Chemosphere 267 (2021) 129251

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Pesticides contamination in the Thamirabarani, a perennial river in

peninsular India: The first report on ecotoxicological and human
health risk assessment
Ulaganathan Arisekar a, *, Robinson Jeya Shakila a, **, Rajendran Shalini a,
Geevaretnam Jeyasekaran b
a
Department of Fish Quality Assurance and Management, Fisheries College and Research Institute, Tamil Nadu Fisheries University, Tuticorin, 628 008,
Tamil Nadu, India
b
Tamil Nadu Fisheries University, Nagapattinam, 611002, Tamil Nadu, India

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Pesticide residues in fish were found

below the maximum residual limits
(MRLs).

Pesticides found in sediments were
below the threshold effect level
(TEL).

Endosulfan, aldrin, and endrin were
the predominant OCPs found in the
Thamirabarani River.

Ingestion exposure routes showed a
higher risk than dermal absorption
and inhalation.

Children are more susceptible to
pesticide exposure than adults.

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

This study evaluates the distribution of pesticides and assesses the ecological and human health risks
Article history: associated with pesticide residues concentration in the Thamirabarani River, the only perennial river in
Received 4 October 2020
Tamil Nadu, India. Observed a variation in the pesticide concentration in the water (not detected (ND)-
Received in revised form
31.69 mg/L), sediments (ND-14.77 mg/kg), and fish (0.02e26.05 mg/kg). Endosulfan, aldrin, and endrin
30 November 2020
Accepted 7 December 2020 were the predominant organochlorine pesticides present in water, sediments, and fish. The average
Available online 13 December 2020 concentration of pesticides (except endosulfan) in water and sediments was found to be below the
acceptable threshold as per the water and sediment quality guidelines, posing no ecological hazard to
Handling Editor: A. Gies aquatic organisms. The calculated risk quotient and toxic unit (0.1 > TU/RQ  1) represent low-to-
medium acute and chronic toxicity to the aquatic organisms inhabiting the river basin. The average
concentration of pesticides in fish (Labeo rohita) was also below the maximum residual limits set by the
Keywords: Codex Alimentarius Commission (CAC). However, the calculated daily intakes of endosulfan, aldrin, and
Pesticide residues
endrin were above the CAC-acceptable daily intake guidelines. The human health risk assessment
Bioaccumulation
Risk quotient
showed that children and adults exposed to pesticides in water and sediments through ingestion and
Toxic unit dermal contact could have higher cancer risks (CR > 104) than inhalation. This study recommends

* Corresponding author. Department of Fish Quality Assurance and Management,

Fisheries College and Research Institute, Tamil Nadu Fisheries University, Tuticorin,
628 008, Tamil Nadu, India.
** Corresponding author.
E-mail addresses: [email protected] (U. Arisekar), jeyashakila@gmail.
com (R. Jeya Shakila).

https://doi.org/10.1016/j.chemosphere.2020.129251
0045-6535/© 2020 Elsevier Ltd. All rights reserved.
U. Arisekar, R. Jeya Shakila, R. Shalini et al. Chemosphere 267 (2021) 129251

Fish implementing effective and routine pollution management schemes to avoid pesticide threats to aquatic
Carcinogenic exposure and human health.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction farms and residential houses. It also serves as the essential aquatic
resource and recreational site for the surrounding communities.
The use of organochlorine pesticides (OCPs) is not a significant Thus, the river becomes a suitable site for exploring the occurrence,
problem in developed countries due to the proper monitoring of residual levels, and potential risks of pesticides. There are some
regulatory bodies. However, the indiscriminate use of banned studies on the level of pesticide residues in the Thamirabarani river
pesticides has shown that OCPs in food commodities constitute a system (Kumarasamy et al., 2012; Arisekar et al., 2018, 2019).
significant concern in developing countries, including India (Singh, However, there is a lack of research on the bioaccumulation
2001; Srimurali et al., 2015). Most of the OCPs are of worldwide potential, ecological risk, and human health risks posed by
concern as they are ecologically persistent, potentially poisonous, pesticide-contaminated fish, water, and sediments in the Thamir-
and bio-accumulative potential (Wang et al., 2015). The pesticides abaraniriver. Hence, this study was undertaken with the following
find entry into the freshwater system through agricultural runoff, objectives: (i) to assess the levels of pesticide contaminants in
wastewater discharge, and rural spillovers. The increased concen- water, sediment, and fish in the Thamirabarani River; (ii) to
tration of pesticide residues in water and sediments has impaired determine the bioaccumulation factor (BAF) and biota-sediment
the aquatic ecosystems and caused a considerable loss of biodi- accumulation (BSAF) potential of pesticides in the aquatic organ-
versity (Ginebreda et al., 2014). Fish are considered a bioindicator ism; (iii) to assess the ecological risk of pesticides on non-target
for evaluating freshwater and marine pollution, as they intake organisms using ecological risk quotient (RQ) and toxic units
pesticides directly from the aquatic environment and through the (TUs); and (iv) to estimate the carcinogenic and non-carcinogenic
diet (Lana et al., 2010). Therefore, the study of pesticide residues in human health risks from pesticide-contaminated water, sedi-
fish, water, and sediments is vital for human wellbeing (Munaretto ment, and fish.
et al., 2013), as the consumption of pesticide-contaminated fish
poses serious health risks (Dang et al., 2016). Humans expose
themselves to pesticides through ingestion, inhalation, and dermal 2. Materials and methods
contact. Pesticides are linked to short-term and long-term health
effects such as leukemia, non-Hodgkin’s lymphoma, brain, bone, 2.1. Study area
breast, ovarian, prostate, testicular, and liver cancers, reproduction,
gastrointestinal, neurological, congenital disabilities, immune sys- The investigation zone selected for this study was the Thamir-
tem dysfunction, respiratory, and endocrine disruption (WHO, abarani waterway located in the Western Ghats of South India,
1990; Dang et al., 2016). which flows at 8 300 and 9150 N latitude and 77100 and 78 100 E
Ecological risk assessment (ERA) is necessary to evaluate the longitude (Fig. 1). It starts from the Pothigai Hills, flows through
adverse environmental effects of pesticides on non-target organ- Thoothukudi and Tirunelveli districts, and drains into the Bay of
isms, which deserve greater consideration. The route of exposure Bengal in the Gulf of Mannar. The river has rich fish biodiversity and
includes dietary and non-dietary sources (Ogbeide et al., 2016). diverse biota. It navigates a distance of 125 km and has a catchment
Dietary exposure involves consumption of foods and drinking wa- area of approximately 5896 km2, watering around 1.17 lakh ha area
ter contaminated with pesticides (Tsakiris et al., 2011), whereas of crops. About 20.70 million liters of water are drawn for resi-
non-dietary exposure includes dermal contact with polluted sedi- dential use from this river by the Municipal Corporation, and about
ments and water, inhalation of residues in sediments, and unin- 1480 kg L/day (KLD) of sewage is discharged into the river (TNPCB,
tentional ingestion of contaminated sediments (Yang et al., 2005; 2011).
Huang et al., 2013; Zhou et al., 2006; Qu et al., 2015). A joint report
published by the WHO and UNEP states that around the world,
2.2. Sample collection
about 0.2 million individuals die, and 3 million people are affected
every year by pesticides. Among them, almost 95% of the cases are
Four main areas of interest around the Thamirabarani river ba-
reported from developing countries (WHO/UNEP, 1989 FAO/WHO,
sin were identified, viz., Manimuthar (site 1), Tirunelveli (site 2),
1997).
Srivaikuntam (site 3), and Authoor (site 4) (Fig. 1). The sample were
In India, only limited information is available on the presence of
collected during March to July (summer season). The water samples
organochlorine pesticide (OCPs) residues in the sediment, fish, and
(five composite samples per site) were collected in MeOH pre-
water systems and assessing the health risk posed by them (Ali
rinsed amber bottles, and the sediment samples (five composite
et al., 2014; Sharma et al., 2014). In Tamil Nadu, a southern State
samples per site) were collected using a stainless-steel Peterson
of India, reports on pesticides in the aquatic ecosystem and human
grab sampler (0e3 cm). Rohu (Labeo rohita) fish were selected for
health risk assessment (HRA) are very few. The State has a culti-
the study as it has high productivity and bioaccumulation potential
vable area of 1.3 lakh km2. About 4.97 lakh metric tons (MT) of
and is the most preferred one by the local fish consumers. Fish
pesticides and 16.03 lakh MT of agrochemicals are used annually in
samples, each weighing 800 ± 40 g, were obtained from the local
the State. The use of pesticides and agrochemicals in the Thami-
fishermen and packed in zipped polyethylene bags. Each water,
barani river basin was reported as 10,178 MT and 57, 596 MT,
sediment, and fish sample was a composite of five subsamples
respectively, during 2016e17 (State Department of Agriculture,
collected from about a 1 km radius of the sampling site to reduce
Chennai, 2017). Thamirabarani River, a perennial of Tamil Nadu,
variation. All the samples were immediately transported to the
irrigates several agrofarms situated along its entire stretch of
laboratory under the chilled condition and stored at 20  C until
120 km. Water from this river is also drawn off for horticultural
analysis (within 48 h of the collection).
2
U. Arisekar, R. Jeya Shakila, R. Shalini et al. Chemosphere 267 (2021) 129251

Fig. 1. Location of the area of study in Thamirabarani river (Tamil Nadu, South India).

2.3. Extraction of pesticides from water, sediments, and fish The mean recovery percentage indicates a good correlation
between spiked and obtained concentrations. The mean recovery
A mixture of a standard solution containing seven OCPs such as percentage ranged from 79.65 ± 9.71 (DDT) to 94.13 ± 13.23%
benzene hexachloride (a-BHC), heptachlor, aldrin, endrin, endo- (methoxychlor). The mean linearity (r2) ranged from 0.981 ± 0.008
sulfan (I), dichloro-diphenyl-trichloroethane (p,p’-DDT), methoxy- to 0.998 ± 0.000 (Table S1). According to the EU guidelines (EC/
chlor (cat. No. M-8270-14-ASL) and one pyrethroid pesticide, SANTE/11813/2017; EC, 2017), the recovery (%) of the compounds
cypermethrin (a) (cat. No. Pe225 N) was obtained from AccuS- must be within the range of 80%e120% (except DDT), with standard
tandard (USA). The pesticides analyzed in this study were banned deviation (SD) < 20%. The limit of detection (LOD) is the lowest
for agricultural use in India under the Indian Insecticides Act (1968) point of the six-point standard calibration curve (1, 5, 10, 50, 100,
and are listed under “Dirty Dozen” persistent organic pollutants and 250 ppb) (Shrivastava and Gupta, 2011). The limit of quantifi-
(POPs) (except cypermethrin) defined by Stockholm Convention. cation (LOQ) was assessed by doubling the LOD value (AOAC, 2015).
Extraction of pesticide residues from water (1 L) was done by The detection limits of all the analytes ranged from 1.05 to 2.60 ppb.
standard liquid-liquid partition method (525.2; EPA, 1995). Sedi- For every ten samples, a procedural blank, a spike blank, and
ment and fish (5 g) were extracted as per the AOAC 2007.01 method triplicate samples were performed to assure precision and accuracy
using a QuEChERS kit (AOAC, 2007; Lehotay, 2007). The extracted of method and instrument. The results were obtained after sub-
pesticides were analyzed by a gas chromatography-mass spec- traction of procedural blank value from the analyte value.
trometry system (Trace 1300 and ISQ LT Single Quadrupole Mass
Spectrometer; Thermo Fisher, Waltham, MA) fitted with a TG-5MS
2.5. Ecological risk assessment (ERA)
column (30 m  0.25 mm  0.25 mm). The QuEChERS kit compo-
sition, reagents, detailed extraction procedure (stepwise), and in-
The ecological RQ was assessed to determine the potential
struments conditions followed have been described in a previous
hazard caused due to the presence of pesticides in the aquatic
study (Arisekar et al., 2019). Pesticide compounds were detected
environment. The potential ecological risks do not depend only on
using four selected fragment ions of each compound by selecting
the concentration of a pesticide in an environment but also on its
the ion-monitoring mode (SIM). The target ions for the identifica-
toxicity (Kouzayha et al., 2013). The RQ method, defined as the
tion of the pesticides and their retention times are given in Table S1
proportion of the measured environmental concentration (MEC) of
(supplementary materials). Six standard concentrations (1, 5, 10,
a particular pesticide to the predicted no-observed-adverse-effect
50, 100, and 250 ppb) were drawn for the calibration curve to
concentration (NOAEC) on a non-target organism, was used to
quantify the pesticides.
calculate the potential hazard (Zheng et al., 2016).

2.4. Quality assurance and quality control check MEC

RQ ¼ (1)
NOAEC
To find out the accuracy of the method, samples were spiked
with four different concentrations of pesticides (5, 10, 50, and The NOAEC values were obtained from the USEPA, IRIS database
100 ppb). The linearity (r2) and the recovery percentage were (USEPA, 1989) (Table S2). According to the literature, RQ  1 in-
calculated (EC, 2017) and given in Table S1. dicates high risk, 0.1 ¼ RQ < 1 suggests medium risk, and
0.01 ¼ RQ < 0.1 expresses a low risk to aquatic organisms (Palma
Calculated amount et al., 2014; Zheng et al., 2016).
Recoveryð%Þ ¼  100 The cumulative RQ values were applied to categorize the sam-
Spiking concentration
pling sites based on the sum of individual ERQ of each pesticide at a
3
U. Arisekar, R. Jeya Shakila, R. Shalini et al. Chemosphere 267 (2021) 129251

specific sampling point, according to the given equation. regular exposure to pesticides in water (Yang et al., 2014). The
selected sites of the river are situated within the urban area that
X
n
draws numerous local people, especially children and youngsters,
RQs ¼ ðRQ 1 þ RQ 2 þ RQ 3 þ … þ RQnÞ (2)
who gather for laundry and recreational purposes. Besides, water
i¼n
from this river is continually supplied for households, industries,
where RQs is the sum of RQ of each pesticide. The RQ > 1 suggests corporations, and farms, increasing the need to evaluate the risk to
high acute risk, and RQ < 1 represents a low acute risk to the aquatic human health.
organism. Exposure of children and adult through various routes (inges-
tion, contact, and dermal contact) was examined to assess the po-
tential risk of exposure to water contaminated with pesticide, as
2.6. Toxic unit (TU)
estimated by the chronic daily intake (CDI) formula given below
(He et al., 2012; Baqar et al., 2018):
The TU was calculated to estimate the risk of pesticide residues
in the water on aquatic organisms (Ccanccapa et al., 2016). The TU Cw  IRw  EF  ED
of each pesticide in the water sample was estimated based on acute CDIðingestionÞ ¼ (7)
Bw  AT
toxicity values (LC50) (Papadakis et al., 2015). The TU is expressed as
the ratio of pollutant concentration in water (Cw) to its acute  
TB 0:5
toxicity value LC50, as given in the below equation: CDIðbathingÞ ¼ 6t þ
p
 
Cw Cw  K  DAF  EF  ED  BF
TU ¼ (3)  (8)
LC50 BW  AT  500  f

where Cw is the measured concentration (mg/l) of a pesticide in Abbreviations and details of the parameters are given in
water samples, and LC50 is the effective concentration of 50% of the Table S3.
individual organism (Table S2). According to the literature, TU  1
indicates high risk, 0.1 ¼ TU < 1 represents a medium risk, and 2.8.2. Calculation of CDI from sediments
0.01 ¼ TU < 0.1 expresses low risk to aquatic organisms (Palma All three exposure routes (ingestion, inhalation, and dermal
et al., 2014; Zheng et al., 2016). contact) were considered for risk estimation. Human exposure to
The cumulative TU was used to categorize the sampling sites pesticide-contaminated sediments was predominantly caused by
based on the total of TUs of each compound at a particular ingestion, inhalation, and dermal contact. Equations (9)e(11) were
inspecting point, as per the below equation. used to estimate the CDI for sediments (Ogbeide et al., 2019; Baqar
et al., 2018). The details of the parameters are given in Table S3.
X
n
TUs ¼ ðTU1 þ TU2 þ TU3 þ … þ TUnÞ (4)
Cs  IRs  EF  ED  CF
i¼n CDIðingestionÞ ¼ (9)
Bw  AT
where TUs is the sum of the toxic units. The TUs> 1 suggests a high  
risk and TUs <1 indicates a low risk to the aquatic organisms. Cs  InhR  1  EF  ED
PEF
CDIðinhalationÞ ¼ (10)
2.7. Calculations of BAF and BSAF Bw  AT

Bioaccumulation is the action by which organisms take in con- Cs  SA  CF  ED  EF  DAF  DSF

CDIðdermalÞ ¼ (11)
taminants from the environment or diet. The BAF is used to Bw  AT
investigate an aquatic organism’s capability to uptake the pollut-
ants present in water. The BSAF is used to define the enrichment of
contaminants from sediments. The BAF and BSAF were calculated
2.8.3. Carcinogenic and non-carcinogenic risk assessment
using the following equations (van der Oost et al., 2003):
Carcinogenic (CR) and non-carcinogenic risks (NCR) of pesti-
Cf cides for adults and children were calculated (USEPA-IRIS; USEPA,
BAF ¼ (5) 2017). The hazard quotient (HQ) was used to calculate the NCR
Cw
for humans by direct ingestion of surface water used as drinking
water and fish used as food (Shi et al., 2011). Other routes of
Cf
BSAF ¼ (6) exposure, such as dermal contact and inhalation with surface water
Cs and sediment during the shower, were also considered.
where Cf is the concentration of a pollutant in fish, Cw is the con- CDI
centration of pollutants in water, and Cs is the concentration of HQ ¼ (12)
RfD
pollutants in sediments. If BAF and BSAF are >1, they indicate the
hyperaccumulator potential of the contaminants from the aquatic where chronic daily intake (CDI) is the estimated quantity of
environment. ingested pesticide per kilogram body weight, and RfD is the pre-
scribed amount of the contaminant (mg/kg/day) by oral exposure
2.8. Human health risk assessment (HRA) through the water and (Table S2). The HQ < 1 indicates no possibility of an adverse health
sediments effect, and HQ > 1 suggests the possibility of an adverse health
effect.
2.8.1. Calculation of chronic daily intake (CDI)from water To assess potential effects exerted by more than one pesticide,
Human exposure to pesticides can occur through either the the calculated HQs for each pesticide were summed up and
intake of contaminated water/bathing/recreational activities or expressed as a hazard index (HI) (USEPA, 1996):
4
U. Arisekar, R. Jeya Shakila, R. Shalini et al. Chemosphere 267 (2021) 129251

in pesticide concentrations in water, sediments, and fish species

n 
X used the one-way analysis of variance (SPSS, version 25.0).
HI ¼ HQ 1 þ HQ 2 þ HQ 3 þ … þ HQn (13)
i¼n

where HI < 1 indicates no chronic health effect and HQ > 1 suggests 3. Results and discussion
an adverse health effect.
Carcinogenic risk (CR) was calculated as per the equation given 3.1. Ecotoxicological risk assessment (ERA)
below (USEPA, 2000; Kim et al., 2013):
Determining the acute toxic risk posed to the aquatic environ-
CR ¼ CDI  CSF  ADAF (14) ment by pesticides through water is a challenging task. Pesticides
with different modes of action are expected to show individual or
where CSF is the cancer slope factor (mg/kg/day) (Table S2), which cumulative synergistic and antagonistic effects on aquatic organ-
reflects the probability of the individual substance to cause cancer isms (Carazo-Rojas et al., 2018). RQ (risk quotient), RQS (sum of the
through the oral path, and ADAF is the age adjustment factor (3 for risk quotient at a particular site), TU (toxic unit), and TUS (sum of
children and 1 for adults). ADAF values are default adjustments to the toxic unit at a particular site) are used for ERA, ranking each
the cancer slope factor that considers the increased vulnerability to pesticide based on its toxicity to the aquatic organisms and ranking
cancer from an early-stage exposure. For hazard management, the sampling sites based on the pollution level. However, to the best of
CR values for cancer risk (CR) range from 106 to 104 (USEPA, 1996, our knowledge, no study has used RQ, RQs, TU, and TUS approaches
2011). for ERA in the lakes and rivers of Tamil Nadu.
The ERA of the eight most commonly noticed pesticides is
2.9. Human health risk assessment (HRA) through fish consumption presented in Table S4. The RQ and TU values of the pesticides were
less than 1 (<0.1) at all the sites. The RQ value of individual and
2.9.1. Estimated daily intake (EDI) mixture of pesticides (RQS) ranged from NERO (no ecological risk
To evaluate the potential health hazards posed by the con- observed/detected) to 0.10 and from 0.10 to 0.16, respectively,
sumption of pesticide-tainted fish, the estimated daily intake (EDI) which indicates the no-ecological-risk to low-ecological-risk effect
was determined (WHO/FAO, 1987). on the aquatic organisms. The RQ and RQS values were found in the
order of methoxychlor < heptachlor < cypermethrin < BHC
Cf  FCR
EDI ¼ (15) < DDT < aldrin < endrin < endosulfan. The RQ and RQS values of
Bw
pesticides are below the acute toxicity risk to the aquatic organisms
where Cf is the average concentration of pesticides in fish, FCR is the (<1) when the pesticide concentration present in water and the
estimated daily fish consumption rate (g d1), and Bw is the average toxicity to the aquatic invertebrates are less (Papadakis et al., 2015).
body weight (kg) set at 60 kg for adults and 20 kg for children Conversely, many researchers reported higher RQ and RQS values in
(WHO, 2012). Lake Pamvotis in Greece (Hela et al., 2005), Alqueva reservoir in
To evaluate the risk of consuming contaminated freshwater Portugal (Palma et al., 2014), Lake Amvrakia in Western Greece
fishes, a questionnaire-based pre-sampling survey was conducted (Thomatou et al., 2013), La Mula Creek in Costa Rica (Carazo-Rojas
by randomly selecting and surveying 300 families consisting of 750 et al., 2018), Ikpoba River in Nigeria (Ogebeida et al., 2019), and
individuals from the general population. All the participants were Hooghly and Brahmaputra Rivers in India (Chakraborty et al., 2016),
local residents and living for a minimum period of 20 years in one which were much higher than those found in the Thamirabarani
place. Direct face-to-face interviews collected dietary data. The data river system. In this study, none of the pesticides (individual and
collected included frequency of fish consumption per day/week/ mixture) showed any ecological impact on aquatic organisms’
month and the type of preferred fish. The fish consumption rate habitat in this river.
was calculated based on the daily consumption of fish divided by Toxic unit and the sum of the toxic level at the sites (TUS) were
the individual’s body weight. The average fish consumption of used to evaluate the individual and the cumulative potential
adults was estimated as 18 g/day and of children as 10.0 g/day. For harmful effects of pesticides on the aquatic organisms. The TU value
risk assessment, bodyweight was taken as 70 kg for adults and of each pesticide was aggregated to estimate the sum of TUS. These
20 kg for children, based on the standard protocol (USEPA, 2017; indices are useful for assessing the toxic effect of the individual and
Jiang et al., 2005). total pesticides at different sampling sites along the river. The
poisonous effect of the individual (TU) and a mixture of pesticides
2.9.2. Hazard quotient (HQ) (TUS) ranged from NTRO (no toxic risk observed/detected) to 0.01
The HQ approach was used to assess the hazard to people on (Table S4). The potential toxic risk of the individual and total sum of
exposure to pollutants through a single pathway. The HQ is char- pesticide was found in the order of methoxychlor < cypermethrin
acterized as the proportion between the EDI and the acceptable < DDT < BHC < heptachlor < aldrin < endrin < endosulfan. The
daily intake (ADI) levels or the reference dose (RfD) of the indi- observed TU and TUS values for water were <0.1, indicating no
vidual pollutant. The HQ assessment of each pollutant was done acute toxicity to the aquatic organisms associated with the
based on the following equation (USEPA, 1989; Buah-Kwofie et al., contamination of pesticides in water. Similarly, no significant toxic
2018; Varol and Sunbul, 2019): ecological effect was reported by Ccanccapa et al. (2016) in Ebro
River (Spain) and Ogbeide et al. (2019) in the Ikpoba River (Nigeria).
EDI EDI Contrarily, Carazo-Rojas et al. (2018) reported an ecotoxicological
HQ ¼ ðorÞHQ ¼ (16)
ADI RfD effect (TU > 1) in the water samples collected from La MulaCreek,
Costa Rica, which was 2 to 10-fold higher than that observed in the
whereEDI is the estimated daily intake (mg/kg/day), ADI is the ADI Thamirabarani river. Based on the ecological RQs and toxicological
level (mg/kg/day) (Table 2), and RfD is the recommended daily (TUs) risk assessment, it was found that the Thamirabarani River is
intake (mg/kg/day). The HQ < 1 indicates no adverse health effects, not polluted with pesticides and is suitable for aquatic organisms
and HQ > 1 suggests possible adverse health effects. The differences and the cultivation of crops.

5
U. Arisekar, R. Jeya Shakila, R. Shalini et al. Chemosphere 267 (2021) 129251

3.2. BAF and BSAF potential of fish samples in the selected study area is given in Table 1. The one-way
ANOVA Kruskal Wallis independent shows the significant differ-
Pesticide residues found in L. rohita were close to the concen- ence in the pesticide residues in water, sediment, and fish shown in
trations found in the water and sediments of the Thamirabaranir- Table 3 and Fig. 5. The pesticide concentration in the water samples
iver, which were similar to the previous studies reported in this was ranged from not detected (ND) to 31.69 mg/L. The minimum
river (Arisekar et al., 2019; Kumarasamy et al., 2012). The BAF and concentration was recorded for methoxychlor at site 3 and the
BSAF values ranged from ND to 83 and 1 to 850, which was 80- to maximum for endosulfan at site 1. The pesticide residues were
800-fold higher than those observed for sediments and water present in the order of methoxychlor < heptachlor
(Table S5). The BAF and BSAF values of the pesticides were found in < BHC < cypermethrin < aldrin < DDT < endrin < endosulfan. Based
the order of endosulfan < DDT < endrin < cypermethrin on the World Health Organization (WHO, 2011) drinking water
< methoxychlor < heptachlor < aldrin < BHC, and endrin guidelines, the concentration of the pesticides was well within the
< endosulfan < aldrin < BHC < cypermthrin accepted threshold, except for endosulfan (site 1), aldrin (all sites),
< DDT < methoxychlor < heptachlor. The result indicated that and heptachlor (sites 1, 2, and 3) (Table 1). Based on the USEPA
L. rohita bioaccumulated a higher amount of pesticides from the ambient water quality guidelines, most of the pesticides’ concen-
water than sediments. During the fry stage, rohu is predominantly a tration was below the toxic/threshold effect level (TEL) for fresh-
planktivorous surface feeder. From the fingerling stage onward, the water aquatic organisms, except endosulfan and endrin (Table 1).
feeding habit changes, and the fish feed in the water column, The sum of pesticide residues followed an ascending trend from the
mainly on filamentous algae, and decomposed vegetation, sug- upstream to the downstream region of the river, i.e., site 1> site 2
gesting that the species is also capable of filter-feeding (Chondar, >site 3 > site 4. Earlier reports also stated a higher concentration of
1999), which could be the reason behind the high BAF and low pesticide residues in the upstream waters than the downstream
BSAF values. Feeding behavior and habitat play an important role in waters of the Thamirabarani River (Arisekar et al., 2019;
accumulating organic contaminants from the environment to the Kumarasamy et al., 2012)) and Uruguay River Basin, Argentina
aquatic organisms. Supporting this statement, Buah-Kwofie et al. (Williman et al., 2017).
(2018) and Yohannes et al. (2013, 2014) reported a higher BSAF Our study results indicate that indiscriminate use of pesticides
potential in the bottom feeder (Clarias gariepinus) than surface in the upstream region (sites 1 and 2) due to the cultivation of cash
feeder (tilapia) of iSimangaliso wetlands of South Africa and Rift crops such as tea, cashew, cotton, paddy, and rubber has resulted in
Valley Lakes of Ethiopia. their high concentration. Endosulfan contributes approximately
In the BAF calculation, methoxychlor, heptachlor, and BHC 94% of the total pesticide residues. Water accumulated more
values were higher than the other five pesticides. Similarly, Cui endosulfan compared to sediment samples. Williman et al. (2017)
et al. (2015) have also reported a higher BAF value for heptachlor recorded high concentrations of endosulfan (344 mg/L) and chlor-
and methoxychlor in silver and bighead carps collected from East pyrifos (133 mg/L) in the water samples compared to the sediment
Lake of China. Pesticide concentrations in fish tissues varied with samples (109 mg/kg and 15 mg/kg) collected from Uruguay River,
each site, reflecting the difference in the site-wise pesticide Argentina. The water solubility and Kow (octanol-water partition
contamination (Buah-Kwofie et al., 2018). The BAF potential of coefficient) of each pesticide are the determinant factors that in-
L. rohita not only reflects the availability of pesticides for its bio- fluence the accumulation of pesticides in water and sediments
logical uptake in the study area but also indicates potential con- (Carazo-Rojas et al., 2018). The utilization rate of endosulfan in
centration to which humans may become exposed upon India was 12 million liters in 2007 (Guide, 2011). The presence of
consumption. residues of BHC, DDT, heptachlor, and endosulfan in the surface
water of the Thamirabarani River was much lower than that in the
Rivers Brahmaputra and Hooghly (Chakraborty et al., 2016), upper
3.3. Pesticide residues in water stretches of Ganga river (Singh et al., 2007), Gomti river in Uttar
Pradesh (Malik et al., 2007), Yamuna river in Delhi (Kaushik et al.,
The mean concentration of pesticide residues in the water

Table 1
Pesticides residues in water, sediments and fish collected from the Thamirabarani river basin.

Samples Site BHC Heptachlor Endosulfan DDT Aldrin Endrin Methoxychlor Cypermethrin

Water (mg/l) 1 0.083 ± 0.03 0.095 ± 0.02 31.690 ± 3.40 0.075 ± 0.05 1.385 ± 0.47 0.148 ± 0.07 0.091 ± 0.05 0.043 ± 0.02
2 0.107 ± 0.04 0.088 ± 0.08 9.235 ± 1.02 0.099 ± 0.08 0.081 ± 0.02 0.266 ± 0.18 0.008 ± 0.01 0.033 ± 0.01
3 0.002 ± 0.003 0.036 ± 0.01 6.276 ± 1.39 0.351 ± 0.31 0.044 ± 0.03 0.260 ± 0.15 0.002 ± 0.003 0.027 ± 0.01
4 0.004 ± 0.003 0.002 ± 0.003 1.776 ± 0.36 0.120 ± 0.02 0.098 ± 0.01 0.246 ± 0.07 0.023 ± 0.02 0.077 ± 0.02
WHO-MRL (mg/L)a 2 0.03 20 1 0.03 0.6 20 0.1
USEPA-WQG (mg/L)b 2 0.5 0.2 1 0.3 0.19 0.03 e
Sediments (mg/kg) 1 0.594 ± 0.10 0.117 ± 0.02 14.773 ± 2.65 0.186 ± 0.21 0.270 ± 0.13 0.295 ± 0.19 0.500 ± 0.25 0.059 ± 0.01
2 0.174 ± 0.04 0.047 ± 0.02 13.373 ± 1.48 0.034 ± 0.02 0.336 ± 0.13 0.568 ± 0.31 0.036 ± 0.01 0.058 ± 0.006
3 0.259 ± 0.06 0.001 ± 0.001 10.261 ± 1.31 0.079 ± 0.03 0.520 ± 0.23 2.242 ± 0.42 0.018 ± 0.007 0.411 ± 0.18
4 0.177 ± 0.02 0.000 ± 0.001 7.958 ± 1.24 0.347 ± 0.08 0.528 ± 0.08 2.190 ± 0.26 0.019 ± 0.009 0.498 ± 0.11
SQG-TEL (mg/kg)c 0.94 2.26 e 1.19 2 e e e
Fish (mg/kg) 1 0.485 ± 0.07 0.025 ± 0.10 26.055 ± 1.27 0.143 ± 0.05 0.406 ± 0.49 0.441 ± 0.34 0.356 ± 0.10 0.163 ± 0.04
2 0.329 ± 0.06 0.023 ± 0.005 21.509 ± 1.26 0.681 ± 0.18 0.616 ± 0.07 1.822 ± 0.18 0.778 ± 0.87 0.908 ± 0.68
3 1.986 ± 0.25 0.056 ± 0.01 23.347 ± 3.98 0.593 ± 0.34 0.646 ± 0.37 3.837 ± 2.82 0.273 ± 0.03 0.471 ± 0.07
4 0.436 ± 0.10 0.685 ± 0.08 17.951 ± 2.12 1.996 ± 0.17 1.922 ± 0.26 1.967 ± 0.80 0.175 ± 0.03 0.537 ± 0.15
CAC-MRL (mg/kg)d e 200 200 5000 200 100 e 2000
a
World Health Organization-Maximum residual limit for drinking water (WHO-MRL; WHO, 2011).
b
United States Environmental Protection Agency - Water Quality Guidelines for Freshwater Aquatic Organisms (USEPA, 1980a; 1980b; 1980c; 1980d, 1980e, 1980f, 1986).
c
Sediment Quality Guidelines (SQG)-Threshold Effect Level (TEL) for Bottom Dwelling Aquatic Organisms (Smith et al., 1997; Ogbeide et al., 2019).
d
Codex Alimentarius Commission- Maximum Residual Limits (CAC-MRL) for Meat and Meat Products (CAC, 2020).

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U. Arisekar, R. Jeya Shakila, R. Shalini et al. Chemosphere 267 (2021) 129251

Table 2
Estimated daily intake (EDI) and hazard quotient (HQ) of pesticides through consumption of contaminated fish (mg kg1).

Sites Site 1 Site 2 Site 3 Site 4 ADIa (mg/

kg)
Pesticides Children Adult Children Adult Children Adult Children Adult

BHC 0.24 0.12 0.16 0.08 0.99 0.51 0.21 0.11 e

Heptachlor 0.01 0.00 0.01 0.00 0.02 0.01 0.34 0.17 0.1
Endosulfan 13.02 6.70 10.75 5.53 11.67 6.00 8.97 4.61 6.0
DDT 0.07 0.03 0.34 0.17 0.29 0.15 0.99 0.51 10.0
Aldrin 0.20 0.10 0.31 0.16 0.32 0.16 0.96 0.49 0.1
Endrin 0.22 0.11 0.91 0.47 1.91 0.98 0.98 0.50 0.2
Methoxychlor 0.17 0.09 0.39 0.20 0.13 0.07 0.08 0.04 e
Cypermethrin 0.08 0.04 0.45 0.23 0.23 0.12 0.26 0.13 20
HQ
Pesticides Children Adult Children Adult Children Adult Children Adult
BHC NR NR NR NR NR NR NR NR
Heptachlor 0.12 0.06 0.12 0.06 0.28 0.14 3.42 1.76
Endosulfan 2.17 1.12 1.79 0.92 1.95 1.00 1.50 0.77
DDT 0.01 0.00 0.03 0.02 0.03 0.02 0.10 0.05
Aldrin 2.03 1.04 3.08 1.58 3.23 1.66 9.61 4.94
Endrin 1.10 0.57 4.56 2.34 9.59 4.93 4.92 2.53
Methoxychlor NR NR NR NR NR NR NR NR
Cypermethrin NR NR 0.02 0.01 0.01 0.01 0.01 0.01
a
NR-No hazard risk observed; Codex Alimentarius Commission (CAC) - Acceptable Daily Intake (ADI) Guidelines (CAC, 2020).

Table 3 water (Table S7). Compared to other sites, site 1 showed a con-
Principal Component (PC) analysis and Kruskal Wallis test for pesticides residues in centration above the ATV (HQ > 1), indicating the possible adverse
the Thamirabarani river.
NCR effects on health. The HQ value of aldrin exceeded ATV
Pesticides PC-1 PC-2 PC-3 (HQ > 1). This finding is similar to that reported by Papadakis et al.
BHC 0.477 0.521 0.407 (2015), who found pesticide residues in 6 lakes and 10 rivers in
Heptachlor 0.692 0.648 0.076 Greece. The cumulative NCR (HI) (sum of the HQ of each pesticide)
Endosulfan 0.506 0.171 0.704 suggested possible NCR health effects at site 1. The HI values in
DDT 0.854 0.358 0.260
children and adults ranged from 2.05E01 to 2.59 and from
Aldrin 0.779 0.437 0.237
Endrin 0.611 0.359 0.026
1.19E01 to 1.50, respectively. The highest and lowest NCR (HQ and
Methoxychlor 0.438 0.555 0.272 HI) were found at sites 1 and 3. This result indicated high pesticide
Cypermethrin 0.675 0.439 0.480 contamination in the upstream region (sites 1 and 2) compared to
Eigenvalues 3.319 1.669 1.095 the downstream region (sites 3 and 4). The HQ value of each
% Variance 41.498 20.872 13.699
pesticide in the sediments ranged from 1.90E12 to 2.20E07 in
Cumulative % of variance 41.498 62.370 76.069
Kruskal-Wallis independent test, p values (significance at p < 0.05) children and 5.44E13 to 6.28E08 in adults for the risk associated
Pesticides Water Sediment Fish with dermal contact while bathing. The individual (HQ) and cu-
BHC 0.033 0.053 0.041 mulative (HI) non-cancer risk from the pesticides were found to be
Heptachlor 0.066 0.021 0.025
below the ATV (HQ and HI < 1). Children were found to be more
Endosulfan 0.019 0.029 0.066
DDT 0.145 0.055 0.028
susceptible to pesticide risk compared to adults. Similar results
Aldrin 0.035 0.113 0.082 were reported in the previous studies conducted on contamination
Endrin 0.578 0.034 0.135 in Chongqing River, China (Hu et al., 2011); freshwater lakes in East
Methoxychlor 0.111 0.043 0.077 China (Shi et al., 2011); lakes and rivers in Northern Greece
Cypermethrin 0.147 0.040 0.081
(Papadakis et al., 2015); Ikpoba River in Nigeria (Ogbeide et al.,
2019); Illushi River in Nigeria (Ogbide et al., 2016); and River Ravi
in Pakistan (Baqar et al., 2018).
2008), and Ghaggar river in Haryana, India. The carcinogenic risk (CR) estimation for the CR listed pesticides
in Table S8 exceeds the ATV of 104 set by the USEPA (2011),
indicating potential carcinogenic effects of the drinking water on
3.4. Human health risk assessment from water
children and adults. However, none of the pesticides exceeded the
ATV for HQ, HI, and CR for dermal absorption through bathing. Our
The essential function of aquatic ecosystems is providing clean
finding is similar to that of Yang et al. (2014), who reported that
and safe water to diverse consumers (Ogbeide et al., 2019). There-
water quality in East Lake, China, was not suitable for consumption
fore, estimating the potential human health risk at a low concen-
and bathing. Also, Baqar et al. (2018) reported low HQ and HI values
tration of pesticide residue has become an essential aspect of the
but high CR values of each pesticide in River Ravi, Pakistan, sug-
HRA process. Human exposure to the pesticide residues includes
gesting that it be unfit for drinking and other recreational activities.
direct/indirect ingestion of river water and dermal absorption
Ogbeide et al. (2019) studied the OCP residues in Ikpoba River,
through day-to-day activities such as bathing and washing. Ac-
Nigeria, and found that its water was not suitable for drinking and
cording to the USEPA guidelines, the acceptable threshold value
bathing. Overall, the HQ and Hi values imply that the water quality
(ATV) for NCR assessment is 1 (HQ and HI < 1), above which it
in the Thamirabarani River is ideal for drinking and aquaculture,
implies a potential for non-cancer risk.
and agricultural activities. However, the CR assessment indicated a
The CDI, HQ, and HI values for the most frequently detected
possible carcinogenic effect on the local inhabitants’ health, sug-
pesticides at all the sites were calculated and are shown in Tables S6
gesting that the water was not fit for drinking, but it was suitable
and S7. The HQ value in children and adults ranged from 1.97E05
for recreational activities. To the best of our knowledge, this is the
to 2.28 and from 1.14E05 to 1.32, respectively, by ingestion of
7
U. Arisekar, R. Jeya Shakila, R. Shalini et al. Chemosphere 267 (2021) 129251

Fig. 2. Eigen value biplot (A), score plot (B) and scree plot (C) for pesticides analysis (-Fish, -Sediments and -Water).

first report on the estimation of carcinogenic and non-carcinogenic in Table 1. In the sediments collected from the Thamirabarani River,
risks of pesticides in the Thamirabaraniriver in South India. Hence, a high concentration of endosulfan (14.77 mg/kg) can be seen at site
further in-depth monitoring and risk assessment studies are 1 whereas heptachlor is not detected at sites 3 and 4. Endosulfan,
required for the Thamirabarani River system. endrin, aldrin, and BHC are the most prevalent compounds iden-
tified along the river basin. The pyrethroid pesticide (cypermeth-
3.5. Pesticides residues in sediments rin) was found at the highest concentration in the downstream
region (sites 3 and 4), indicating recent usage of pyrethroids in
Contamination of sediments by pesticide residues is a common agricultural activities. The concentration of pesticides observed in
feature in rivers. The total pesticide contamination in sediment this study varied from one site to another (within the river). This
samples ranged from ND to 16.79 mg/kg. The pesticide residues could be associated with the physicochemical properties of sedi-
present in sediment samples of the Thamirabarani River are shown ments present at each site of the river. Sediment physiochemistry
8
U. Arisekar, R. Jeya Shakila, R. Shalini et al. Chemosphere 267 (2021) 129251

Fig. 3. Pesticide percentage composition plot (A) and Bivariate Pearson correlation plot (B) (2-tailed) (n ¼ 3).

Fig. 4. Denderogram showing Bray-Curtis Similarity Index between pesticides (A) and Samples (B).

influences the distribution and availability of pesticides in sedi- the presence of pesticides in the sediment. Pesticide residues enter
ments (Bhattacharya et al., 2003; Idowu et al., 2013; Ogbeide et al., into the river basin through the agricultural runoff, and anthropo-
2016). Our study results are congruent with the previously reported genic activities bind to suspended particles in sediments and settle
concentration of endosulfan, aldrin, and endrin in the same river down at the bottom of the river, reducing the sediment quality of
(Kumarasamy et al., 2012; Arisekar et al., 2019). Similarly, Carozo- the river (Ogbeide et al., 2016, 2019; Olatunbosun et al., 2011;
Rojas et al. (2018) found endosulfan to be the most predominant Hellar-Kihampa et al., 2013; Carazo-Rojas et al., 2018). BHC, hep-
and frequently observed pesticide in La Mula catchment, Tempis- tachlor, aldrin, endrin, and DDT concentrations were found below
que River basin, Costa Rica. the TEL in the sediment, based on the sediment quality guidelines
The prolonged application of pesticides for cultivation increases prescribed by Smith et al. (1996) and Ogbeide et al. (2019) (Table 1).

9
U. Arisekar, R. Jeya Shakila, R. Shalini et al. Chemosphere 267 (2021) 129251

Fig. 5. Kruskal-Wallis independent test analysis of variance with pesticides in waters (A), sediments (B) and fish (C).

It indicates that the pesticide contamination in the Thamirabarani exposed skin, and inhalation of resuspended particles radiated
River sediment would not affect the bottom-dwelling aquatic or- from sediments through the nose and mouth (Qu et al., 2015). The
ganisms. In the case of a higher level of pesticides in the sediment NCR assessment value of pesticides in sediments through ingestion
samples, it could hinder the microbial activity and influence the route ranged from 3.95E07 to 1.04E02 (children) and from
degree of organic substance degradation, leading to anaerobic 4.70E10 to 1.24E05 (adult); that for inhalation route ranged
conditions that may affect the growth of aquatic organisms from 2.54E14 to 6.70E10 (children) and 8.29E15 to 2.19E10
(Amaraneni, 2002). (adult); and for dermal absorption ranged from 5.97E07 to
1.58E02 (children) and 3.02E07 to 7.69E03 (adult). The CDI,
HQ, and HI values of the pesticides observed through ingestion,
3.6. HRA through sediments
inhalation, and dermal contact were below ATV (i.e., HQ and HI < 1)
in the sediments (Tables S6 and S7). The highest HQ value was
The most important exposure routes considered for the evalu-
observed for aldrin at site 4, and the lowest for heptachlor at site 3.
ation of the CR and NCR hazards of pesticides in sediments include
The results indicated that the pesticide residues in the sediments
direct/indirect ingestion of pesticide-contaminated sediments,
pose no potential CR to humans (children and adults) through
dermal absorption of trace sediment particles adhered to the
10
U. Arisekar, R. Jeya Shakila, R. Shalini et al. Chemosphere 267 (2021) 129251

Fig. 5. (continued).

ingestion, inhalation, and dermal absorption. studies by Qu et al. (2015) in the Hill region of China; Ogbeide et al.
However, the CR showed above the ATV (104) in sediments (2019) in Illushi River, Nigeria; Ogbeide et al. (2016) in Ikpoba River,
through ingestion and dermal absorption but not through inhala- Nigeria; Lopez-Espinosa et al. (2008) in agrisoil, Spain; and Shalat
tion (Table S8). The estimated CR value for ingestion was above the et al. (2003) in agricultural soil, the USA.
ATV of 104, indicating that exposure to the contaminated sedi-
ment can pose a potential carcinogenic risk for the children and the
3.7. Pesticides residues in fish and HRA
adult population. Similarly, Ogbeide et al. (2019), Ogbeide et al.
(2016), Qu et al. (2015), Lopez-Espinosa et al. (2008), and Shalat
The concentration of pesticide residues in fish (rohu) muscle
et al. (2003) have reported high carcinogenic risk by sediments
tissues is presented in Table 1. Pesticides were found in a compar-
through ingestion and low carcinogenic risk through the inhalation
atively lesser concentration in the muscle than water, indicating
route. This research has shown that the mouthing (direct intake of
low-level contamination in aquatic organisms. Total pesticide
sediments via putting hand/fingers into the mouth) behavior of
concentration in rohu fish ranged from 25.67 to 31.20 mg/kg.
children makes them more susceptible to non-dietary exposure via
Pesticide residues in the fish muscle were found in the following
ingestion of pesticides in sediments (Ogbeide et al., 2019; Qu et al.,
order: heptachlor < methoxychlor < cypermthrin < BHC < DDT <
2015). Our results agree with those of a few previously reported
aldrin < endrin < endosulfan. The pesticides with the highest and
11
U. Arisekar, R. Jeya Shakila, R. Shalini et al. Chemosphere 267 (2021) 129251

Fig. 5. (continued).

lowest concentrations in rohu were endosulfan (26.05 mg/kg) and residues found in the Thamirabarani River’s rohu fish were 10 to
heptachlor (0.02 mg/kg), respectively. This result correlated with 250-fold lower than the reported values.
pesticide residues found in the water. The predominant pesticides The EDI values of heptachlor, DDT, and cypermethrin residues
found in the fish sample were endosulfan, aldrin, and endrin, the did not exceed those recommended in the CAC (ADI/PTWI) guide-
same as observed in the water samples. Rohu being a column line for both children and adults (Table 2). Yet, their intake of
feeder, has direct contact with water; this could be the reason endosulfan, endrin, and aldrin was found above the ADI, indicating
behind the significant correlation of pesticide residues in water and possible health risks associated with rohu fish consumption. The
fish (p < 0.05). The concentrations of (all) pesticides in fish were calculated HQ values also revealed that endosulfan, aldrin, and
found below the maximum residual limits (MRLs) prescribed by the endrin had ATV of 1 (Table 2). The HQ value in children and adults
Codex Alimentarius Commission (CAC, 2020) (Table 1). On the ranged between ND (cypermethrin)-9.59 (endrin) and ND (cyper-
contrary to our results, Buah-Kwofie et al. (2018) reported a high methrin)-4.94 (aldrin), respectively, for the consumption of
OCP concentration ranging from 3563 to 7533 mg/kg in magur and contaminated fish. Similarly, a few researchers reported a higher
2953e5874 mg/kg in tilapia collected from iSimangaliso wetland, risk (HQ > 1) for aldrin and endrin from consumption of contami-
South Africa. Ccanccapa et al. (2016) and Aamir et al. (2016) have nated fishes (Buah-Kwofie et al., 2018; Barnhoorn et al., 2015;
also reported higher concentrations of OCP in carps (ND to 840 mg/ Gerber et al., 2016).
kg) and freshwater fish (51.9e493 mg/kg) collected from Embro However, the risk estimates presented here show a preliminary
River, Spain, and Kabul River, Pakistan. In our study, the pesticide screening. The human health risk was estimated based on the FCR

12
U. Arisekar, R. Jeya Shakila, R. Shalini et al. Chemosphere 267 (2021) 129251

surveyed by the upstream region’s inhabitants (sites 1 and 2). 4. Conclusion and future perspective
Moreover, sites 3 and 4 were located near the estuary/sea (around
30 km), which indicates they may prefer marine fish compared to This study aimed to provide first and new information regarding
freshwater fish. This is also a significant limitation in this risk the distribution of pesticide and ecological and human health risk
assessment study. Another limitation of this risk assessment in- assessment of pesticides in the Thamirabarani River, which runs
cludes potential variation in the quantity of fish consumed by local through two districts of Tamil Nadu. Based on the ERA (RQ and TU),
inhabitants, who are all not surveyed (Sereda et al., 2009; Buah- pesticide residues in water do not show a potential risk to the
Kwofie et al., 2018). Also, exposure levels derived by the conven- aquatic organisms inhabiting the river basin. The sum of RQs and
tional solvent extraction techniques could prompt an over- TUs values used to identify the contamination level of the four sites
estimation for the potential health hazards, as a limited proportion within the river shows the risk of low, acute, and chronic toxicity to
of pesticides present in fish tissues might be bioaccessible (Wang the aquatic organisms. This study revealed the historical use of
et al., 2011; Buah-Kwofie et al., 2018). A certain assumption OCPs (especially endosulfan), which could still persist and cause a
considered during the human health risk assessment as per the potential health risk to humans. Heptachlor, aldrin, and endosulfan
USEPA guidelines through the food/meat was that cooking does not levels were found above the MRL prescribed by the CAC (2020).
affect the pollutants (Forti et al., 2011), and the ingested dose of However, the concentration of pesticides in sediments was below
pollutant is equal to the absorbed dose (USEPA, 1989). To limit the the SQG. It was observed that there could be a probability of cancer
impact of such factors, any in-depth risk assessment study is rec- risk to humans through different exposure pathways. The human
ommended in the future. health risk estimate showed a carcinogenic effect (CR > 104) of
The Principal component analysis (PCA) was used to identify the water through drinking and sediments through ingestion and
source of the pollutants using SPSS software (25 V). After the Kaiser dermal contact. However, no cancer (CR < 104) or non-cancer (HQ
Normalization and Varimax rotations, three major PC were iden- and HI < 1) risk were observed by water through bathing and
tified. The first three PCs were reflected as a key factor, which may sediments through inhalation. Pesticide concentrations in fish
influence the variation in concentration of pesticides in the samples (rohu) were found much lower than the MRL set by the CAC.
collected from the river is shown in Fig. 2. Based on the correlation However, the calculated EDI of endosulfan, aldrin, and endrin
matrix, a Bray-Curtis bi-plot was obtained using the first two axes exceeded the CAC-ADI guidelines. Moreover, the HQ values of
of PCA. The first axis explained 49.49% total variance, and the sec- endosulfan, aldrin, endrin, and heptachlor (site 1 only) exceeded
ond axis accounted for 20.87% variance. The cumulative percentage the ATV (HQ > 1) for the consumption of contaminated fish. This
of variance and eigenvalues of the analyzed parameters ranges study found that the children’s group showed a higher vulnerability
from 49.49 to 3.31 for PC-1, 62.37 to1.66 for PC-2, and 78.06 to 1.09 to pesticide residues in water, sediment, and fish consumption.
for PC-3 (Table 3). PC-1 shows positive loading of all pesticides, These findings suggest the need for increased pesticide moni-
endosulfan, endrin, methoxychlor, and cypermethrin shows posi- toring programs with a broader scope for both currently used and
tive loading in PC-2 and BHC, endosulfan, and aldrin shows positive banned pesticides. This is useful for developing and monitoring
loading in PC-3. The percentage composition of the pesticides strategies to control and mitigate pesticide pollution risks in the
recorded during the study period along the sampling sites was aquatic environment. Further work is also needed to understand
depicted in Fig. 3a. The correlation plot reveals that the strong better the potential impact and risk associated with pesticide
positive correlation between heptachlor vs DDT; a moderate cor- exposure in trophic-level organisms and to study the bioaccessible
relation level was found between aldrin vs heptachlor, aldrin vs potential, excretion, and degradation metabolism of pesticide res-
DDT, endrin vs BHC, cypermethrin vs DDT, cypermethrin vs hep- idues in fish.
tachlor, aldrin vs endosulfan; and the less correlation was found
between endosulfan vs BHC, aldrin vs endosulfan, endrin vs DDT
(Fig. 3b). Hierarchical Cluster (HC) analysis based on resemblance Credit author statement
similarity by Bray-Curtis Similarity index (BCSI) for pesticides
revealed the formation of two primary clusters, one by aldrin and Ulaganathan Arisekar, Writing e original draft, Sample collec-
DDT (73%) and the second by BHC and cypermethrin (52.15%). tion, Sample Formal analysis and Data curation. Robinson Jeya-
Similarly, secondary and tertiary clusters are formed for cyper- Shakila, Conceptualization, Investigation, Supervision, Writing e
methrin with aldrin and DDT (61.21%) and BHC with cypermethrin review & editing. Rajendran Shalini, Conceptualization, Data cura-
(48.85%), respectively. HC analysis based on resemblance similarity tion, and Writing e review & editing. Geevaretnam Jeyasekaran,
by BCSI for samples (water, sediment, and fish) revealed four pri- Investigation, draft correction, Supervision and Funding
mary clusters, three secondary clusters, and four tertiary clusters acquisition.
are formed within the samples (Fig. 4). The first three components
are heavily influenced by heptachlor, DDT, aldrin, cypermethrin, Declaration of competing interest
and endosulfan, widely used as a persistent pesticide in farmlands
and biocides in human medicines. Therefore, this component in- The authors declare that they have no known competing
dicates the release of these pesticides from the land side, through financial interests or personal relationships that could have
agricultural runoff (during the rainy season), discharge from appeared to influence the work reported in this paper.
sewage, and municipal waste into the river. Endosulfan is a banned
pesticide; however, its presence in the river indicates its illegal
usage in this region and specifies its potential to be persistent for Acknowledgment
ages. Other pesticide presence in this river basin represents their
recent utilization in agricultural and allied activities. Hence, this The authors are grateful for the financial support provided by
result agrees with few previously reported studies carried out by the Indian Council for Agricultural ResearcheNiche Area of Excel-
Kumarasamy et al. (2012) in the Thamirabaraniriver, lence in “Fish Safety and Quality Assurance”. The TNFU (Tamil Nadu
Gurusubramanium et al. (2008) in the Tea ecosystem, and Xie et al. Fisheries University) merit fellowship awarded to the first author to
(2019) in Liaodong Peninsula, China. undertake the research as part of his master’s degree program is
now acknowledged.
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U. Arisekar, R. Jeya Shakila, R. Shalini et al. Chemosphere 267 (2021) 129251

Appendix A. Supplementary data Report No. 751). World Health Organisation-Food Agriculture Organisation.
Cambridge University Press.
FAO/WHO, 1997. Guidelines for Predicting Dietary Intake of Pesticide Residues
Supplementary data to this article can be found online at (Revised). Global Environment Monitoring 12 J. S. BEDI ET AL. System - Food
https://doi.org/10.1016/j.chemosphere.2020.129251. Contamination Monitoring and Assessment Programme (GEMS/Food) in
Collaboration with the Codex Committee on Pesticide Residues WHO/FSF/FOS/
97.7. Food and Agriculture Organization and World Health Organization Rome,
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