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Environment International 32 (2006) 240 – 243

www.elsevier.com/locate/envint

Distribution and fate of persistent organochlorine pesticides


in coastal marine environment of Mumbai
G.G. Pandit *, S.K. Sahu, S. Sharma, V.D. Puranik
Environmental Assessment Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085, India
Available online 5 October 2005

Abstract

Multi-compartment monitoring of residue levels of OCPs in coastal marine environment of Mumbai has been studied. The concentration
of total HCHs in seawater varied from 0.16 to 15.92 ng/L and concentrations of total DDT varied from 3.01 to 33.21 ng/L. The total HCH
concentration in the sediment samples was in the range of 3.8 to 16.2 ng/g. g-HCH contributed almost 55% to the total HCH. In sediment
samples the DDT has higher mean concentration in comparison to its metabolite DDE and DDD. The concentration of total HCHs in
different marine species varied from 0.87 to 33.73 ng/g and concentrations of total DDT varied from 0.38 to 34.1 ng/g. The variation in the
h-HCH in different compartments is not significant and this could be due to the high persistence and metabolically inactive nature of this
isomer. The a-HCH is found to be more dominant in fish samples whereas the g-HCH is major contributor in the sediment samples.
D 2005 Elsevier Ltd. All rights reserved.

Keywords: OCPs; GC-ECD; Marine environment; BCF

1. Introduction Bidleman et al., 1993). However, most of these are confined to


the northern hemisphere and little information is available on
Persistent organochlorine pesticides (OCPs) are of concern their distribution in the tropical region (Pandit et al., 2001,
because of their high bioaccumulation potential and harmful 2000). A special feature of the OCPs in tropical marine
biological effects (Tanabe et al., 1994; Tanabe, 1991). The environment is their volatile nature and hence they may be
ubiquity of such toxic chemicals as global marine pollutants released into the air and travel long distances as an aerial source.
has been well documented (Wania and Mackay, 1996; Iwata et Our study on the distribution of OCPs in air and seawater at
al., 1994). The residence time of persistent organochlorines in Mumbai, India has shown the active transfer of these dissolved
the ocean environment appears to be very long and ocean acts OCPs into the atmosphere due to volatilization (Pandit and Sahu,
as a sink for such chemicals. High levels of organochlorines 2001).
have been detected in semi-enclosed coastal areas, which Multi-compartment monitoring is essential to elucidate the
receive direct discharges from rivers and industrial/agricultural behavior and fate of organochlorine pesticides and to assess the
sources. The removal rate of organochlorines from semi- current status of these contaminants. This paper describes the
enclosed seas is slow and this places marine organisms at risk
(Wu et al., 1999).
Once discharged into the ocean, these chemicals disperse into Table 1
Analytical conditions for gas chromatographic analysis
three phases, viz., water, sediment and marine organisms. Hence
it is important to understand the distribution of released Column DB-5 wide bore column (15 m  0.53 mm i.d.);
film thickness 5 Am
compounds in all three compartments. Studies on the distribu-
tion of organochlorine pesticides in the marine environment Temp. prog. Initial temp. 185 -C; rate: 5 -C/min;
final temp. 200 -C
have been reported by several authors (Everaarts et al., 1991;
Injection port 250 -C
Detector 290 -C
* Corresponding author. Tel.: +91 22 25590233; fax: +91 22 25505151. Carrier gas Nitrogen
E-mail address: ggp@apsara.barc.ernet.in (G.G. Pandit). Flow rate 7.5 ml/min

0160-4120/$ - see front matter D 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envint.2005.08.018
G.G. Pandit et al. / Environment International 32 (2006) 240 – 243 241

Table 2
Range and mean values of organochlorine pesticide residues in seawater, sediment and marine biota
Compounds Seawater (n = 35) Sediment (n = 35) Marine biota (n = 38)
Range (ng/l) Mean (ng/l) Range (ng/g) Mean (ng/g) Range (ng/g) Mean (ng/g)
a-HCH 0.16 – 4.39 1.23 0.70 – 4.30 1.62 0.87 – 5.3 2.12
h-HCH 0.07 – 7.74 1.41 0.10 – 4.40 2.63 ND – 6.53 2.60
g-HCH 0.10 – 7.05 2.09 0.2 – 11.8 5.96 ND – 24.7 5.51
y-HCH 0.14 – 5.89 2.62 0.30 – 1.7 0.74 ND – 7.4 1.54
~ HCH 0.16 – 15.92 5.42 3.8 – 16.2 9.90 0.87 – 33.7 11.60
DDE 0.32 – 1.84 0.87 0.03 – 0.64 1.92 0.38 – 4.78 1.71
DDD ND ND ND – 0.5 0.20 ND – 5.36 1.82
DDT 3.02 – 33.21 8.52 0.23 – 7.60 3.64 ND – 29.84 10.63
~ DDT 3.01 – 33.21 12.45 0.5 – 9.6 5.68 0.38 – 34.1 14.12

distribution and fate of persistent organochlorine pesticide in compounds (mostly fats) in the extract. Excess acid was removed
seawater, sediment and biota of coastal marine environment of by washing with de-ionized water. The extract was dried by
Mumbai. passing through a glass column filled sodium sulfate anhydrous (1
cm dia and 3 cm long). The hexane fraction was then passed
2. Materials and methods through the Florisil column for further cleanup. The cleaned up
extract was dried in a stream of nitrogen gas. 100 Al of n-hexane
2.1. Sample collection was added to the dried extract of seawater sample and 1 Al was
injected into gas chromatograph for quantification.
Seawater, sediment and fish samples were collected from the
coastline of Mumbai (latitude 18-53Vto 19-04VN; longitude 72-48Vto 2.2.2. Soxhlet extraction of sediment samples
72-53VE). The seawater samples were collected in pre acid-washed and 3 g of freeze-dried sediment was taken in a glass soxhlet extraction
cleaned polythene bottles of 5 l capacity, using a water sampler from apparatus and extracted with 60 ml of n-hexane for 16 h. The extract
various depths up to 3 m. Forty seawater and surface sediment samples was filtered using glass wool packing. The filtrate is subjected to the
were collected. Samples of eight different species of marine biota were clean up procedure as described above. The cleaned up extract was
also collected from the same sites. The sediment and fish samples dried and redissolved in 100 Al of hexane for injection into a gas
were stored in sealed polythene bags during transportation and freeze chromatograph.
dried at 40 -C before extraction. Water samples were kept at 4 -C
before extraction. 2.2.3. Soxhlet extraction of fish samples
The edible parts (mainly muscles) were dissected, homogenized in
2.2. Sample processing a mixer and then freeze dried. 5 g of the dried samples were extracted
with hexane in a soxhlet apparatus for 16 h. The extract is filtered
Water, sediment and fish samples need processing before they are using glass wool packing. The filtrate is subjected to the clean up
subjected to analysis for OCPs. These are essentially the same except procedure as described above. The cleaned up extract is dried and
that the water samples are subjected to liquid – liquid extraction whereas redissolved in 100 Al of hexane for injection into a gas chromatograph.
sediment and fish samples are subjected to soxhlet extraction. The
actual procedures are described below: 2.3. Analytical technique

2.2.1. Solvent (liquid – liquid) extraction of water samples A Gas chromatograph model 8610 HT (Chemito Instruments)
500 ml of filtered seawater sample was extracted twice with 25 equipped with pulsed type Electron Capture Detector (ECD) is used
ml of hexane. Few grams of mercury was added to the extract and for the quantification of pesticides in the sample extracts. The
stored for 24 h to remove sulphur compounds in the sample. operating conditions are listed in Table 1. Synthetic mixture of
Concentrated sulfuric acid was then used for oxidizing organic pesticides containing 50 pg/Al is used for calibration. Linearity of

Fig. 1. Percentage distribution of organochlorine pesticide residues in seawater, sediment and marine biota.
242 G.G. Pandit et al. / Environment International 32 (2006) 240 – 243

3000
samples. In the sediment samples the gamma HCH contributes 36% of
2500 total organochlorine pesticides measured, while the contribution from
2000 DDT is found to be 22%. In the marine biota samples DDT contributes
Kd

1500 41% while its metabolite DDD contribute 7% to the total quantified
1000 OCPs.
500
The distribution coefficients of OCPs between sediment and
seawater (K d value) have been shown in Fig. 2. The K d values for
0
OCPs are in the range of 427 to 2851. The gamma HCH was found to
H

T
have highest K d value which implies the higher affinity of this HCH

D
C

D
H

D
D
α-

β-

γ-

δ-

isomers towards the sediment in the sampling region. The K d value of


Fig. 2. K d value of OCPs in the coastal marine environment of Mumbai. DDE was found to be almost five times than that for the DDT. This
could be due to the conversion of DDT to its metabolites DDE.
response of the ECD has been tested by using different synthetic Concentration of total HCHs in different marine species varied
mixtures in the range of 5 to 100 pg/Al. from 0.87 to 33.73 ng/g and concentrations of total DDT varied from
0.38 to 34.1 ng/g (Table 3). The concentration of organochlorine
3. Results and discussion pesticides in fish samples was found to be lower than those in fish of
temperate regions. The reason that fish from tropical latitudes
The range and mean concentration of organochlorine pesticide accumulate lower concentrations of organochlorine compounds than
residues in the seawater, sediment and fish samples from the coastline fish from temperate regions may be explained by the shorter residence
of Mumbai are presented in Table 2. The concentration of total HCHs time of these compounds in the tropical environment. For instance,
in seawater varied from 0.16 to 15.92 ng/L and concentrations of total DDT and HCH are likely to rapidly volatilize in the tropical
DDT varied from 3.01 to 33.21 ng/L. The high concentration of DDT environment (Wania and Mackay, 1993). Also, higher temperatures
in comparison to its metabolite (DDE) in the seawater samples in the tropics could enhance the elimination rate of chemicals in fish
indicates the fresh input of DDT. In addition to DDT levels providing due to the influence of temperature on respiratory requirements of the
insight to emission sources of this chemical, the ratio of DDT and its fish, as the biological half-lives of compounds such as HCH and DDT
metabolite DDE can also serve as a guide to magnitude of source are shorter at high temperature.
emission. High ratios of DDT to DDE in seawater samples indicate the The bioconcentration factor (BCF) of OCPs for the species
presence of a significant source of DDT in this region. considered in this study has been shown in Fig. 3. The BCF values
The total HCH concentration in the sediment samples was in the of OCPs were in the range of 588 to 2636. The lower BCF observed in
range of 3.8 to 16.2 ng/g. g-HCH contributed almost 55% to the total the study region may be due to higher elimination rate of OCPs from
HCH. The lower alpha to gamma HCH ratio in the sediment samples the marine biota in the tropical climate. There is not much difference
implies the usage of lindane formulation in this region. The DDT has in the BCF values for HCH isomers, except delta isomer, that was
higher mean concentration in comparison to its metabolite DDE and observed. The low value of BCF for the delta HCH could be due to it
DDD. The significant level of concentration of DDE in comparison to higher water solubility. The BCF for DDT was found to be lower than
DDD may be attributed to presence of various kinds of marine benthic its metabolites DDE.
organism, which accelerate the biodegradation process of DDT to The variation in the beta HCH isomer in different compartment is
DDE. The marine sediments were found to be alkaline with high not much significant this could be due to the high persistence and
salinity and organic matter (humic substances). Organic matter is also metabolically inactive nature of this isomer. The alpha HCH is found
likely to play an important role towards the degradation of DDT to to be more dominant in fish samples whereas the gamma HCH is the
DDE. major contributor in the sediment samples. The variation in
The percentage distribution of organochlorine pesticide residues in composition of alpha and gamma HCH isomers in different marine
the seawater, sediment and fish samples from the coastline of Mumbai compartments may be due to the differences in degradation rate of
are shown in Fig. 1. In seawater samples DDT contributes more than these insecticides. In marine biota DDT is mostly converted into its
50%. Among HCH isomers delta HCH contributed most in seawater metabolites namely DDE and DDD, which could be due to its short

Table 3
Concentration (ng/g) of organochlorine pesticide residues in different marine biota
Species Common name a-HCH h-HCH g-HCH y-HCH ~ HCH DDE DDD DDT ~ DDT
Rastrelliger kanagurta Bangda 3.01 2.10 7.79 1.12 14.02 3.70 5.36 25.09 34.15
Parastromateus niger Halwa 0.87 BDL BDL BDL 0.87 0.56 BDL BDL 0.56
Scoliodon laticaudus Dog fish 1.28 6.53 24.68 1.24 33.73 0.59 2.13 29.84 32.56
Pampus argenteus Paplet 5.26 3.96 6.32 BDL 15.54 0.48 4.07 29.50 34.05
Eleutheronema tetradactylum Rawas 1.31 2.95 1.40 2.31 7.97 0.77 BDL BDL 0.77
Panaeus monodon Prawn 1.31 1.33 BDL BDL 2.64 0.38 BDL BDL 0.38
Portunus sanguinolentus Crab 2.01 1.97 3.43 7.41 14.82 2.47 BDL BDL 2.47
Villorita cyprinoids Clam 1.93 1.62 BDL BDL 3.55 4.78 3.11 BDL 7.89
*BDL = Below Detection Limit.
G.G. Pandit et al. / Environment International 32 (2006) 240 – 243 243

3000
seawater and sediment samples the ratio of DDE to DDT
2500
was found to be very less, which can be attributed to the
2000
fresh input of DDT.
BCF

1500
1000
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500
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H
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D
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