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Environ Monit Assess (2010) 160:61–69

DOI 10.1007/s10661-008-0657-z

Pesticide pollution of River Ghaggar in Haryana, India


A. Kaushik · H. R. Sharma · S. Jain ·
J. Dawra · C. P. Kaushik

Received: 16 May 2008 / Accepted: 5 November 2008 / Published online: 24 December 2008
© Springer Science + Business Media B.V. 2008

Abstract Ghaggar, one of the major rivers of diphenyltrichloroethane (DDT) were traceable
northern India originating in outer Himalayas and in all the water samples. High concentration
flowing through the state of Punjab, Haryana, of β-HCH among HCH indicates old pollu-
and Rajasthan, is put to multiple uses. Along its tion source whereas predominance of p,p -DDT
course of 464 km, it receives discharge from var- among DDT reflects its recent use in the catch-
ious cities and runoff from agricultural lands. ment area of the river. The concentrations of
Punjab and Haryana are two predominantly agri- HCH and DDT in all the samples were above
cultural states of India using substantial amounts the permissible limits prescribed by the European
of agrochemicals, yet there are no reports avail- Commission Directive for drinking purposes.
able in literature on the level of pesticides in
the stretch of river Ghaggar through Punjab and Keywords Organochlorine · Pesticide residues ·
Haryana. This is the first report on pesticide pol- Agrochemicals · Ghaggar · River · Haryana ·
lution of the river Ghaggar in Haryana. Water Water pollution
samples along the 230-km stretch of the river
in Haryana were analyzed for the presence of
organochlorine insecticide residues. While aldrin Introduction
and dieldrin were below detection limits, both
hexachlorocyclohexane (HCH) and dichloro- Pesticides reach aquatic ecosystems by direct ap-
plication, spray drift, aerial spraying, atmospheric
fallout, soil erosion and runoff from agricul-
tural areas, discharge of industrial and domes-
A. Kaushik · H. R. Sharma · S. Jain · J. Dawra · tic sewage, leaching, careless disposal of empty
C. P. Kaushik (B) containers, and equipment washing. In aquatic
Department of Environmental Science bodies, these pesticides affect many nontarget
and Engineering, Guru Jambheshwar University of
organisms including fish and birds due to bio-
Science and Technology, Hisar, 125 001,
Haryana, India magnification through food chains. Occurrence of
e-mail: cpkaushik@rediffmail.com organochlorine pesticides in various Indian rivers
like Krishna and Godavari (Reddy et al. 1997),
Present Address:
Hindon (Ali et al. 2008), Gomti and Ganga (Singh
H. R. Sharma
Department of Environmental Health, University of and Singh 2008), and Yamuna (Kaushik et al.
Gondar, P.B. No. 196, Gondar, Ethiopia 2008) and in the Bay of Bengal (Rajendran et al.
62 Environ Monit Assess (2010) 160:61–69

2005) has been reported. River Ghaggar, a major near Kalka, there is little anthropogenic activity.
river of northern India, originates from the The river after flowing into Punjab for a distance
Shivalik mountain ranges of outer Himalayas touches the border of Ambala city in Haryana
(900–2,300 m) in Himachal Pradesh between near Devigarh (G-03). Being just downstream to
River Yamuna and Satluj, enters Haryana near Punjab, effluents from various industries in Patiala
Kalka, and receives most of its water from rain- and Rajpura area of Punjab finally find their way
fall. Ghaggar–Yamuna alluvium plain has mainly into Ghaggar. Various medium-scale industries in-
sand, clay, silt, and hard calcareous balls like cluding pesticide industry, paper industry, refined
gravel, locally know as kankar. The river flows oil, and food processing industries are located in
alternately through the states of Haryana and this region. After flowing through Kaithal dis-
Punjab to Rajasthan where it disappears in the trict in Haryana, it again enters Punjab and then
Thar desert. During its course of flow in Haryana reenters Haryana at Chimmoo (G-05), which is
and Punjab, the river Ghaggar receives domes- an agricultural area. At Ratia (G-06), there are
tic and industrial wastes along with agricultural industries like sugar mill, rice mill, and paper
runoff. Consumption of pesticides in Haryana mill. The river once again flows through a part of
and Punjab during the study period (1999–2000) Punjab and then flows through Fatehabad district
was 5,030 and 7,100 MT, respectively (Agnihotri of Haryana. At downstream Sirsa (G-08), all the
2000). The river water is used for irrigation, drink- domestic sewage of the city and effluent from
ing by cattle, and occasionally for bathing. During the cotton mill, flour mill, paper mill, cardboard
1996, there were media reports of large-scale fish factory, milk plant, iron works, etc. are discharged
mortality that was supposed to be due to dis- into the river. At Ottu (G-10), the polluted water
charge of industrial and domestic sewage or runoff of Ghaggar is partly mixed into the canal water
from agricultural fields containing agrochemicals of SGC Jalwara to increase the water flow in this
(The Tribune 1996). Being agriculture-intensive canal and after Shekhukhera (G-12) it diminishes
states, pesticide use in Haryana and Punjab has in the Thar desert of Rajasthan. The canal water
been quite high. There is a high probability of is used for irrigation purpose.
these pesticides finding their way into Ghaggar
along with runoff. Though organochlorine pesti- Sampling and analysis
cides have already been reported in the water of
Yamuna, another major river of Haryana state Sampling of Ghaggar water between Chandi Devi
flowing through its eastern border (Agarwal et al. Mandir to Shekhukhera was done from 12 sites
1986; Kaushik et al. 2008), there are no such re- (Table 1; Fig. 1) in winter season. Water samples
ports on river Ghaggar except that by the authors were collected in precleaned, oven-dried, hexane-
on physicochemical characteristics (Kaushik et al. rinsed, and amber-colored bottles of 1-L capac-
2001) and heavy metals (Kaushik et al. 2000). This ity and were sealed with screw caps lined with
study presents the first report on the magnitude of aluminum foil. The samples were extracted with
contamination of Ghaggar by banned chlorinated hexane immediately after they were brought to
pesticides. laboratory by using conventional liquid–liquid ex-
traction method. This method is frequently used
for the determination of organic pollutants in
Materials and methods water (Tan 1992). The 1,000-mL water sample
was extracted with 40 mL of distilled hexane and
Sampling stations 2 g of anhydrous sodium sulfate in 2-L separat-
ing funnel and shaken well for 4–5 min. Emul-
Sampling of water was done from a stretch of sion, if formed, was broken by the addition of
approximately 230 km long in the course of river a few drops of concentrated solution of anhy-
Ghaggar through Haryana and some parts of drous sodium sulfate–absolute alcohol. The upper
Punjab adjoining Haryana border. At the point of hexane layer was collected in a flat-bottomed flask
origin of the river at Chandi Devi Mandir (G-01) and the remaining portion was extracted twice
Environ Monit Assess (2010) 160:61–69 63

Table 1 Site specification of various sampling stations along the route of river Ghaggar in Haryana
Sampling site specification Sampling station Distance from origin
in Haryana (km)
I Panchkula zone Hilly area, three streams G-01 Chandi Devi Mandir 01
meet together
Near highway, G-02 Ramgarh 10
residential area
II Ambala–Kaithal Residential, agricultural, G-03 Devigarh 31
zone industrial area
Agricultural area G-04 Lamba 79
III Fatehabad zone Agricultural area G-05 Chimmoo 116
Industrial area G-06 Ratia 136
(Sugar mill, Rice mill)
IV Sirsa zone Residential area G-07 Bhunder 171
Agricultural area, G-08 Sirsa 184
near highway; residential,
small industrial area
Residential G-09 Ottu 204
Agricultural area G-10 Ottu (mixing) 204
Residential, G-11 Ottu 204
agricultural area
Residential, G-12 Shekhukhera 229
agricultural area
In between all these four zones, the river flows through Punjab. Sampling stations G-03, G-05, G-07, and G-08 in Haryana
are downstream stations of Punjab state

with 30 mL of hexane each by gently mixing from Labor Dr. Ehrenstorfer, D-8900 Augsburg,
the sample for 15 min, each time using Teflon- Germany. Qualitative and quantitative analyses
coated magnet on a magnetic stirrer. A total of were done by comparing the retention time and
100 mL hexane was pooled and demoisturized peak area of the samples, respectively, with those
by passing over Na2 SO4 (anhydrous) and con- of the calibrated reference standards.
centrated to about 5–6 mL in a rotary evaporator Analysis of pesticide residues was carried
(Buchhi type) at 50–60˚C. The extract was cleaned out on a Chemito series 2865 microprocessor-
by column chromatography using 25 g deacti- controlled gas chromatograph equipped with
vated alumina (basic, 100 meshes) and 100 mL of electron-capture detector having 63 Ni foil as the
hexane. The eluate was concentrated to 2 mL for electron source. The column specifications and
analysis on a gas liquid chromatograph equipped operating conditions were:
with electron-capture detector (63 Ni). For recov-
ery experiment, 100–200 ng of each pesticide, its Column: 2-m glass, 0.25-in. I.D., packed
isomer–metabolite, were added to 1,000-mL river with 1.5% OV-17–1.95% QF-1
water samples, which were processed in a similar on Gas Chrom Q, 100–120 mesh
manner. Recorded percent recovery in each case Temperatures: Column 200˚C (6 min), 215˚C
is a mean of three replicates. (5 min), and 230˚C (5 min)
Hexane used as solvent was of pesticide residue Detector 280˚C
analysis grade and were distilled in all glass dis- Injector 220˚C
tillation apparatus prior to use. The peaks were Carrier gas: Nitrogen at a flow rate of
identified by comparison of retention time with 50 mL/min
those of corresponding standards. Calibration of
the instrument was done before sample analy- Confirmation of the identity of the organochlo-
sis using standards of the pesticides obtained rine residues was done on Hewlett Packard series
64 Environ Monit Assess (2010) 160:61–69

Fig. 1 Course of river


Ghaggar and the
sampling locations (inset:
map of Haryana)
Environ Monit Assess (2010) 160:61–69 65

5890 II gas chromatograph in splitless mode with et al. 1995; Ramesh et al. 1990), which may be due
the following operating conditions: to its least reactiveness and maximum persistence
out of all the HCH isomers (Wang et al. 2003),
Column BP5 Capillary 30, 0.25-mm I.D.
stable chemical structure, low vapor pressure, and
Temperatures Column 135˚C (20 min), 155˚C
high resistance to microbial degradation. The con-
(15 min), 210˚C (10 min), and
centration of β-HCH showed a decreasing trend
250˚C (5 min) Detector 300˚C
in downstream sites of the river after Sirsa (G-08)
Injector 250˚C
which might be due to the mixing of canal water
Carrier gas Nitrogen at a flow rate of
at Ottu (G-09) site with river water. The mean
1 mL/min
concentration of HCH found in the present in-
All analyses were done in triplicate. vestigation (119.74 ng/L) was quite low as com-
pared to that of HCH concentration reported in
other Indian rivers like 245 ng/L in river Ganga
Results and discussion (Agnihotri et al. 1994), 21,100 ng/L in river
Gandak (Srivastava et al. 1996), 50,690 and
Retention times, mean percent recoveries, and 43,900 ng/L in rivers Krishna and Godavari, re-
minimum detection limits for various pesticides spectively (Reddy et al. 1997), 1,200 ng/L in river
are shown in Table 2. Their identities were further Yamuna (CPCB 2000), and 310.25 ng/L in river
confirmed by chemical dehydrochlorination and Yamuna (Kaushik et al. 2008). In about 58%
subsequent gas chromatography. samples, the HCH concentration exceeded the
The concentration of hexachlorocyclohexane permissible standards of 100 ng/L recommended
(HCH; sum of α-, β-, γ -, and δ-HCH) ranged be- for drinking purpose (EC directive 1998).
tween 21.13 and 244.16 ng/L with an average value Residues of various isomers of hexachlorocy-
of 119.74 ng/L (Table 3). Among HCH isomers, clohexane are being reported from various rivers
α and δ remained nontraceable at all sampling because HCH had been in extensive use in India
sites, γ -HCH was detected in only one sample (G- during the last five decades. During the commer-
05), while β-HCH contributed mainly to the total cial synthesis of HCH, four isomers, namely, α, β,
HCH residues in the river water indicating an old γ , and δ, are formed in proportion of 55–80%, 5–
pollution source. The β-HCH residues have also 14%, 8–15%, and 2-16%, respectively. It is only
been reported in some other Indian rivers (Kumar the γ isomer that has insecticidal properties while

Table 2 Retention time, OCPs Retention time on % Recoveries Minimum detection


mean percent recoveries,
glass column (min) limit (ng)
and minimum detection
limits of organochlorine α−HCH 3.83 90 0.5
pesticides (OCPs) by γ −HCH 4.77 87 0.4
liquid–liquid extraction β−HCH 5.60 92 0.6
(LLE) with hexane as δ−HCH 6.40 85 0.8
extracting solvent Aldrin 7.35 88 0.04
o, p -DDE 10.40 83 0.7
α−endosulfan 11.50 88 0.3
p, p -DDE 12.30 86 0.4
Dieldrin 13.11 87 0.14
o, p -DDT 15.11 82 0.7
o, p -DDD 15.79 80 0.4
p, p -DDD 16.15 86 0.5
β−endosulfan 16.67 87 0.4
p, p -DDT 17.25 83 0.7
66 Environ Monit Assess (2010) 160:61–69

587.30 ± 201.18
238.59–1,005.43
all other isomers become environmental contam-
inants. Preparation of γ -HCH is costly. A ban on

1,005.43
238.593
369.551

657.983
815.847
580.515

521.454
521.272
446.582
705.911

565.223
the use of HCH was imposed in 1997, although
DDT

619.93
restricted use of γ -HCH (lindane) is allowed in
India. Industries engaged in export of γ -HCH

48.52 ± 31.14
generate α, β, and δ as by-products and discard

9.29–104.12
p,p -DDD

101.918 their waste in the open (Prakash et al. 2004).

104.116
28.848
33.186

58.860

49.906
40.000

54.663
66.279
25.372

9.290 Occurrence of various HCH isomers formed


9.884

during their persistence and interconversion


(Steinwandter and Schluter 1978) in the soil from

1.47 ± 2.23
BDL–5.21
o,p -DDD

previous applications, and the current use be-


5.212
4.682

3.112
4.525

comes the source of pesticide pollution of river


BDL
BDL

BDL
BDL

BDL
BDL

BDL
BDL

water during agricultural runoff. The occurrence


105.02 ± 98.66 of relatively higher proportions of β- and γ -HCH
27.33–367.51

as compared to α and δ is due to the fact that


p,p -DDE

β-HCH is recalcitrant and the use of γ -HCH,


123.953
367.511

116.337
214.128
41.081
43.163

89.988
32.744

27.325

31.279
74.942
97.907

though restricted, still continues. Kumari et al.


(2007) have reported total HCH residues in field
1.41 ± 3.55

soil. Prakash et al. (2004) have reported HCH


BDL–12.3
o,p -DDE

concentration in soil up to 0.051 μg/g. Still higher


12.301
1.711

2.964
BDL
BDL
BDL

BDL
BDL
BDL
BDL

BDL
BDL

concentration of total HCH (637.00 mg/kg) was


reported by them in soil sample of Indian Pes-
427.84 ± 139.08
α– and δ-HCH, α- and β-endosulfan, aldrin, and dieldrin remained BDL in all the samples

ticide Limited, Lucknow. Pesticides contaminate


165.62–675.41

drinking water also. HCH up to 24.10 μg/L


p,p -DDT

(Prakash et al. 2004) has been reported from vari-


165.615
288.409
628.036

436.072
675.409
503.084
463.156

429.036
376.939
449.952
342.771

355.711

ous brands of mineral water and a high concentra-


tion of lindane (up to 0.0042 mg/L) has been found
3.00 ± 2.85

in various brands of soft drinks by CSE (2003).


Table 3 Concentration of HCH and DDT (ng/L) in Ghaggar river water

BDL–7.19
o,p -DDT

The concentration of dichlorodiphenyltrich-


3.049
4.793

4.793
7.195

6.476
4.158
5.634
BDL

BDL
BDL

BDL
BDL

loroethane (DDT), i.e., the sum of p, p -DDT,


p, p -DDE, and p, p -DDD and o, p -DDT, o, p -
DDE, and o, p -DDD, varied from 238.59 to
119.74 ± 76.54
21.13–244.16

1,005.43 ng/L with a mean concentration of


142.815
141.358

122.416
174.391
244.159

132.652
241.663
HCH

587.30 ng/L. The minimum and maximum con-


80.391

81.608

21.130
33.054
21.304

centrations were observed at Chandi Mandir (G-


01) having least anthropogenic activities and at
115.68 ± 70.38

Devigarh (G-03), respectively. The main contri-


21.13–241.66

bution (72.85%) was due to p, p -DDT in DDT


β-HCH
142.815
141.358

174.391
195.435

132.652
241.663
122.456

residues followed by that of p, p -DDE (17.88%)


80.391

80.608

21.304
21.130
33.054

and p, p -DDD (8.26%). The high concentration


of p, p-DDT indicates recent use of DDT in the
BDL below detection limits
4.06 ± 14.06
BDL–48.72

catchment area of the river or its release from a


Sampling site γ -HCH

previously dormant source. In our country, out of


48.724
BDL
BDL
BDL
BDL

BDL
BDL
BDL
BDL
BDL
BDL
BDL

the total production of DDT, 85% has been used


for vector control under the National Malaria
Eradication Program of the government (Singh
Mean ± SD

et al. 1988) and being stable it may persist for a


Range

long time in soils. Relatively higher concentration


G-10
G-11
G-12
G-1
G-2
G-3
G-4
G-5
G-6
G-7
G-8
G-9

of DDT as compared to HCH detected in water


Environ Monit Assess (2010) 160:61–69 67

from all sampling sites may be attributed either In natural environment, the chemical and bi-
to greater persistence of DDT in the environment ological processes slowly degrade p, p -DDT to
or its current use in vector control or its illegal p, p -DDE and p, p -DDD (Baxtor 1990). The ra-
use in the catchment area. Furthermore, higher tio of ( p, p -DDE + p, p -DDD) to p, p -DDT pro-
vapor pressure for HCH isomers than that of vides an indication of how recently DDT has been
DDT facilitates relatively more rapid atmospheric released into the environment. In all the samples,
dissipation of the former pesticide in the tropics, the ratio was less than 1, which indicates that
leaving fewer residues in soils and water (Kannan p, p-DDT residues were recently introduced to
et al. 1995; Kaushik 1991). Relative abundance of the waters (Wang et al. 2003). The mean DDT
DDT and its metabolites and isomers of HCH in residues of 587.30 ng/L in the present study were
the river water observed in the present study is low when compared with other Indian rivers, i.e.,
shown in Fig. 2. 3,400 ng/L in river Yamuna (Agarwal et al. 1986),
4,000 ng/L in river Ganga (Halder et al. 1989), and
4,060 ng/L in river Krishna (Reddy et al. 1997).
However, the values were more than that for river
p,p' DDT
72.85%
(a) Ganga and Yamuna reported on a later date, i.e.,
247.2 ng/L in river Ganga (Agnihotri et al. 1994)
and 93.4 ng/L (Sharma et al. 2003) and 387.9 ng/L
(Kaushik et al. 2008) in river Yamuna.
In all the water samples, the concentration
of DDT exceeded the standard of 1.0 ng/L
o,p' DDT (USEPA 1995) for freshwater aquatic life and
0.5% o,p' DDE for drinking, i.e., 100 ng/L (EC directive 1998).
p,p' DDD 0.24%
o,p' DDD p,p' DDE The DDT metabolites may affect the growth and
8.26%
0.25% 17.88%
development of aquatic life in the river and subse-
quently that of birds and mammals through food
β-HCH (b) chain by disrupting the endocrine functions, in-
96.6%
terfering with growth and development, and caus-
ing egg-shell thinning, egg breakage, and reduced
clutch size, hatching success, and subsequent
productivity.
It is concluded from the present study that
the water of river Ghaggar contains both HCH
γ -HCH
and DDT residues that may be attributed, respec-
3.4% tively, to their previous use and continued use,
mostly in vector control programs (Joia and Battu
DDT
(c) 2000) in some catchment areas of the river in
83.07%
three states of Himachal Pradesh, Haryana, and
Punjab. Consequent upon the imposed ban and
strict registration of the persistent organochlorine
compounds in India, the levels of their residues
have been decreasing in the rivers. There is,
however, a need to implement complete ban on
sale and use of banned pesticides like DDT and
HCH HCH by the government. Also, awareness may be
16.93% created among the farmers to follow good agri-
cultural practices to avoid excessive residues in
Fig. 2 Relative abundance of DDT and its metabolites (a),
isomers of HCH (b), and total DDT and total HCH (c) in different components of the environment includ-
water of river Ghaggar, Haryana ing food items and water.
68 Environ Monit Assess (2010) 160:61–69

Acknowledgements The authors are thankful to Er. Kaushik, A., Garg, V. K., Sharma, P., & Bishnoi, M. (2001).
Anil Haritash, Department of Environmental Science and Monitoring the water quality of major rivers and
Engineering, Guru Jambheshwar University of Science and canals of Haryana—a status report (1998–99). Chandi-
Technology, Hisar for his contribution in many ways. garh: Department of Environment, Govt. of Haryana.
Kaushik, C. P., Sharma, H. R., Jain, S., Dawra, J.,
& Kaushik, A. (2008). Pesticide residues in river
Yamuna and its canals in Haryana and Delhi, India.
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Kumar, S., Kunwar, P. S., & Gopal, K. (1995). Organochlo-
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