0% found this document useful (0 votes)
25 views7 pages

Fate and Distribution of Organochlorine Insecticides (OCIs) in Palakkad Soil, India

Fate and distribution of organochlorine insecticides (OCIs) in Palakkad soil, India, Nisa KG And Sujatha CH

Uploaded by

Nisa Kg
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
0% found this document useful (0 votes)
25 views7 pages

Fate and Distribution of Organochlorine Insecticides (OCIs) in Palakkad Soil, India

Fate and distribution of organochlorine insecticides (OCIs) in Palakkad soil, India, Nisa KG And Sujatha CH

Uploaded by

Nisa Kg
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 7

Sustainable Environment Research 28 (2018) 179e185

Contents lists available at ScienceDirect

Sustainable Environment Research


journal homepage: www.journals.elsevier.com/sustainable-
environment-research/

Original Research Article

Fate and distribution of organochlorine insecticides (OCIs) in Palakkad


soil, India
Nisa Kulangaravalappil Gopalan, Sujatha Chenicherry*
Department of Chemical Oceanography, Cochin University of Science and Technology, Kochi 682016, India

a r t i c l e i n f o a b s t r a c t

Article history: Organochlorine insecticides (OCIs) are considered as one of the cost effective insecticides to provide
Received 25 July 2017 quick impact on weed and pest control in agricultural application. The present investigation describes
Received in revised form the spatio-temporal distribution pattern of OCIs and their concurrent environmental fate in surface soil
7 November 2017
samples collected from six provinces during monsoon and summer season from Palakkad district, the
Accepted 26 January 2018
Available online 6 February 2018
largest productive sector in the State of Kerala, India. The samples were analyzed to determine the re-
sidual levels of persistent OCIs (a-BHC (Cyclohexane), b-BHC, g-BHC, heptachlor, aldrin, heptachlor
epoxide (isomer B), 4,40 -DDE, dieldrin, endrin, 2,40 -DDD, 4,40 -DDD, 2,40 -DDT, 4,40 -DDT, a-endosulfan and
Keywords:
b-endosulfan), by gas chromatographic technique using electron capture detector. The revealed results
OCIs P
Surface soils showed that the concentrations of OCIs in soils of Palakkad ranged from non-detection to 150 ng g1.
Distribution The analysed samples mainly constitute endrin, followed by 2,40 -DDD, aldrin and g-BHC. These xeno-
Residual levels biotic residues could have resulted from the direct application into the soils and its persistent character
Endrin in environment. These findings point out that their accumulation in the soil and risk of mobilization into
the aquatic system would pose serious health hazards in the biota and in turn in the ecosystem. It was
statistically interpreted that the sorption of OCIs in the soil matrix is influenced by the presence of
organic matter, pH, temperature and the texture of the soil. The findings highlight the need of periodical
monitoring of soil quality in and adjacent to the agricultural zones.
© 2018 Chinese Institute of Environmental Engineering, Taiwan. Production and hosting by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).

1. Introduction Fate and distribution of OCIs in soil are influenced by the climate
and geochemistry of the site, the nature of the chemical, its
It has been seen that rapid use of organochlorine insecticides magnitude of applications and their period of exposure. Earlier
(OCIs) has increased manifolds and posed serious threat to the researchers have reported the influence of periodically changing
quality of the environmental niche and has created various health humid climate on the sorptional potential of laterite rich soils [5].
issues for the public [1,2]. Moreover, storing of locally manufac- However, the nature of the soil and chemical will determine the
tured insecticides like the dichlorodiphenyltrichloroethane (DDT), overall sorption rate and behavior of these chemicals in the agro-
the group of cyclodiene (aldrin, dieldrin, endrin, chlordane, non- field. The extent of soil lipophilicity has prominent influence on
achlor, heptachlor and heptachlor-epoxide), benzene hexachloride the retention of OCIs of soils along with pH and periodically
(BHC/HCH/lindane) and endosulfan in warehouses [3], for future changing humidity [6]. Hence the evaluation of interaction be-
use to enhance the crop production [4] is another possible source of tween labile organics, pH and pesticide persistence is vital to assess
OCI contamination. Though regions continue usage of these the status of the environment and in formulating remediation
persistent organic compounds, the background data base is lacking. strategies.
OCIs were used worldwide as active insecticide in the past to
control pests in agricultural fields and also as vector control. Ac-
cording to the statistical data of 2016, Kerala consumes an average
of 380 tons of insecticides [7]. Palakkad is known to be the major
* Corresponding author.
E-mail address: [email protected] (S. Chenicherry). agrarian district of Kerala; hence, the application of these persistent
Peer review under responsibility of Chinese Institute of Environmental OCIs is necessary. Informal interaction with the labourers working
Engineering.

https://doi.org/10.1016/j.serj.2018.01.007
2468-2039/© 2018 Chinese Institute of Environmental Engineering, Taiwan. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
180 N.K. Gopalan, S. Chenicherry / Sustainable Environment Research 28 (2018) 179e185

in the farms and some local people confirms the usage of OCIs in were freeze dried and grinded to fine powder. Approximately 5 g
the area. This research intends to develop a background database of sample was weighed and extracted twice with hexane: acetone
persistent organic pollutants used in these locations and the in- (1:1) mixture and was subjected to a cleanup procedure involving
fluence of climate prevailing in these zones and their retention and elution through florisil column (60 cm  22 mm i.d.) with hexane:
fate. Besides, this investigation focuses on understanding the syn- acetone (1:1). The extract was concentrated to about 5e6 mL by
ergistic/antagonistic behavior of labile organic materials on the means of the rotary evaporator at 50e60  C for further analysis
passive diffusion of pesticides into the soil matrix. The retention of using gas chromatograph (GC) with electron capture detector.
these persistent organic pollutants is linked to the lipophilic nature
of labile organic materials [8] and the present study also highlights 2.2. Quality control
these controlling factors.
All data were subject to strict quality control procedure. For every
2. Materials and methods set of samples, procedural blanks and spiked samples with stan-
dards were used to check interference, cross contamination and
2.1. Sampling and sample processing instrument performance. Surrogate standards in sediment samples
were used to determine result precision. The mean recovery of
Field investigations in agricultural and industrial areas of Pal- surrogate standards was 90 ± 5% in the extraction method. The
akkad were carried out in monsoon and summer during the month detection limit of the method ranged from 0.01 to 0.08 ng g1. Each
of June 2013 and March 2014 respectively. A total of six stations sample extract was analyzed in triplicate and relative standard de-
were selected with three sites from agricultural zone (CI, CII, CIII) viations were 15%. The spiked samples in each set of ten samples
and three from industrial zones (KI, KII, KIII) (Fig. 1). From each were analyzed with mean recoveries ranging from 85 to 109%.
station three soil samples were collected and analysed and esti-
mated as their mean values ± standard deviation (Table 1). All the 2.3. Reagents and calibration
soil samples after collection were immediately transferred to brown
glass bottles and transported to the laboratory where they were The OCIs standards, a-hexachlorobenzene (BHC), b-BHC, g-BHC,
kept at 20  C till analysis. Prior to OCIs extraction, soil samples heptachlor, aldrin, heptachlor epoxide (isomer B), 4,40 -DDE,

Fig. 1. Location map of the study area and sampling sites.


N.K. Gopalan, S. Chenicherry / Sustainable Environment Research 28 (2018) 179e185 181

dieldrin, endrin, 2,40 -DDD, 4,40 -DDD, 2,40 -DDT, 4,40 -DDT, a-endo-

a -ENDO b -ENDO
sulfan and b-endosulfan were obtained from EPA (USA) and

BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
Supelco (USA).

2.4. Chromatographic systems and conditions


BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
Results were obtained by using GC (model 7890A, Agilent,
4,40 -DDT

Waldbronn, Germany) equipped with a split/splitless injector, an


electron capture detector and a 30 m  0.320 mm i.d., HP-35
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
capillary column with 0.5 mm film (35% e (phenyl)-methyl poly-
siloxane phase). The injector port temperature was maintained at
2,40 -DDT

250  C and detector temperature at 350  C. The GC oven temper-


BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
ature was programmed from 110  C at 5  C min1 to 190  C at
5  C min1 and held for another 2 min, then to 280  C at a heating
4,40 -DDD

rate of 15  C min1. This temperature was held constant for 10 min.


Nitrogen was used as the carrier gas at a flow rate of 1.0 mL min1
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL

with the split ratio 1:50.


59 ± 22.2

59 ± 14.6
2,40 -DDD

2.5. Other analyses


BDL
BDL
BDL
BDL
BDL
BDL
BDL

BDL
BDL
BDL

The soil characteristics were analyzed by standard protocols:


4,40 -DDE

0.3

0.4

2.4

0.2

textural analysis using Pipette analysis [9], protein by Lowry et al.


4.6 ±

5.4 ±

5.4 ±

5.5 ±
BDL

BDL
BDL
BDL
BDL
BDL

BDL

BDL

[10], carbohydrate by phenol-sulphuric acid method [11] and lipid


using sulphophosphovanillin method [12]. Statistical Package for
± 18.1
± 15.4

± 22.3
± 11.1

Social Sciences (SPSS) software version 20.0 was used to generate


Endrin

the means of the results.


63.9
65.1

63.8
63.8
BDL
BDL
BDL
BDL
BDL
BDL
BDL

BDL

3. Results and discussion


7.51 ± 1.1
7.4 ± 1.3
7.7 ± 3.1

7.3 ± 2.3
Dieldrin

BDL
BDL
BDL
BDL
BDL
BDL
BDL

BDL

The results of four different OCI groups [first group - DDT; sec-
ond group e cyclodiene (aldrin, dieldrin, endrin, chlordane, non-
Heptachlor epoxide (B)

achlor, heptachlor and heptachlor-epoxide); third group e benzene


hexachloride (BHC/HCH/lindane); and fourth group e endosulfan]
examined during monsoon and summer season are depicted in
P
Table 1. The results of OCIs in soils of Palakkad shown in Fig. 2,
ranged from non-detection to 150 ng g1. Among the four OCIs
4.2
0.4

2.2
1.1

2.1
1.1
2.3
1.1
1.2
4.7 ±
7.5 ±

1.1 ±
4.2 ±

4.8 ±
0.4 ±
7.6 ±
4.1 ±
4.1 ±

investigated, cyclodiene compounds, HCBs and chlorinated deriv-


BDL
BDL

BDL

ative of diphenyl ethane were observed in the Palakkad soils,


whereas endosulfan was not detected in these zones. One of the
20.3 ± 11.2

13.2 ± 12.2
1.6 ± 1.5

1.9 ± 1.8

1.3 ± 0.1
1.4 ± 1.2
1.3 ± 1.1

1.4 ± 0.3

most prominent OCIs observed in Palakkad was endrin, a con-


Aldrin

spicuous member of cyclodiene group and its concentration in the


BDL
BDL
BDL

BDL

soils was approximately 64 (63e65) ng g1. Other prominent


members of cyclodiene compounds observed in this soil were
Heptachlor

1.2

1.2
1.1

1.1
0.1

0.4
2.4 ±

1.1 ±
0.9 ±

0.4 ±
0.7 ±

0.6 ±
Concentration of OCIs (ng g1) in the surface soil of Palakkad district.

BDL

BDL
BDL

BDL

BDL
BDL
15.9 ± 3.4
1.1 ± 1.5
0.6 ± 1.1

0.9 ± 2.2
0.7 ± 1.1

0.6 ± 1.6
0.7 ± 1.1
0.6 ± 0.1
0.6 ± 0.6
0.6 ± 1.3
g-BHC

BDL

BDL
6.3
4.5
4.3

0.5
4.2
3.6
2.1
5.1
b-BHC
9.7 ±
7.3 ±
6.6 ±

0.7 ±
6.8 ±
6.7 ±
6.7 ±
6.8 ±
BDL
BDL
BDL
BDL
0.6
0.2
0.2
1.3

0.3
0.6

1.4
1.1
a-BHC
1.9 ±
1.0 ±
0.8 ±
1.1 ±

0.8 ±
0.8 ±

0.8 ±
0.9 ±
BDL
BDL
BDL

BDL
Stations

KIII

KIII
CIII

CIII
KII

KII
CII

CII
KI

KI
CI

CI
Monsoon 2013
Sampling No.

Summer
2014
Table 1

P
Fig. 2. Concentration of OCIs in soil of Palakkad district.
182 N.K. Gopalan, S. Chenicherry / Sustainable Environment Research 28 (2018) 179e185

aldrin, heptachlor epoxide (B), dieldrin and heptachlor. However, conducted earlier all over the world. Intra specious transport of
during the monsoon month, endrin was found to be below detec- these OCIs to food has been observed for endrin. In Togo, West
tion level (BDL) in all the six stations under investigation. However, Africa, they were observed in cowpea [16], cucumbers in Tokyo and
aldrin was recorded in the soil samples during monsoon month as winter squash in the USA [17,18].
well as in the summer month. The values ranged from BDL to The highest concentration of aldrin was found only in agricul-
20 ng g1 in the monsoon month and BDL to 13 ng g1 in the tural zones, indicating a large input of these xenobiotics to the area
summer month. The level of dieldrin and heptachlor epoxide (B) in leading to hazardous influence on the environment [13]. Aldrin is
the soil samples exhibited a similar trend, or BDL to 7.7 and BDL to rarely distinguished in monitoring studies due to its degradation
7.6 ng g1 during summer, respectively. On the other hand, dieldrin pattern as it breaks quickly to dieldrin, which is considerably more
was observed as BDL in all the six stations during monsoon month, resistant to further degradation. Therefore, the high rate of detec-
whereas heptachlor epoxide (B) levels were significant in all the tion for dieldrin combined with the infrequent discovery of aldrin is
stations except one station with the levels BDL. Finally, heptachlor a common outcome in contaminant scrutinizes [19]. In contrast, the
was recorded in both the seasons, but their levels were consider- persistent nature of aldrin as compared to dieldrin confirms the
ably low (0.4e2.4 ng g1), when compared to other cyclodiene fresh input and common source for these contaminants in the study
compounds in soil samples. Among the DDT class of insecticides, region. The manufacture, use and import of aldrin and dieldrin have
major OCIs observed was 2,40 DDD. During summer their concen- been banned in India since 2013 and their detection denotes the
tration reached 59 ng g1 in CII and in KIII. Another major metab- illegal usage [20].
olites of DDT observed was 4,4’ DDE. During monsoon, it was noted Other prominent OCI, heptachlor epoxide (B), observed in the
only in CII (4.6 ng g1) and in the summer month this station study, are also derived from the agricultural zone and indicates a
showed a slight increase in its concentration (5.4 ng g1). All the direct source rather than from remote transport to these provinces.
other metabolites of DDT under investigation showed BDL in all the However, the presence of degradation products of heptachlor and
stations in both the sampling seasons. their prominence when compared to heptachlor epoxide (B)
Third class of OCIs detected in the soil samples was HCB; the highlight prolonged usage of these chemicals. Their residues and
major group observed from this class of xenobiotics was lindane their degradation products are a matter of serious concern as they
and the concentrations were significant in both seasons. The are very stable and possibly enter the food web leading to lethal
highest was recorded during monsoon (15.9 ng g1). In summer the hazardous effect to the ecosystem [21].
concentration in the stations was BDL. Second prominent HCB Although the insecticides such as DDT were banned in India for
observed was b-BHC and the levels during monsoon dropped to enhancing agricultural output as early as 1989. Their presence in
BDL during the summer month. At the same time, in summer in all these studied provinces is an indirect evidence for the usage of
the stations, their levels ranged between 0.7 and 6.8 ng g1. How- dicofol and historically used DDT due to its longer half-life. As DDT
ever, a-BHC was recorded during both seasons ranging between is a prominent intermediate used for the synthesis of dicofol, their
BDL to 1.9 ng g1. higher level hints to an extensive usage of dicofol in these locations
These findings indicate that agricultural activities within the under various brand names [22]. Under aerobic and anaerobic
vicinity of the sampling site have affected the quality of the surface conditions in the soil, DDT can be converted into its major toxic
soil due to their application and the extensive degradation. Indus- metabolites, DDD and DDE [23]. The detection of 2,40 DDD and 4,40 -
trial and domestic usage of organic pollutants also contributes to a DDT in the present investigation implies extensive and prolonged
certain extent of the entry of such menacing substances into the usage of DDT [24]. Their residual levels in these zones highlight the
soil and these findings are well supported by earlier reports [13]. possibility of their mobilization into the adjacent water reservoirs
Stations which detected the prominent presence of endrin were and aquifers raising serious threat to the human population [23].
along the fringes of industrial hub including the samples selected Similar observations were reported in Kasargod district, Kerala,
from agricultural zone. This perennial class of OCIs in excessive India, in which the presence of DDT was found to be BDL whereas
amounts indicates long term accumulation from prolonged their metabolites were spotted in the groundwater system clearly
discharge from industries and their direct application to soil and showing their persistent nature in the environment [25].
crops. Their persistence in the environment is directly influenced The residual levels of BHC and its metabolites were detected at
by the chemistry of the soils which could influence the retention, almost all the stations in the present study, apparently due to the
transport, or degradation process within the soil matrix [14]. Other irregular usage as previously reported by Leena et al. [26] in Delhi.
factors, particularly volatilization, leaching, wind erosion, surface According to Sankararamakrishnan et al. [27], the source of g-BHC
run-off, and crop uptake are also major factors influencing the fate (lindane) in water is from direct application used for the control of
and transport of endrin as reported previously by Harris et al. [15]. mosquitoes, for various purposes in the field of agriculture and
High levels of insecticides have been detected in various studies forestry and to a lesser extent, from occasional contamination of

Table 2
Physico-chemical properties of surface soils of Palakkad district.

Sampling Season Stations TOC (%) Sand (%) Clay (%) Silt (%) Soil class Protein (mg g1) Carbohydrate (mg g1) Lipid (mg g1)

Monsoon 2013 CI 0.28 ± 0.1 90.2 6.4 3.4 Loamy sand 1330 ± 240 1718 ± 116 495 ± 151
CII 1.14 ± 0.12 22.2 55.2 22.6 Clay 2580 ± 140 3008 ± 145 209 ± 102
CIII 1.03 ± 0.2 91.1 4.2 4.7 Sand 3142 ± 310 2295 ± 124 490 ± 142
KI 1.46 ± 0.14 52.5 36.9 10.7 Sandy clay 5602 ± 142 2052 ± 231 478 ± 121
KII 1.77 ± 0.21 85.5 1.3 13.2 Loamy sand 1239 ± 146 1948 ± 214 414 ± 101
KIII 1.92 ± 0.14 17.1 11.7 71.2 Silt loam 4905 ± 214 2430 ± 271 249 ± 213
Summer 2014 CI 0.36 ± 0.11 64.9 27.8 7.4 Sandy clay loam 3740 ± 143 6773 ± 186 105 ± 140
CII 0.67 ± 0.10 65.9 28.1 6.0 Sandy clay loam 3061 ± 301 3453 ± 140 111 ± 134
CIII 2.32 ± 0.22 67.8 28.6 3.6 Sandy clay loam 3869 ± 110 6775 ± 171 196 ± 123
KI 0.37 ± 0.13 62.3 28.3 9.4 Sandy clay loam 3712 ± 214 8615 ± 164 173 ± 151
KII 0.74 ± 0.02 68.3 14.5 17.2 Sandy loam 3291 ± 154 3270 ± 210 118 ± 147
KIII 0.44 ± 0.13 69.4 25.3 5.3 Sandy clay loam 3849 ± 114 6206 ± 113 197 ± 131
N.K. Gopalan, S. Chenicherry / Sustainable Environment Research 28 (2018) 179e185 183

wastewater from industrial plants. Similar studies were carried

Heptachlor epoxide(b) Dieldrin Endrin 4,40 -DDE 2,40 -DDD


out in various types of soil from India with the concentration
lindane (g-BHC) in Delhi region ranging from 0.01 to 94.7 mg kg1

1
[28] whereas in two districts studied from Assam ranged from 0.10
to 1.9 mg kg1 [29]. Contaminations of soils by OCIs were also

0.776**
reported in the agriculture sector of Haryana [30]. Among the BHC
isomers, g-BHC reported the highest concentration in ground-

1
water systems in Kasargod district, Kerala [25].

0.628*
0.405
The physico-chemical properties of surface soils of Palakkad

1
district are presented in Table 2. Total organic carbon (% TOC) was

0.935**
determined in soils ranging from 0.28 ± 0.1 to 2.32 ± 0.22%. Soil

0.587*
0.348
texture in terms of sand, clay and silt (%) were in the range from

1
17.1 to 91.1, 1.3 to 55.2, 3.4 to 3.5, respectively (Table 2). The result
revealed that the dominance of sandy clay loam in all the stations
with no much variation among them. This consistently high sandy
clay loam values may be attributed to the winnowing activity of
sediment transport system prevailing in the location. Perennial

0.847**
flow of rainwater in Palakkad district, influenced by gentle slope of

0.362
0.436

0.469
the environment, may be the reason for this dominant sandy clay

1
loam nature of the soil.

0.036
0.026
Heptachlor Aldrin
The statistical analyses by means of SPSS revealed a noticeable

0.402
0.495
0.545
correlation as depicted in Table 3. Endrin has a significant positive

1
correlation between sand, proteins and strongly correlated to lipid
content in the soil. Dieldrin showed significant positive correla-

0.399
0.078
0.348
0.308
0.207
0.27
tion with lipid. But in the case of heptachlor epoxide (B) along
with protein and lipid, it shows significant correlation with car-

1
bohydrate and negatively to silt. In comparison to endrin, hepta-

0.206
0.224
0.209
0.173
0.133
g-BHC

0.13
0.467
chlor epoxide (B) lacks any correlation with sand. Heptachlor

1
exhibits a negative correlation with protein, whereas positive

0.131
correlation with silt. b-BHC has a strong correlation towards lipid
b-BHC

0.172

0.517
0.597
0.591
0.594
0.373
0.13
content and a significant correlation with protein and carbohy-

1
drate content. These findings indicate that the distribution and

0.995**

0.116
0.217
0.198
0.175
0.177
0.108
a-BHC

0.186

0.426
sorption of these xenobiotics depend on the nature and organic
content present in the soil [31].

1
The part played by different labile organic matters in the Pal-

0.794**

0.711**
0.263

0.267
0.482

0.668*
0.627*

0.616*
0.311
Carbohydrate Lipid

0.44
akkad soils in determining the OCI sorption has been clearly
1

observed in this investigation. Previously, potential of lipid con-


tents in the soil matrix towards the retention of nonionic com-
pounds has been reported [32]. This has been further supported
0.932**

0.289
0.504
0.641*

by the works of Schnitzer and Khan [33], in which long chain 0.633*
0.163

0.352
0.441
0.568
0.265
0.3

hydrophobic phase on the surface of soil results from fatty acids


1

and phospholipids. Hydrogen bonding resulting from lipids may


0.576*
0.945**
0.958**
Protein

0.293

0.298
0.650*

0.647*

0.670*

be playing a vital role in the immobilization of OCIs. In general


0.376

0.555
0.406
0.56

alkyl composition along with aromatic content contributes the


1

hydrophobic partitioning effect of soil solution [32]. Other factors


Correlation between the soil parameters and OCIs of Palakkad district.

0.879**
0.903**

0.663*

0.684*
0.968**

0.577

0.418

0.514

0.559
0.434

influencing the sorptional features of soil arise from the hetero-


0.651*
0.171

0.186
Silt

geneous sorption sites in refractive organics. In general, correla-


1

tion values of lipids with OCIs in the present study strongly


0.795**
0.725**
0.757**
0.808**

0.051
0.584
0.015

0.348
0.548
0.516
0.566
0.461
0.357

depend on the lipid content and negatively to silt. Earlier, inves-


0.311
Clay

tigation of pyrene binding by a model compound, humic acid,


**Correlation is significant at the 0.01 level (2-tailed).
*Correlation is significant at the 0.05 level (2-tailed).
1

observed significant modification as the aliphatic/aromatic


0.722**
0.778**
0.720**
0.749**

0.395
0.279

0.607*

chemical moieties in humic matter varied [34]. Similarly,


0.48

0.43
0.536

0.538
0.533

0.455
0.381
Temperature Sand

0.37

depending on the chemical and physical nature of the OCIs,


1

sorptional features are significantly modified in the presence of


lipid contents. Chin et al. [35], observed a reduced binding affinity
for hydrophobic compounds in the presence of aliphatic rich
0.228

0.394

0.363
0.34
0.429

0.478
0.456
0.467

0.361

0.056

0.353
0.536
0.348

0.239
0.23

refractive organic compounds.


0.3
1

Significant negative correlation towards protein may be due to


Heptachlorepoxide(b)

the masking of active sites by charged moieties in the molecules. It


has been observed by Barriuso and Koskinen [36] the blocking of
atrazine sorption of hydrophobic moieties by silt and fine clay
Carbohydrate
Temperature

Heptachlor

particles bound to charged polyelectrolytes when compared to


Variables

2,40 -DDD
4,40 -DDE
Dieldrin
Protein

coarse particles without these surface modifications. Differential


Endrin
g-BHC
a-BHC
b-BHC

Aldrin
Table 3

Lipid
Sand
Clay

distribution, however, was observed for OCIs in the present


Silt

investigation may be due to the difference in the protein


184 N.K. Gopalan, S. Chenicherry / Sustainable Environment Research 28 (2018) 179e185

composition of these organic materials. However, evidence for such References


interactions cannot be deduced from this study. Our investigation
highlights the dependence of OCI sorption on the nature of organic [1] Gama AF, Cavalcante RM, Duaví WC, Silva VPA, Nascimento RF. Occurrence,
distribution, and fate of pesticides in an intensive farming region in the Brazilian
matrix and their significance while assessing the fate and transport semi-arid tropics (Jaguaribe River, Ceara ). J Soils Sediments 2017;17:1160e9.
in soil, particularly in Palakkad. [2] Sankoh AI, Whittle R, Semple KT, Jones KC, Sweetman AJ. An assessment of the
Ahmad et al. [32] observed synergistic influence of proteina- impacts of pesticide use on the environment and health of rice farmers in
Sierra Leone. Environ Int 2016;94:458e66.
ceous materials on the sorption of hydrophobic materials into the [3] Bhardwaj T, Sharma JP. Impact of pesticides application in agricultural in-
soil matrix. Role of proteins rich in aliphatic amines in contrast the dustry: an Indian scenario. Int J Agric Food Sci Technol 2013;4:817e22.
sorption of atrazine in soils with reduced aliphatic carbon content [4] Kabir ER, Rahman MS, Rahman I. A review on endocrine disruptors and their
possible impacts on human health. Environ Toxicol Phar 2015;40:241e58.
has been reported by Piccolo et al. [37]. Role of aliphatic induced [5] Ten Hulscher TEM, Cornelissen G. Effect of temperature on sorption equilib-
hydrophobic phase towards significant positive correlations to rium and sorption kinetics of organic micropollutants e a review. Chemo-
proteinaceous organic matter observed in this study has been sphere 1996;32:609e26.
[6] Fredrickson DR, Shea PJ. Effect of soil pH on degradation, movement, and plant
further supported by works of Dunigan and McIntosh [38], in which
uptake of chlorsulfuron. Weed Sci 1986;34:328e32.
proteinaceous moieties showed two to four times enhanced bind- [7] DOA. An analytical Study of Agriculture in Kerala. Thiruvananthapuram, India:
ing affinities when compared to polysaccharide enriched models Directorate of Agriculture; 2016.
[8] Tatarkova V, Hiller E, Halko R. Retention characteristics of acetochlor in soils
[39]. Influence of vegetation and microbes on the structure and 
collected from different depths in relation to soil properties (Zitný ostrov
hydrophobic properties of humic acid has been observed adjacent Area, SW Slovakia). Soil Water Res 2014;9:58e65.
to the study area [40,41]. [9] Lewis DW. Practical Sedimentology. Stroudsburg, PA: Hutchinson Ross Pub-
A limitation of this study is the small sample set and lack of data lishing Co.; 1984.
[10] Lowry OH, Rosebrough NJ, Farr AL, Randall RJ. Protein measurement with the
regarding the vertical distribution of OCIs in these zones, therefore Folin phenol reagent. J Biol Chem 1951;193:265e75.
a better spatial resolution of surface and sub soils along with higher [11] Dubois M, Gilles KA, Hamilton JK, Rebers PA, Smith F. Colorimetric method for
replication of samples is necessary in future studies. determination of sugars and related substances. Anal Chem 1956;28:350e6.
[12] Barnes H, Blackstock J. Estimation of lipids in marine animals and tissues:
detailed investigation of the sulphophosphovanilun method for ‘total’ lipids.
4. Conclusions J Exp Mar Biol Ecol 1973;12:103e18.
[13] Subramani T, Mangaiyarkarasi M, Kathirvel C. Impact of sewage and industrial
effluent on soil plant health act on environment. Int J Eng Res Appl 2014;4:
The study describes the evidence for the presence of OCIs in 270e3.
Palakkad soils and the role for various labile organic matter present [14] Donoso J, Dorigan J, Fuller B, Gordon J, Kornreich M, Saari S, et al. Reviews of
in soils for binding the hydrophobic OCIs and showcases that the the Environmental Effects of Pollutants: XIII. Endrin. Cincinnati, OH: US
Environmental Protection Agency; 1979.
dissimilarities exist in the chemical composition of the soil matrix
[15] Harris CR, Sans WW, Miles JR. Exploratory studies on occurrence of organo-
which could be included while assessing the fate of OCIs. Further chlorine insecticide residues in agricultural soils in southwestern Ontario.
key to the fate and transport of these OCIs may be influenced by the J Agr Food Chem 1966;14:398e403.
[16] Mawussi G, Sanda K, Merlina G, Pinelli E. Assessment of average exposure to
charged particles and their interaction with binding sites. In
organochlorine pesticides in southern Togo from water, maize (Zea mays) and
conclusion, proteinaceous materials in the Palakkad soil are a cowpea (Vigna unguiculata). Food Addit Contam A 2009;26:348e54.
decisive factor in regulating the OCI sorption where aliphatic car- [17] Jorgenson JL. Aldrin and dieldrin: a review of research on their production,
bon contributed by lipid hydrophobic phase is much lower. Hence, environmental deposition and fate, bioaccumulation, toxicology and
epidemiology in the United States. Environ Health Perspect 2001;109:
detailed analysis of labile organic matter composition in these soils 113e39.
is vital in order to establish the interactions of hydrophobic organic [18] Hashimoto Y. Dieldrin residue in the soil and cucumber from agricultural field
compound within the Palakkad soil organic matter. Even though in Tokyo. J Pestic Sci 2005;30:397e402.
[19] Miglioranza KSB, Aizpún de Moreno JE, Moreno VJ. Dynamics of organo-
several OCIs like aldrin, lindane, and DDT were banned in various chlorine pesticides in soils from a southeastern region of Argentina. Environ
countries including India, its metabolites were still detected in Toxicol Chem 2003;22:712e7.
trace amounts in the sampled area of the present investigation as [20] Acton QA. Issues in Environmental Law, Policy and Planning: 2011 Edition.
Atlanta, GA: Scholarly Editions; 2012.
well as studies conducted elsewhere. Henceforth it can have a [21] Singh KP, Malik A, Sinha S. Persistent organochlorine pesticide residues in soil
major threat to the public health when the area is completely uti- and surface water of northern Indo-Gangetic alluvial plains. Environ Monit
lized for grazing purposes or recharging the groundwater bodies Assess 2007;125:147e55.
[22] Qiu XH, Zhu T, Yao B, Hu JX, Hu SW. Contribution of dicofol to the current DDT
beneath the bottom. There is utmost need to have more awareness
pollution in China. Environ Sci Technol 2005;39:4385e90.
as well as stricter and stringent monitoring program for the illegal [23] Kumar B, Mishra M, Verma VK, Kumar S, Sharma CS. Distribution of dichlor-
use of synthetic organic insecticides for agriculture deeds for the odiphenyltrichloroethane and hexachlorocyclohexane in urban soils and risk
assessment. J Xenobiotics 2013;3:1e8.
prevention of health issues and promoting the health of individuals
[24] Bossi R, Larsen B, Premazzi G. Polychlorinated biphenyl congeners and other
for the development of economics. The necessity of biodegradable chlorinated hydrocarbons in bottom sediment cores of Lake Garda (Italy). Sci
insecticides and practising eco-friendly, adaptable farming Total Environ 1992;121:77e93.
methods are required to check the frequent use of synthetic in- [25] Akhil PS, Sujatha CH. Prevalence of organochlorine pesticide residues in ground-
waters of Kasargod District, India. Toxicol Environ Chem 2012;94:1718e25.
secticides and mitigate the damage in and around Palakkad [26] Leena S, Choudhary SK, Singh PK. Pesticide concentration in water and sedi-
ecosystem, India. ment of River Ganga at selected sites in middle Ganga plain. Int J Environ Sci
2012;3:260e74.
[27] Sankararamakrishnan N, Sharma AK, Sanghi R. Organochlorine and organo-
Acknowledgements phosphorous pesticide residues in ground water and surface waters of Kan-
pur, Uttar Pradesh, India. Environ Int 2005;31:113e20.
This work was financially supported by the Kerala State Council [28] Kumar B, Gaur R, Goel G, Mishra M, Singh SK, Prakash D, et al. Residues of
persistent organochlorine pesticides in soils from variable cropping pattern
for Science, Technology & Environment, Grant No: 013/E&E/12/ agriculture areas. Organohalogen Compd 2011;73:1851e4.
CSTE dated 15/02/2017, Government of Kerala (Order No. 404/2013/ [29] Mishra K, Sharma RC, Kumar S. Contamination levels and spatial distribution
KSCTE). The authors also acknowledge the Head, Department of of organochlorine pesticides in soils from India. Ecotox Environ Safe 2012;76:
215e25.
Chemical Oceanography, School of Marine Sciences, Cochin Uni-
[30] Kumari B, Madan VK, Kathpal TS. Status of insecticide contamination of soil
versity of Science and Technology for providing laboratory facilities. and water in Haryana, India. Environ Monit Assess 2008;136:239e44.
We would like to express heartfelt gratitude for the sensible and 
[31] Skrbi 
c BD, Marinkovi c V, Antic I, Gegi
c AP. Seasonal variation and health risk
assessment of organochlorine compounds in urban soils of Novi Sad, Serbia.
fruitful criticism from the colleagues, of the same department
Chemosphere 2017;181:101e10.
mentioned above, during the course of research work.
N.K. Gopalan, S. Chenicherry / Sustainable Environment Research 28 (2018) 179e185 185

[32] Ahmad R, Kookana RS, Alston AM, Skjemstad JO. The nature of soil organic matter [37] Piccolo A, Conte P, Scheunert I, Paci M. Atrazine interactions with soil
affects sorption of pesticides. 1. Relationships with carbon chemistry as deter- humic substances of different molecular structure. J Environ Qual 1998;27:
mined by 13C CPMAS NMR spectroscopy. Environ Sci Technol 2001;35:878e84. 1324e33.
[33] Schnitzer M, Khan SU. Humic Substances in the Environment. New York: [38] Dunigan EP, McIntosh TH. Atrazine-soil organic matter interactions. Weed Sci
Marcel Dekker; 1972. 1971;19:279e82.
[34] Prashob PKJ. Modulation of Hydrophobic Partitioning Affinity of Humic Acid [39] Chaplin AV, Efimov BA, Smeianov VV, Kafarskaia LI, Pikina AP, Shkoporov AN.
from Mudbank Sediments and its Potential Applications [Ph.D. Dissertation]. Intraspecies genomic diversity and long-term persistence of Bifidobacterium
Kochi (India): Cochin Univ Sci Technol; 2014. longum. PLoS One 2015;10:e0135658.
[35] Chin YP, Aiken GR, Danielsen KM. Binding of pyrene to aquatic and com- [40] Prashob PKJ, Nair SM. Genesis of structural features of humic acids from the
mercial humic substances: the role of molecular weight and aromaticity. sediments of a high productive coastal zone. Geochem J 2014;48:247e58.
Environ Sci Technol 1997;31:1630e5. [41] Peter KP, Manu N, Chacko J, Nair SM. Synthesis of silver nanoparticles and of
[36] Barriuso E, Koskinen WC. Incorporating nonextractable atrazine residues into self assembled supramolecules from marine humic acid. J Exp Nanosci
soil size fractions as a function of time. Soil Sci Soc Am J 1996;60:150e7. 2014;9:719e27.

You might also like