductivity 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 water quality of river Yamuna at the studied sites has already been discussed elsewhere by Ravindra et al. (2003) and the presence of heavy metals in these water bodies by Kaushik et al. (2001, 2003). The levels (range and arithmetic mean±SD values) of pesticides detected in water samples of river Yamuna and its canals are discussed here. All the samples were analyzed in triplicates. Residues of HCH and DDT were found in all the water samples from river and canals while aldrin and dieldrin remained below detection limit (BDL) (Table 3). The mean concentration of HCH and DDT at different sites is depicted in Table 3 and Figs. 2 and 3. The maximum mean HCH was found in Gurgaon canal (338.21 ng/l) followed by river Yamuna (310.25 ng/l), SB (184.58 ng/l), AC (161.26 ng/l) and WYC (76.75 ng/l). The relative abundance of HCH isomers in river Yamuna and its canals has been given in Figs. 2 and 3. In river Yamuna the concentration of HCH ranged between 12.76–593.49 ng/l with an average value of
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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
2.
+-HCH
3.
β-HCH
4.
δ-HCH
BDL–13.68 3.85±6.00 11.78–47.78 25.86±15.85 19.09–70.90 45.60±20.44 BDL
BDL–134.73 30.03±40.65 BDL–218.99 81.42±77.47 13.05–162.77 71.17±59.99 BDL
BDL–39.9 16.97±13.10 BDL–81.50 48.86±33.57 11.91–164.68 92.32±59.53 BDL
BDL–16.81 2.80±6.87 19.06–246.64 145.61±96.15 22.60–316.98 184.91±118.64 BDL
BDL–134.73 16.28±26.87 BDL–246.64 76.11±74.25 11.91–316.98 96.13±83.59 BDL
5.
ΣHCH
6.
o.p′-DDT
38.23–134.59 76.75±38.60 BDL
42.23–571.98 338.21±219.04 BDL
p.p′-DDT
8.
o.p′-DDE
9.
p.p′-DDE
10.
o.p′-DDD
164.54–743.41 421.19±163.97 BDL–1.66 0.20±0.59 31.84–375.00 193.50±120.52 BDL
11.
p.p′-DDD
12.
ΣDDT
35.01–455.86 184.58±135.89 BDL–11.54 2.06±4.40 33.77–183.07 101.45±45.63 BDL–1.38 0.32±0.51 12.791–123.87 65.13±34.91 BDL–9.00 3.56±3.41 5.67–69.08 16.44±18.88 109.12–291.35 197.10±61.31
12.38–298.41 161.26±108.01 BDL
7.
BDL*–166.89 63.57±59.39 BDL–207.71 113.87±70.88 12.27–242.29 117.46±70.68 BDL–58.81 12.02±18.93 12.76–593.49 310.25±191.57 BDL–20.49 1.46±5.97 25.38–470.67 170.89±134.40 BDL–6.67 0.90±1.99 22.86–402.18 183.91±105.02 BDL–17.99 4.12±4.99 BDL–57.20 19.14±15.36 66.17–722.94 387.90±181.18
307.54–1423.44 843.02±462.72 BDL–2.00 0.56±0.89 124.29–233.13 179.48±43.03 2.14–4.92 3.37±0.97 BDL–159.52 83.13±72.71 680.25–1572.21 1114.51±383.26
12.38–571.98 191.34±157.14 BDL–11.54 0.47±2.22 33.77–1423.44 343.36±363.47 BDL–2.00 0.34±0.63 12.79–375.00 124.88±91.02 BDL–9.00 2.61±2.69 BDL–159.52 31.29±43.24 109.12–1572.22 506.74±427.56
78.70–123.19 103.11±18.18 BDL–1.54 0.35±0.67 29.44–86.22 57.30±23.77 1.56–6.14 3.97±1.99 3.0–29.31 11.64±10.71 113.57–222.21 178.03±40.83
5.16–50.23 23.28±14.79 308.11–1141.83 643.43±261.56
* BDL – Below detection limit, Mean of three replicates.
310.25 ng/l. The minimum and maximum concentrations were observed at Bhairabakipur and Kalanor sites of the river. To determine the pollution load of the river in Haryana and Delhi states, the concentration of OCPs was studied under three sections of river i.e. Section-I of Haryana state and Delhi upstream (Y-01 to Y-10), Section-II of Delhi State (Y-11 and Y-12) and Section-III (Y-13 and Y-14) again of Haryana state and Delhi down stream. The mean concentration of ΣHCH in upstream, Delhi and down stream of river Yamuna were 248.89, 468.40 and 458.88 ng/l, respectively. The high concentration of ΣHCH in Delhi section in the present study and in different lakes/ reservoirs of Delhi (CPCB 2000) and in their benthic macroinvertebrates (Sharma et al. 2000) has been due to 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 concentration of 134.59 ng/l at Munak (WYC-04) having agricultural fields. The concentration of HCH prior to the origin of WYC at Y-1 was 298.54 ng/l which shows that the intake water is a source of pesticide pollution. In SB the minimum and maximum concentrations of HCH were observed in Karela (SB-08) and Bodipul (SB-05) sites, respectively. The SB originates from WYC at Munak (WYC-04) having ΣHCH concentration of 134.58 ng/l and in 60% of the sampling sites of SB, the concentration of ΣHCH exceeded the values that of its intake water, indicating other sources of HCH pollution. In Agra canal the concentration of ΣHCH ranged from 12.38 to 298.41 ng/l. At all the sampling
Fig. 2 Relative abundance of DDT and its metabolites (a), isomers of HCH (b), and total DDT and total HCH (c) in water of river Yamuna
b
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Fig. 3 Relative abundance of DDT and its metabolites (a), isomers of HCH (b), and total DDT and total HCH (c) in water of canals of river Yamuna
sites, concentration of ΣHCH remained lower than that of intake water of AC i.e. river Yamuna at Okhla (Y-12) had ΣHCH of 572.10 ng/l. As discussed above the already contaminated water of river Yamuna of Delhi section was one of the main sources of ΣHCH pollution
for AC water. Except some sites of AC, a declining trend in ΣHCH concentration was observed. The concentration of ΣHCH in Gurgaon canal was minimum at 42.23 ng/l at Meethapur (GC-01) and maximum at 571.98 ng/ l at Bijopur (GC-05). In the studied Yamuna river and
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all canals the maximum mean concentration of ΣHCH was in this canal which showed further increasing trend from upstream to downstream sites indicating additional pollution sources of Gurgaon canal. All the studied water samples were within maximum permissible limit (MPL) of 3,000 ng/l for ΣHCH residues in drinking water (WHO 1971). However, on comparing with that of the European Commission (1998) only 37% were within MPL of 100 ng/l. The mean concentration of ΣHCH in river Yamuna (310.25 ng/l) was less as compared to that observed in some other Indian rivers i.e. river Krishna and Godavari during 1993 (Reddy et al. 1997), river Gandak during 1995–1996 (Srivastava et al. 1996). The ΣHCH concentration in river Ganga during 1991–1992 (Agnihotri et al. 1994) was comparable to the levels found in the present study. However, when compared with that of world rivers the mean concentration of ΣHCH in Yamuna River was still high as compared with that of river Liaohe in China during 1998 (Zhang et al. 2000), Yongding River in China during 2000 (Wang et al. 2003) and Tana River in Kenya (Lalah et al. 2003). In the present study the mean concentration of ΣHCH in all the studied canals (191.34 ng/l) was quite low when compared with ΣHCH concentration in canals studied in 1991 and 1999 from Andhra Pradesh and Tamil Nadu states of India, respectively (Reddy et al. 1997; Krishnamurthi 1999). However, when the concentration of ΣHCH in western Yamuna canal was compared with that of our earlier investigation the present levels were found to be higher. Among HCH isomers, β-HCH was found in all water samples and had concentration more than αHCH and +-HCH in more than 80% samples. In river water the concentration of β-HCH ranged between 12.27–242.29 ng/l with a mean value of 117.46 ng/l while in four canals the range was found between 11.91–316.98 ng/l with an average concentration of 96.13 ng/l. The presence of β-HCH as the main isomer contributing to ΣHCH in the studied river and canals indicates an old source of pollution due to this isomer’s least reactiveness and most persistence among HCH 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 +
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HCH) were used. Although restricted use of lindane is allowed in India, industries engaged in export of + HCH generate α, β and δ as by-product and discard this waste in the open (Prakash et al. 2004). Even in countries where the use of insecticide HCH has been discontinued for a number of years, the problem of residues of all isomers of HCH remains because of the high persistence and inter-conversion of these isomers in soil (Steinwandter and Schluter 1978). The pesticide residues which lie in the soil due to earlier applications become a source of pesticide pollution of river water during agricultural run-off. The occurrence of relatively higher proportions of β and + HCH as compared to α and δ is due to the fact that β HCH is recalcitrant and the use (though restricted) of + HCH still continues. Moreover, the loss of various isomers due to volatilization depending upon their vapour pressure (Kaushik 1989) from the time of application and run-off to join water bodies and differential solubility explains variation in distribution and abundance in relation to the proportion of their occurrence in the in the river/canal water. Kumari et al. (2007b) have reported HCH concentration up to 0.051 μg/g in the paddy 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 surface soils of Delhi and adjoining areas of Haryana and Uttar Pradesh. They have reported still high concentration of total HCH i.e. 637.00 mg/kg in soil sample of Indian Pesticide Limited (IPL), Lucknow. These pesticides contaminate drinking water, the fact which had caused considerable concern as various laboratories detected pesticide residues in different brands of mineral water with the total HCH concentration of 24.10 μg/l (Prakash et al. 2004), and the highest concentration of lindane i.e. 0.0042 mg/l in various brands of soft drinks (Centre for Science and Environment 2003). Water samples were also analysed for aldrin, dieldrin, α- and β-endosulfan. These pesticides remained below the detection limit. Endosulfan sulfate could not be analysed. Singh (2001) also could not detect endosulfan sulfate in any soil or groundwater sample from Agra City. Sankararamakrishnan et al. (2005) reported absence of endosulfan residues in Ganga River water and groundwater from agricultural and industrial areas of Kanpur, Uttar Pradesh, India, which may be attributed to limited application of this pesticide in this region.
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The mean concentration of ΣDDT in studied river and canals was observed in the order: Guargon canal > Agra canal > Yamuna > Sunder branch and Western Yamuna canal. Except 19% samples, the concentration of ΣDDT was more than ΣHCH in all the water samples analysed. HCH and DDT remain in soil for quite sometime. The high value of DDT reported in water is either from its residues in the environment or its current use in mosquito control/public health programmes in the catchment areas. However, higher vapour pressures of HCHs than DDTs facilitate relatively rapid atmospheric dissipation in the tropics, leaving fewer residues in soils and water (Kaushik 1991; Kannan et al. 1995). In river Yamuna the maximum and minimum value of ΣDDT was found at Kalanor (702.94 ng/l) and Okhla barrage (66.17 ng/l), respectively. However, in three segments of river Yamuna the most polluted stretch, Delhi (Section II) had minimum concentration of ΣDDT in water, the maximum being in downstream stretch of the river. The organic matter adsorbs these pesticides and other pollutants and settles down in form of sludge (CPCB 2000). In this section the estimated BOD load of 682.70 MT/day, was contributed 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 metals and organochlorine pesticides were earlier observed in water of this stretch by Kaushik et al. (2001) and Sharma et al. (2003), respectively while the accumulated highest levels of OCPs in this section of river in benthic macroinvertebrates was observed by (Sharma et al. 2000). The present study was conducted during February, 1999, a period having no or scanty rains. Although not much load of agricultural run-off/dilution by rain is experienced and the sediments were also not analysed for pesticide residues, it was thought worthwhile to conduct the study in order to assess pesticide residue concentration during this period of time as the water is used for drinking purposes throughout the year. In fact, extensive regular monitoring should be done to evaluate the extent of pesticide pollution of this 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 all the sampling sites of WYC when compared with its
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sources of origin source (Y-1) indicating the origin itself as a source of pollution. In SB the minimum and maximum values of ΣDDT were found in Mall Savana Head (SB-04) and Karela (SB-08), respectively. The first four sampling (SB-01 to 04) sites showed a declining while others (SB-05 to 09) an increasing trend. The high concentration of p.p′-DDT in these sites reflects the current use of DDT in the corresponding areas. In Agra canal the concentration of ΣDDT ranged between 308.11–1141.83 ng/l at Hassanpur (AC-08) and Faridabad 37 bridge (AC-02) with a mean concentration of 643.43 ng/l. The canal water contained very high concentration of ΣDDT when compared to its source of origin (Y-12), indicating use of DDT in the area. In 1996–1997 concentration of ΣDDT ranged between BDL-511.80 ng/l in the canal water at 26 km downstream of Delhi (CPCB 2000). Gurgaon canal had the highest concentration of ΣDDT among all the studied canals and the river, had further its minimum and maximum values of 680.25 ng/l to 1,572.22 ng/l observed at Pratapgarh (GC-04) and Bijopur (GC-05), respectively. As observed earlier in case of SB and Agra canal, Gurgaon canal also has high concentrations of ΣDDT from its source of origin. The consumption of technical grade pesticide in India during the study period (1998–1999) was 57,240 MT (of which 60%, 34,628 MT, were insecticides) and in Haryana it was about 5,030 MT (Agnihotri 2000). The relative abundance of DDT and its metabolites in river Yamuna and its canals has been given in Figs. 2 and 3. The mean concentration of ΣDDT in river Yamuna (387.90 ng/l) was quite low as compared to values 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 less when compared with earlier studies on the river during 1976–1978 (Agarwal et al. 1986) and 1996–1997 (CPCB 2000). Similarly, the mean concentration of ΣDDT in water of canals was 506.74 ng/l which was low when compared with other canals in different states 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 chemical and biological processes (Wedemeyer 1967; Baxtor 1990). The ratio of (p.p′-DDE+p.p′-DDD)/
Environ Monit Assess (2008) 144:329–340
p.p′-DDT provides an indication of the extent of recent release of DDT into the environment, with the ratio increasing over time as the DDT degraded. In river Yamuna the ratio was between 0.15–13.07 and at only four sites the ratio was less than one. In canals, except in five samples the ratio was less than one. From the ratio and nature/types of metabolites we can say that in river Yamuna it was the earlier use of DDT in the catchment areas, as a possible source of pollution. In canals the illegal use of these pesticides by the users and release from contaminated soils were the main sources of pollution.
Conclusions and control measures From the present study it can be concluded that river Yamuna and its canals are contaminated with HCH and DDT residues. In river water HCH was more while in canals more DDT residues were observed. All the studied water samples were within the maximum permissible limit (MPL) of 3,000 ng/l for ΣHCH residues while 03 samples had crossed the MPL of 1,000 ng/l of ΣDDT in drinking water (WHO 1971). However, on comparing with European Commission (1998) only 37% were within MPL of 100 ng/l of ΣHCH while all the samples crossed 100 ng/l of ΣDDT. Consequent upon banning/restriction on the use of persistent organochlorine compounds in India, the levels of their residues have been coming down in river and canals also. Treatment of water should be done before use as in many samples the concentration of the studied pesticides exceeded the permissible limits. There is a need for awareness among farmers so that illegal use can be controlled. Strict action against sellers of banned or spurious pesticides and adoption of integrated pest management practices could be the possible ways to overcome/bring down the present levels in future. The illegal use of DDT in cattle sheds and vegetable fields was observed in the command areas of both Gurgaon canal and Agra canal which should be monitored for corrective measures. Acknowledgements The authors wish to thank Environment Department, Govt. of Haryana for providing financial assistance in the form of major research project ‘Water quality of major rivers and canals in Haryana’ under which the sampling for the present study was also done. Assistance provided by Er. Anil Haritash in various forms is also thankfully acknowledged.
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