Pahs, Pcbs, Pcbzs and Ocps) in the Surface Sediments of Hooghly Estuary, India

Chemosphere 221 (2019) 154e165

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Characterization, source identiﬁcation and risk associated with polyaromatic and chlorinated organic contaminants (PAHs, PCBs, PCBzs and OCPs) in the surface sediments of Hooghly estuary, India

* Soumita Mitra a, Simonetta Corsolini b, , Karla Pozo c, d, Ondrej Audy c, Santosh Kumar Sarkar a, Jayanta Kumar Biswas e a Department of Marine Science, University of Calcutta, 35 Ballygunge Circular Road, Calcutta 700019, India b Department of Physical, Earth and Environmental Sciences, University of Siena, I-53100 Siena, Italy c Research Center for Toxic Compound in the Environment (RECETOX), Masaryk University, Brno, Czech Republic d Facultad de Ingeniería y Tecnología, Universidad San Sebastian, Lientur 1457 Concepcion, Chile e Department of Ecological Studies and International Centre for Ecological Engineering, University of Kalyani, Kalyani, Nadia 741235, India highlights

High exposure through ingestion suggests higher risk due to biomagniﬁcation. PAH sources were both from pyrolytic and petrogenic origins together. PAH carcinogenic potential were lower than other Indian and Asian river estuaries. p,pʹ-DDE and o,pʹ-DDT exceeded the average global concentration. a-HCH/g-HCH indicated sources from lindane and HCH technical mixtures. article info abstract

Article history: The spatial distribution, source identiﬁcation and ecotoxicological impact of a group of persistent organic Received 18 September 2018 pollutants (POPs: dichlorodiphenyltrichloroethane (DDT), hexachlorocyclohexanes (HCHs), poly- Received in revised form chlorobiphenyls (PCBs), polychlorobenzenes (PCBzs)), and polyaromatic hydrocarbons (PAHs) were 21 December 2018 investigated in surface sediment samples (0e5 cm, <63 mm grain size) along the ecologically stressed Accepted 22 December 2018 Hooghly River estuary, East India. The results demonstrated a wide range of concentrations (ng/g dry Available online 27 December 2018 P P P e > e > weight)P with the following decreasingP order: 16PAHs (3.3 630) 6DDTs (0.14 18.6) 7PCBs (0.28 0 Handling Editor: J. de Boer e7.7) > 2PCBzs (0.01e1.3) > 5HCH (0.10e0.6), with a dominance of p,p -DDT and higher molecular weight PAHs. Selected diagnostic ratios indicated a mixture of both pyrolytic and petrogenic sources of Keywords: PAHs, inputs of weathered DDT and their degradation in oxidizing environment, and a predominance of Risk assessment industrial input over the agricultural wastes. The cumulative impact of the pollutants (effective range Sediment quality analyses e ﬂ medium quotient (ERMq): 0.01 0.16) re ected minimal to low ecotoxicologicalP risk, with highest Cancer risk probability of toxic effects towards surrounding biota at Barrackpore (21%). 6DDTs exceeded the effect Persistent organic pollutants (POPs) range low value resulting occasional adverse impact to the sediment dwelling organisms. Among the Polyaromatic hydrocarbons (PAHs) PAHs, the 4-ringed compounds accounted for 68% of the PAHs. Further, carcinogenic PAHs (BaA, Chry, BbF, BkF, BaP, DahP, Inp) possessed highest cancer risk (CR ¼ 2.09 10 3) to the local population when exposed to the sediments from the studied area and ingestion was found to be the primary process of contamination. The study strongly recommends a systematic monitoring of POPs and PAHs, being the Hooghly River water used by local people for their livelihood. © 2018 Elsevier Ltd. All rights reserved.

1. Introduction

* Corresponding author. Department of Physical, Earth and Environmental Sci- In recent years, the rapid growth in human population and ences, University of Siena via P.A. Mattioli, 4 I-53100 Siena, Italy. E-mail address: [email protected] (S. Corsolini). industrialization has led to an increase of the waste and emission of https://doi.org/10.1016/j.chemosphere.2018.12.173 0045-6535/© 2018 Elsevier Ltd. All rights reserved. S. Mitra et al. / Chemosphere 221 (2019) 154e165 155 pollutants in the environment. Among all types of pollutants, the discharge from the tributaries provide huge load of pollutants to chemical ones gain major concern due to their ecological and so- the estuary. This is a cause of concern for the sustainability of the cioeconomic implications (loss of biodiversity, contamination of ecosystem and restoration of the estuary. food, degradation of habitat, deprivation of livelihood) as well as In order to provide valuable information for developing pollu- human health (Botwe et al., 2017). tion prevention and management strategies for the estuary, the Persistent organic pollutants (POPs) are synthetic chemicals of present study aims the following objectives: (i) to assess the levels global concern; they show potential for long-range transport (via and spatial distribution of PAHs, PCBs, DDTs, PCBzs, and HCHs in air mass movements or oceanic streams), persistence in the envi- surface intertidal sediments of the Hooghly estuary, (ii) to assess ronment and in organisms, ability of bioaccumulation, and elicit the possible sources of these pollutants from several diagnostic toxic effects on biota, including humans (SC-POPs, 2009). For these ratios, and (iii) to evaluate the ecological risk and human health risk reasons, the Stockholm Convention on Persistent Organic Pollut- associated with these pollutants. ants was adopted in 2001 by the Conference of Plenipotentiaries in Stockholm, Sweden, and entered into force on 17 May 2004 (SC- 2. Method and materials POPs, 2009). It is a global treaty to protect human health and the environment from POPs. Among them, the organochlorinated Surface sediment samples (0e5 cm) collected from the Hooghly pesticides (OCPs) include the dichlorodiphenyltrichloroethane estuary were analysed for the following contaminants: a, b, d, g, ε (DDT), hexachlorocyclohexanes (HCHs), pentachlorobenzene isomers of HCH, p,p0- and o,p0 -DDT, PeCB, HCB, seven PCB indicators (PeCB) and hexachlorobenzene (HCB), that are synthetic organic (congener IUPAC nos. 28, 52, 101, 118, 153, 138, 180), and 16 EPA compounds that have been used as pesticides globally. They are priority PAHs (Naphthalene, Acenaphthylene, Acenaphthene, Flu- currently banned or restricted but their inherent nature, long half- orene, Phenantrene, Anthracene, Fluoranthene, Pyrene, Benz [a] life and illegal uses have led to the occurrence of OCPs in many anthracene, Chrysene, Benzo [b]fluoranthene, Benzo [k]fluo- environment matrices (SC-POPs, 2009). It is worth to mention that ranthen.Benzo [a]pyrene, Dibenz [ah]anthracene, Benzo [ghi]per- DDT is still permitted for use for malaria control in those countries ylene, Indeno [1,2,3-cd]pyrene). Among these PAHs, only the where malaria is endemic (Ntow and Botwe, 2011; Botwe et al., following 2e4-rings PAH compounds were detected: PAHs [ace- 2017). However, in 2009 the DDT production in India has been naphthylene (Acy), acenaphthene (Ace), fluorene (Fl), phenan- 3 3 raised to 3314 10 kg of technical grade DDT and 6830 10 kg of threne (Phe), anthracene (An), fluoranthene (Flu), pyrene (Py), DDT50 formulation (UNEP-NIP, 2011). Once in the environment, benz(a)anthracene (BaA) and chrysene (Chry)]. DDT breaks down into its metabolites DDE and DDD. Polychlorinated biphenyls (PCBs) are the key representatives of the industrial POPs (SC-POPs, 2009). The different 209 congeners of 2.1. Study area PCBs generated by the chlorination of the biphenyl ring differ widely in toxicity and properties depending on the number and The study was carried out along the Hooghly river estuary position of chlorine atoms (Guzzella et al., 2005). They have been (HRE), the ecologically and economically important viable water used as insulator and dielectric fluids in transformers and capaci- source for the population as it gives perpetual water supply to them fi tors, flame retardants, oil additives, lubricants among others uses for multi-dimensional works, water traf c and industrial purposes. (SC-POPs, 2009). Contemporary sources include the use of equip- Nine sampling stations were selected (S1 to S9), along the north- ment containing PCBs, the emissions from PCB reservoirs, the south gradient of the estuary, depending on the variability of geo- release from old electric systems, and thermal process (SC-POPs, physical environment and tidal condition, distance from the Bay fl 2009; EMEP/CORINAIR, 2004). They were banned in most coun- of Bengal, ux of wave energy, diverse nature of human activities tries since 1970s (SC-POPs, 2009). and several point and nonpoint sources of pollution as shown in Polycyclic aromatic hydrocarbons (PAHs) are not included in the Fig. 1. Two sampling stations (S10 and S11) were additionally list of the Stockholm Convention and mostly derive from incom- considered to get an overview of the status and trends of the plete combustion of organic material. Different compounds of PAHs studied pollutants in the Bengal Basin. These areas are situated in contain two to eight aromatic benzene rings and their hydropho- the eastern part of Indian Sundarban Mangrove Wetland (SMW). bicity and toxicity depends on the number of aromatic rings. Among them, 16 compounds are recognized as main concern pol- 2.2. Sample collection and preservation of the samples lutants by the U.S. Environmental Protection Agency (USEPA) (Wang et al., 2015; Zhao et al., 2017). The sediment samples weighing 10 g were randomly collected The priority chemical pollutants analysed in this study involved in triplicate from the top 3e5 cm at each sampling station during PAHs, PCBs, DDTs, HCHs, and polychlorobenzenes (PCBzs) including low tide using a grab sampler, pooled and thoroughly mixed. HCB and PeCB, that are often found in the different compartments Immediately after collection, the samples were placed in sterilized of the global ecosystem like water, particulate matter, sediment and aluminum containers, put in the ice box and transported to the organisms (Maioli et al., 2010; Karacık et al., 2013; Nguyen et al., laboratory. Samples were oven dried at 50 C, most gently dis- 2014; Li et al., 2014; Tongo et al., 2017). These are of great aggregated, transferred into pre-cleaned glass jars and stored in concern due to their persistent nature, long range transport, bio- deep freeze prior to analyses. Each sample was divided into two accumulation, toxicity as well as carcinogenicity (Willett et al., aliquots: one aliquot (5 g) was used for measuring the sediment 1998; Nyarko et al., 2011). Moreover, because of their low water quality parameters (organic carbon, pH, and percentage of silt, clay, solubility, these pollutants often accumulate in sediments and or- and sand) and the other part was sieved through 63 mm metallic ganisms (Hussain et al., 2016). sieves and stored in pre-cleaned, inert polyethylene bags, and kept The Hooghly River is a 260 km long distributary of the Ganges at 20 C until analyses of the organic pollutants. River and it flows south through West Bengal, India. The Hooghly The organic carbon content was determined following a rapid estuary (21310Ne23300N, 87450E88450E) is the major offshoot titration method (Walkey and Black, 1934), and pH with the help of of river Ganges and it claims to be ecologically very sensitive. a deluxe pH meter (model no. 101E) using combination glass Several fishing harbors, multifarious industries along with electrode manufactured by M.S. Electronics (India) Pvt. Ltd. Me- chanical analyses of sediment were done by sieving in a Ro-Tap 156 S. Mitra et al. / Chemosphere 221 (2019) 154e165

Fig. 1. Map showing the location of 11 sampling stations along the Hooghly estuary: Barrackpore (S1), Agarpara (S2), Dakhineswar (S3), Nimtala (S4), Babughat (S5), Nurpur (S6), Diamond Harbor (S7), Lot 8 (S8), Gangasagar (S9), Caning (S10), Dhamakhali (S11).

Shaker (Krumbein and Pettijohn, 1938) manufactured by W.S. Tyler an insert in a vial. Terphenyl was added as syringe standard, final Company, Cleveland, Ohio, and statistical computation of textural volume was 200 mL. All contaminants were identified and quanti- parameters was done by using formulae of Folk and Ward (1957). fied using a gas-chromatograph coupled to a mass spectrometer (GC-MS, 7890A GC, Agilent, USA) equipped with a 60 m 0.25 mm 2.3. Chemical analysis x 0.25 mm DB5-MSUI column (Agilent, J&W, USA) coupled to 7000B MS (Agilent, USA). Injection was 1 mL splitless at 280 C, with He as Sediment samples (5 g) were homogenized with anhydrous carrier gas at constant flow 1.5 mL/min. The GC programme was sodium sulfate to perform a chemical drying. Samples were spiked 80 C (1 min hold), then 15 C/min to 180 C, followed 5 C/min to with surrogate recovery standards and extracted using automated 310 C (20 min hold). The MS was operated in EI þ mode with warm Soxhlet extraction (40 min warm Soxhlet followed by 20 min selected ion recording (SIR). of solvent rinsing) with dichloromethane (DCM) in a B-811 extraction unit (Büchi, Switzerland). The concentrated extracts 2.3.2. Analysis of indicator PCBs and OCPs were split into 2 portions, 10% was used for PAHs analysis, 90% for The second portion of extract was cleaned-up on a H2SO4 PCBs and OCPs. modified (44% w/w) silica and AgNO3 silica column, analytes were eluted with 30 mL DCM/n-hexane mixture (1:1). The eluate was 2.3.1. Analysis of PAHs concentrated using stream of nitrogen in a TurboVap II concen- The first portion of extract was fractionated on a silica column trator unit and transferred into an insert in a vial. The syringe (5 g of silica 0.063e0.200 mm, activated at 150 C for 12 h). The first standards (native PCB 121) were added to all samples, the final fraction (10 mL n-hexane) containing aliphatic hydrocarbons was volume was 100 mL. discarded. The second fraction (20 mL DCM) containing PAHs was GC-MS/MS was used for indicator PCBs and OCPs analysis. A collected and then reduced by stream of nitrogen in a TurboVap II 7890A GC (Agilent, USA) equipped with a 60 m 0.25 mm x 0.25 (Caliper Life Sciences, USA) concentrator unit and transferred into mm HT8 column (SGE, USA) coupled to a 7000B MS (Agilent, USA) S. Mitra et al. / Chemosphere 221 (2019) 154e165 157 operated in EI þ MRM was used. Injection was pulsed splitless (iii) 0.5 mERMq <1.5: moderate risk with 49% probability of 3 mL at 280 C, He as carrier gas at 1.5 mL/min. The GC temperature toxicity programme was 80 C (1 min hold), then 40 C/min to 200 C, and (iv) mERMq 1.5: high risk with 76% probability of toxicity. finally 5 C/min to 305 C. Moreover, the potential toxicity of the carcinogenic PAHs, i.e. the 2.4. Quality control toxicity equivalent (TEQ) concentration was estimated by calcu- lating the total toxic benzo [a]pyrene (BaP) equivalent (TEQcarc) for High purity analytical reagents and chromatographic grade all carcinogenic PAHs using the equation (ii) as given by Savinov chemicals were used thorough the work. Organic solvents were et al. (2003), and Chen and Chen (2011): supplied by J.T. Baker (Poland). Reference standards were provided © P P by LGC Standards ( LGC Limited, UK), and by Wellington Labora- (ii) TEQcarc ¼ iCi x TEFcarci tories Inc. (Canada). Surrogate extraction standards (D8-naphthalene, D10- where Ci is the concentration of individual carcinogenic PAH (ng/g phenanthrene, D12-perylene, PCB30, PCB185) were spiked on dw) and TEFcarci is the toxic equivalency factor (TEF) of carcinogenic each sample prior to extraction. The volume was reduced after PAHs relative to BaP. The established TEFs by USEPA are the follows: extraction under a gentle nitrogen stream at ambient temperature, 0.1 for BaA, 0.001 for Chr, 0.1 for BbF (Tian et al., 2013). and fractionation was achieved on a silica gel column. In order to check for interference and cross contamination, a 2.6. Human health risk procedural blank consisting of all reagents and spiked samples fi (sediments) were run for every set of ve samples. Blank results Carcinogenic riskP to theP human wasP calculated for the carcino- were very low showing values of <2% of detected PAHs levels. genic PAHs only, 7PCBs, 6DDTs and 5HCHs through the three The limit of detection (LOD) of PAHs, PCBs, and OCPs were possible exposure pathways, i.e. ingestion, dermal and accidental calculated as 3:1 signal versus noise value. The LOD of OCPs ranged inhalation. The following equations have been used to calculate the from 0.01 to 0.06 ng/g dry weight (dry wt). The spiked recoveries risk through the pathways as proposed by USEPA (1997, 2009): were higher than 75% for all samples for OCPs. Recovery factors were not applied to any of the data. In addition, recovery of native (iii) CRing ¼ (Csed x ingR x EF x ED x CF x SFO)/BW x AT analytes measured for a reference material (soil) varied from 75 to (iv) CRder ¼ (Csed xSAXAFsed x ABS x EF x ED x CF x SFO)/(PEF x 98% for OCs. The relative standard deviation ranged from 4 to 9%. AT) Average PAHs recoveries were 62% for D8-naphthalene, 78% for (v) CRinhale ¼ (Csed x IahR x EF x ED x IUR x AFinh)/(PEF x AT) D10-phenanthrene and 87% for D12-perylene. where Cing,Cder and Cinhale are the measured concentration of the 2.5. Environmental risk assessments contaminants due to ingestion, dermal contact and inhalation, respectively; EF is the exposure frequency (350 days/year); ED is The environmental risk assessment was evaluated using the the exposure duration (70 years); CF is the unit conversion factor sediment quality guidelines (SQGs), useful tool to evaluate the (10 6); SFO is the oral slope factor (7.3 mg/kg/day); IngR is the degree of sediment contamination that also allow to prevent ingestion rate (100 mg/day); BW is the body weight (70 kg); AT is additional contamination and the suggested regulatory strategies the average day (25,550 days); SA is the exposed skin surface area 2 (Birch, 2018). The SQGs allow to assess how an organism, popula- (5700 cm ); AFsed is the adherence factor from the sediment to skin tion or community may be affected by contamination, in terms of (0.07 mg/cm2); ABS is the dermal absorption from the sediment their growth, reproduction success, and community dimension. (0.13); IahR is the inhalation rate (15.8 m3/days); IUR is the inha- These ecological characteristics were correlated to measured con- lation unit risk (5.7 10 1 mg/m3); AFinh is the absorption factor centrations of known contaminants in sediment (on dry weight for the lungs (1); PEF is the particle emission factor (1.36 billion m3/ concentrations) to assess the toxicity thresholds for that specific kg). Further, the characteristic of the cancer risk can be qualitatively chemical and site (McCauley et al., 2000). SQGs derived using the described as follows (Man et al., 2013): correlative approach are then applied to sediment chemistry measurements from other sites to indicate possible toxicological CR 10 6: very low risk risks associated with these sediments. 10 6 < CR < 10 4: low risk The risk associated with the individual POPs was estimated 10 4 CR < 10 3: moderate risk using two sets of SQGs: the effects range low (ERL)/effects range 10 3 CR < 10 1 high risk medium (ERM) and threshold effect level (TEL)/probable effects CR 10 1: very high risk. level/(PEL). Further to estimate the risk associated with the combined effects of POPs, mean ERM quotient (mERMq) was calculated 3. Result and discussion following the equation (i) (Long et al., 2006): P 3.1. Sediment geochemistry (i) mERMq ¼ ( Cx/ERMx)/n Sediment quality parameters (pH, organic carbon, textural where Cx is the measured concentration of the examined compo- properties) showed different values depending on the sample nent x in sediments, ERMx is the ERM for those components, and n (Table 1). The sediment textural composition included a higher is the number of components. The present study combined the two proportion of fine particles (silt þ clay: 72.50%e99.40%), compared categorizations that were derived from Long et al. (2000) and to sand particles (0.60%e27.50%) (Table 1). The predominance of stated the following four categories: the finer particles indicated the long transport process along with the erosion and weathering processes (Ünlu and Alpar, 2016). Low (i) mERMq < 0.1: minimal risk with only 9% probability of fluvial discharge or a better mixing of saline and fresh water might toxicity have also facilitated the flocculation process, leading to subsequent (ii) 0.1 mERMq < 0.5: low risk with 21% probability of toxicity settling of suspended particles (Nair et al., 1982). The organic 158 S. Mitra et al. / Chemosphere 221 (2019) 154e165

Table 1 Characteristics of the sediments along with the textural class (Corg ¼ organic carbon).

pH Corg (%) Sand (%) Silt (%) Clay (%) Textural class

Barrackpore (S1) 8.1 0.69 2.49 66.57 30.94 Fine silty Agarpara (S2) 8.3 0.63 1.82 54.2 43.8 Silty clay Dakhineswar (S3) 7.6 0.65 3.12 42.65 54.23 Silty clay Nimtala (S4) 8.3 0.54 9.43 17.47 73.1 Silty clay Babughat (S5) 8.2 0.72 1.48 57.52 41 Silty clay loam Nurpur (S6) 7.9 0.91 0.6 24.35 75.05 Very ﬁne clay Diamond Harbor (S7) 8.6 0.7 27.5 50.56 30.8 Clay loam Lot 8 (S8) 8.1 0.56 27.5 32.54 39.95 Fine clay Gangasagar (S9) 7.9 0.59 19.6 20.2 60.2 Silty clay Caning (S10) 8.0 0.78 4.00 18.2 77.8 Very ﬁne clay Dhamakhali (S11) 8.1 0.43 2.44 54.98 42.58 Silty clay

carbon (Corg) ranged from 0.56% to 0.91% with an average value of in PAH concentrations may be related to multiple factors: a differ- 0.69 ± 0.11% indicating less influence of decomposition of the ence in hydrodynamic regimes related to the river discharge and detritus materials. It also gives indication of some prevalent hy- tidal influx; a change in sediment textural properties; a differential drodynamic factors along with low sedimentation rate, permanent resuspension and re-deposition of sedimentary PAHs; and micro- sediment reworking (El Nemr et al., 2013), and higher rate of bial degradation of PAHs (Boonyatumanond et al., 2006). In addi- microbial-mediated degradation processes (Watts et al., 2017). On tion, no PAH contaminants were at all reported from the two the other hand, the sediment pH showed almost neutral (7.6) to stations Gangasagar (S9) and Canning (S10). Generally, the estua- slight basic nature (8.6). rine areas showed greater concentration than riverine system, as reported for superficial water by Santos et al. (2017). The maximum 3.2. Profile and distribution of POPs concentration in the upstream region might be due to the location of the Kolkata metropolitan area nearby where high traffic related fi The GC-MS analyses con rmed the presence of majority of the activities led to enormous productionP and discharge of the organic studied POPs in the sediment samples from all the stations. The PAHs (Tu et al., 2018). This range of 16PAH values was found to be sampling stations S1eS9 are named following an increasing num- much lower than in previously reported data (2.5e1081 ng/g) in ber from upstream to the Bay of Bengal, thus S1 is the upstream sediments from the region covering Hooghly and Sundarban study station and S9 is the river mouth station (Fig. 1). (Guzzella et al., 2005). According to Bemanikharanagh et al. (2017), the PAH pollution 3.2.1. Polycyclic aromatic hydrocarbons status can be categorized as follows: (i) low polluted (<100 ng/g), Ten PAHs were identified and quantified in the samples. The (ii) moderately polluted (101e1000 ng/g), (iii) highly polluted spatial distribution of the individual compounds including the (1001e5000 ng/g), and (iv) very highly polluted (>5000 ng/g). carcinogens benzo(a)anthracene (BaA), chrysene (Chry), benzo(b) Based on this criteria, the majority of the stations (S4 to S10) can be fl uoranthene (BbF), andP the total concentration of PAHs are re- recognized as low polluted except the stations Barrackpore (S1), fi ported in Table 2. The 16PAHs showed a wide range of concen- Dakhineswar (S3), and Dhamakhali (S11) which can be classi ed as trations: from 3.3 ng/g in the Lot 8 (S8) station to 630 ng/g in the moderately polluted ones. Dakhineswar station (S3), with an average value of 137.7 ± 226 ng/ The contribution of the individual PAH showed the following g. A decreasing trend was observed towards the downstream, decreasing trend across the sampling stations: BaA ± > ± > ± > Pexcept at Dhamakhali (S11), where second highest concentration of (53.3 91.3) Chry (29.8 59.6) BbF (25.4 54.5) Phe ± > ± > ± > ± > 16PAHs was detected (536 ng/g). The prevalent spatial variations (16.7 23.7) Py (6.0 19.1) Flu (4.9 15.8) Acy (1.4 2.5) Fl

Table 2 ¼ ¼ ¼ ¼ ¼ ¼ ¼ ¼ Concentration (ng/g dry wt) of PAHs (Acy Acenaphtylene, Ace Acenaphtene,P Fl Fluorene, Phe Phenantrene, An Antracene, Flu Fluoranthrene, Py Pyrene, BaA Benzo(a)anthracene, Chry ¼ Chrysene, BbF ¼ Benzo(b)ﬂuoranthene), their sum ( 16PAHs; compounds < LOD in all samples are not reported in the table), and effect range low (ERL), effect range medium (ERM), threshold effect level (TEL), and potable effect level (PEL). The ratios LPAHs/HPAHs, Flu/(Flu þ Pyr), and BaA/(BaA þ Chry) are also reported (see the text for explanations). P Acy Ace Fl Phe An Py Flu BaA Chry BbF 16PAHs LPAHs/ Flu/ BaA/ HPAHs (Flu þ Pyr) (BaA þ Chry)

No. of aromatic rings 33333444 4 5 Barrackpore (S1) 0.08 < LOD 0.07 3.81 0.57 63.72 52.49 18.16 8.39 7.91 155.19 0.03 0.45 0.68 Agarpara (S2) 1.15 0.93 < LOD < LOD < LOD 0.02 0.02 6.82 < LOD < LOD 8.94 0.30 0.51 0.61 Dakhineswar (S3) < LOD < LOD 2.18 75.25 < LOD 1.07 0.71 249.42 161.94 138.03 628.61 0.14 0.40 0.65 Nimtala (S4) 7.88 < LOD < LOD 30.49 < LOD 0.14 0.11 39.33 21.09 < LOD 99.06 0.63 0.45 1.00 Babughat (S5) 3.03 < LOD < LOD 15.60 0.00 0.09 0.094 28.33 < LOD < LOD 47.15 0.65 0.50 1.00 Nurpur (S6) < LOD < LOD < LOD 9.15 < LOD 0.10 0.06 8.86 < LOD < LOD 18.17 1.01 0.37 1.00 D. Harbor (S7) < LOD < LOD < LOD 7.83 < LOD < LOD 0.03 9.57 < LOD < LOD 17.43 0.82 1.00 1.00 Lot 8 (S8) < LOD < LOD < LOD < LOD < LOD < LOD 0.02 3.24 < LOD < LOD 3.26 < LOD < LOD 1.00 Gangasagar (S9) < LOD < LOD < LOD < LOD < LOD < LOD < LOD < LOD < LOD < LOD < LOD ee e Caning (S10) < LOD < LOD < LOD < LOD < LOD < LOD < LOD < LOD < LOD < LOD < LOD ee e Dhamakhali (S11) 2.94 < LOD < LOD 41.17 < LOD 0.70 0.576 222.21 136.13 132.96 536.69 0.09 0.45 0.62 ERL 44 16 19 240 85 670 600 261 384 e 4022 ee e ERM 640 500 540 1500 110 2600 5100 1600 2800 e 44792 ee e TEL 5.9 6.71 21.1 86.7 46.9 153 113.0 74.8 108 e 1684 ee e PEL 128 89 144 544 245 1398 1494 693 846 e 16770 ee e S. Mitra et al. / Chemosphere 221 (2019) 154e165 159 P (0.2 ± 0.70) > Ace (0.08 ± 0.28) > An (0.05 ± 0.17). These results levels of DDTs higher than HCHs. The 6DDT concentration in the indicated that the carcinogenic PAHs contributed mostly (about sediment samples ranged 0.14e18.6 ng/g (Table 3), and the highert 79%) to the total concentration of PAHs. Although Phe, Flu and BaA concentrations were found in the extreme upstream of the estuary: were present at almost all stations, Ace and An were exclusively Barrackpore (S1) > Dakhineswar (S3). The pattern of OCP distribu- present at station Agarpara (S2) and Barrackpore (S1), respectively. tion could be inﬂuenced by the physicochemical properties of Moreover, Fl, Chry, BbF and Acy were present in the upstream re- residue compounds along with environmental conditions. In gion of the estuary, especially at stations S1, S3 and S4. It is also addition, topography, redox potential, total organic matter, and reported earlier that not only the textural characteristics but the hydrodynamic condition together with other factors play impor- redox conditions of sediment also play signiﬁcant role in the tant roles in controlling the distribution and fate of OCPs (Su et al., biodegradation of the organic matter leading to the accumulation 2006). of these organic pollutants in the sediments (Lin et al., 2009; Botwe Among the 6 isomers and metabolites of DDT, the p,p'-DDE and et al., 2017). o,p'-DDT were the dominant ones contributing 62% and 15%, Depending on the number of the aromatic rings, the PAHs were respectively, while low concentrations of DDDs were detected in all divided into two groups: low ring PAHs (LPAHs) consisting of 2e3 the sediment samples. This enrichment might be due to the rings, and high ring PAHs (HPAHs) consisting of 4e6 rings (García- continued extensive local use of DDT-based antifouling paints for Falcon et al., 2006). In the studied sediments, the HPAHs were boat maintenance (Lin et al., 2009; Yu et al., 2011). As DDT is ¼ predominant contributingP around 90% (4 rings 77%, 5 banned since 1976, its monitoring is necessary owing to its toxicity, rings ¼ 13%) to the 6PAHs (Fig. 2). HPAHs have greater tendency persistence, illegal uses and existence of stockpiles (Ntow and to accumulate in the sediments (Zhang et al., 2017; Souza et al., Botwe, 2011). 2018), and a similar pattern was also reported by Tu et al. (2018) India is reported to be one of the major consumers of HCHs as in sediments of rivers Lover and Ho-Jin, Taiwan. It is worth to well as the most contaminated nation in the world (Li et al., 2003), mention that while HPAHs originate from combustion products, due to the cumulative use of 45,000 t of HCHs annually (Voldner pyrolytic process or petrogenic sources (Ping et al., 2007), LPAHs and Li, 1995). The technical mixture mainly used in India con- derive from oil or fuel leaks and do not persist in the environment sisted of a-HCH (53e70%), b-HCH (3e14%), g-HCH (10e18%), d-HCH e ε e for long time (Nguyen et al., 2014). The microbial activity was re- (6 10%), -HCH (1 5%), and traces of furtherP isomers and conge- ported to degrade PAHs and the biotransformation as well as ners (SC-POPs, 2006). In this study, the 5HCH concentrations environmental transformation may allow PAHs to degrade to in- were of the same order of magnitude in all stations, varying from termediate chemicals with higher toxicity respect to the parent 0.10 ng/g (Agarpara, S2) to 0.58 ng/g (Barrackpore, S1), with a mean compounds (Souza et al., 2018). The atmospheric temperature and value of 0.22 ± 0.14 ng/g (Table 3). Among the isomers, the g-HCH ± pressure control the hydrophobicity, solubility, volatility, photo- (31%, averageP concentration: 0.07 0.05 ng/g) contributed mostly oxidation, and bioavailability of PAHs (Havelcova et al., 2014). to the 5HCHs followed by d-HCH (29%, average concentration: 0.06 ± 0.04 ng/g), and a-HCH (28%, average concentration: 0.06 ± 0.04 ng/g) (Fig. 2). The b- and ε-isomers contributed 3% and 3.2.2. Organochlorinated pesticides P 9%, respectively, to the 5HCH residue; the detection of the ε- The distribution of OCPs in the sediments from 11 sampling isomer may be due to its release from technical mixtures and/or to stations revealed wide range of concentrations (Table 3), with

Fig. 2. Percentage composition of the isomers or congeners of the different chemical families. 160 S. Mitra et al. / Chemosphere 221 (2019) 154e165

Table 3 Concentration of OCPs and PCBs (ng/g dry wt) in the sediment samples and effect range low (ERL), effect range medium (ERM) threshold effect level (TEL), and potable effect level (PEL). Please see Table 2 for site names.

S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 S11 ERL ERM TEL PEL

a-HCH 0.17 0.03 0.03 0.03 0.04 0.04 0.08 0.07 0.07 0.06 0.06 ee ee b-HCH 0.02 < LOD < LOD < LOD 0.01 < LOD 0.01 0.01 0.01 < LOD 0.01 ee ee g-HCH 0.19 0.03 0.04 0.04 0.04 0.04 0.09 0.08 0.08 0.07 0.06 0.32 1.00 0.32 0.99 d-HCH 0.18 0.03 0.03 0.04 0.04 0.04 0.08 0.07 0.07 0.07 0.06 ee ee ε ee ee P-HCH 0.01 0.01 0.01 0.02 0.03 0.01 0.05 0.02 0.02 0.02 0.02 5HCHs 0.58 0.10 0.12 0.12 0.15 0.13 0.31 0.25 0.26 0.21 0.20 ee ee a-HCH/g-HCH 0.88 0.86 0.90 0.90 1.00 0.90 0.93 0.86 0.95 0.85 0.91 ee ee o,p'-DDE 1.97 0.04 0.11 0.09 0.05 0.02 0.08 0.05 0.01 0.62 0.18 ee ee p,p'-DDE 12.10 0.32 1.97 0.17 0.78 0.19 0.60 0.34 0.04 0.49 0.66 2.20 27.00 2.07 374.00 o,p'-DDD 0.54 0.03 0.05 0.02 0.03 0.02 0.08 0.04 0.01 0.08 0.09 ee ee p,p'-DDD 0.38 0.02 0.01 < LOD 0.01 0.01 0.14 0.06 0.03 0.05 0.11 2.00 20.00 1.22 7.81 o,p'-DDT 2.75 0.13 0.16 0.05 0.09 0.04 0.34 0.15 0.03 0.33 0.24 ee ee < < Pp,p'-DDT 0.83 0.05 0.01 LOD 0.01 LOD 0.33 0.09 0.02 0.10 0.13 1.00 7.00 1.19 4.77 6 DDTs 18.58 0.59 2.31 0.33 0.96 0.29 1.58 0.74 0.14 1.67 1.42 1.58 46.10 3.89 51.70 DDT/DDD þ DDE 0.25 0.08 0.18 0.42 0.11 0.19 0.74 0.50 0.61 0.34 0.36 DDT/DDE 0.25 0.08 0.19 0.49 0.12 0.22 0.98 0.63 1.08 0.38 0.45 PeCB 0.27 0.03 0.08 0.01 0.07 0.02 0.03 0.02 0.01 0.03 < LOD ee ee ee ee PHCB 1.03 0.09 0.15 0.13 0.18 0.05 0.12 0.07 0.03 0.26 0.01 2PCBzs 1.30 0.12 0.23 0.14 0.25 0.08 0.15 0.09 0.04 0.29 0.01 ee ee PCB 28 1.73 0.23 0.45 0.14 0.49 0.12 0.36 0.22 0.05 0.27 0.09 ee ee PCB 52 1.30 0.15 0.40 0.11 0.38 0.08 0.23 0.14 0.03 0.19 0.08 ee ee PCB 101 1.24 0.13 0.36 0.13 0.30 0.06 0.20 0.11 0.04 0.22 0.09 ee ee PCB 118 0.95 0.11 0.38 0.12 0.22 0.05 0.16 0.08 0.05 0.15 0.08 ee ee PCB 153 0.95 0.11 0.34 0.12 0.22 0.04 0.15 0.06 0.05 0.16 0.07 ee ee PCB 138 1.03 0.12 0.38 0.10 0.24 0.04 0.16 0.06 0.03 0.17 0.09 ee ee ee ee PPCB 180 0.52 0.06 0.17 0.04 0.13 0.02 0.09 0.02 0.03 0.12 0.05 P7PCBsP 7.72 0.92 2.48 0.76 1.99 0.40 1.34 0.68 0.28 1.30 0.55 22.70 180.00 22.00 189.00 6 DDTs/ 7PCBs 2.41 0.93 0.43 0.64 0.48 0.72 1.17 1.08 0.50 1.28 2.59 ee ee

analytical interference. After the ban of the technical grade HCH in moreover the number of analysed congeners can also affect results. the agricultural field in 1997, the Government of India has been The PCBs analysed in this study are the most frequently detected encouraging the use of lindane (99% pure g-HCH) that shows all congeners in the environment (e.g. Net et al., 2015). The PCB class of properties of technical HCH (Gupta et al., 2004). These results and isomer abundance followed the pattern tri-CBs > penta- the a-HCH/g-HCH value (Table S1) suggested that the Government CBs > hexa-CBs, and the fingerprints showed a major contribution proposal has been cautiously followed and the application of of PCB28 (22%; range: 0.03e1.7 ng/g) > PCB 52 (17%; range: technical HCH has been drastically reduced in the study area (Wang 0.03e1.3 ng/g) > PCB 101 (16%; range: 0.04e1.2 ng/g) > PCB 138 et al., 2008; Mishra et al., 2013). (13%; range: 0.02e1.03 ng/g) > PCB118 (13%; range: 0.04e1.0 ng/ g) > PCB153 (12%; range: 0.03e1.0 ng/g) > PCB180 (7%; range: 0.02e0.5 ng/g) (Fig. 2). The PCB source could be from the diverse 3.2.3. PCBzs and indicator PCBs industrial activities, electro-thermal power plants, oil spills (Ren PCBzs include PeCB and HCB and from the middle of 20th cen- et al., 2007; Jiang et al., 2011; Ali et al., 2015), and waste water tury they were used as chemical intermediates in commercial treatment discharges (Bettinetti et al., 2016). The total organic chemical production to pesticides; the components of chloroben- carbon also plays an important role by enhancing the capacity of zenes mixture to reduce the viscosity of PCB products for the heat PCB absorption (Fox et al., 2001). transfer, as carriers in dye process and as fungicides (SC-POPs, 2009). Although some PCBzs were banned since decades world- wide being highly hazardous for ecosystems and human health, 3.3. Identification of POP sources they are still detected in the environment (SC-POPs, 2009). The concentration of total PCBzs in sediment samples ranged The identification of the source of any contamination is deemed from 0.01 ng/g (Dhamakhali,S11) to 1.3 ng/g (Barrackpore, S1) necessity for controlling its emission or release. Thus, several (mean value: 0.24 ± 0.36 ng/g). HCB and PeCB concentrations were diagnostic ratios were used to identify the possible sources of 0.19 ± 0.29 ng/g (79% of PCBzs) and 0.05 ± 0.07 (21% of PCBzs), contamination; each source has a characteristic fingerprint, respectively, with similar spatial distribution pattern (Table 3, although, after their release into the environment, they may un- Fig. 2). The major source of PCBzs in the studied region includes dergo transformation and transition (Shi et al., 2015). The diag- wastes from municipal incinerators, uncontrolled combustion nostic ratios along with their categorizations are reported in process, and simultaneous release of ash residues from burning of Table S1. The source of PAHs could be biogenic, pyrogenic, petro- biomass (Nie et al., 2011). genic and diagenic source, however, only the petrogenic and py- fi Regarding PCBs,P a similar signi cant decreasing trend was rogenic PAHs are present at biologically relevant concentration in recognized for 7PCBs towards downstream of the estuary: the marine sediments (Traven, 2013). In most environments, pet- 0.28 ng/g at Gangasagar (S9) and 7.7 ng/g at Barackpore (S1), with rogenic origin makes PAHs as more bioavailable compared to py- an average value of 1.7 ± 2.1 ng/g. Their concentrations were found rogenic and thus they show higher ecotoxicological relevance to be much higher than reported in previous study in the Hooghly (Thorsen et al., 2004). estuary (0.18e2.33 ng/g) (Guzzella et al., 2005) and this difference In the present study, the ratios LPAHs/HPAHs (Budzinski et al., may be due to several factors, e.g. a different sampling season may 1997; Lin et al., 2016; Zhang et al., 2017), Flu/Flu þ Py (Yunker affect the contaminant deposition, evaporation, transport; et al., 2002), and BaA/BaA þ Chry (Budzinski et al., 1997)were S. Mitra et al. / Chemosphere 221 (2019) 154e165 161 used to identify the possible sources of PAHs. The overall ratio of 2011; Li et al., 2014). Both the ratios in the present study were < 1.0 LPAHs/HPAHs and BaA/BaA þ Chry ranged 0.03e0.82 (except (DDT/DDD ¼ 0.08e0.98, DDT/DDD þ DDE ¼ 0.01e0.91) indicating S6 ¼ 1.01) and 0.61e1.00, respectively (Table 2, Fig. 3). Both the that the DDT contamination is likely due to past use of DDT, except ratios indicated the pyrolytic origin that involved mainly the wood at station Gangasagar (S9) where the value was 1.08 indicating a or coal combustion, vehicle exhaustion and burning of dead bodies possible current use of DDT as a component of antifouling paints in the area along with some traces of petrogenic sources. The Flu/ used in local mechanized boats and for controlling vector borne Flu þ Py ratio ranged 0.37e1.00 and allowed to identify three diseases like malaria (Pozo et al., 2017; Li et al., 2007). The ratio of distinct stations with a different source of contamination: <0.40 DDT/DDD þ DDE ranged 0.01e0.91 except at stations Nurpur (S6) (Nurpur, S6), indicating petroleum contamination or oil spills as a and Diamond Harbor (S7) where the values were 1.25 and 1.00, number of mechanized boats are often used in that area for water respectively (Fig. 3a). Thus, the overall abundance of DDE indicated transportation; 0.40e0.50 [Barrackpore (S1), Agarpara (S2), Nim- a past use of this pesticide and an oxidizing environment allowing tala (S4), Babughat (S5), Dhamakhali (S11)], indicating the vehicle aerobic degradation of DDT into its metabolites. exhausts as these study stations are situated adjacent to metro- The a-HCH/g-HCH ratio ranged 0.85e1.00 indicating that a politan megacity Kolkata (former Calcutta), except Dhamakhali potentially mixed technical HCH and lindane emission source exist (S11); > 0.50 (Dakhineswar, Diamond Harbor, Lot 8), indicating in the studied area. Our results agreed with previous findings in combustion of wood, coal and grass that the local people exten- sediments from south east China (Zhang et al., 2011), Indian Sun- sively use mainly for cooking and other household purposes. darban mangrove wetland area (Guzzella et al., 2005), Bohai Sea, DDT in the environment degrades into its metabolites DDD and China (TanP et al., 2009P ), and Huai river, East China (Sun et al., 2010). DDE. The ratios DDT/DDD or DDT/(DDD þ DDE) are used to identify The 6DDTs/ 7PCBs ratio has been used to investigate if the if its use was either recent or past, respectively. The ratio < 1 in- pollutants source is from agriculture or industry (Aguilar et al., dicates a past use of DDT and > 1 indicates its current use (Yu et al., 1999; Lailson-Brito et al., 2011). Our values ranged 0.43e2.59

Fig. 3. Cross-plots for the ratios indicating possible sources of pollution. 162 S. Mitra et al. / Chemosphere 221 (2019) 154e165

(Table 3), suggesting that the contamination of these organic pol- lower than values reported in samples from Meiliang Bay, Taihu lutants mainly originates from the industrial zones. Lake, China (Qiao et al., 2006), Guba Pechenga, Barents, Sea, Russia (Savinov et al., 2003), coastal lagoons in central Vietnam (Giuliani et al., 2008), Yangtze River, China (Liu et al., 2017), Kaohsiung 3.4. Ecotoxicological impact Harbor, Taiwan (Chen and Chen, 2011), Jialu River, China (Fu et al., 2011), and Sundarban mangrove wetland, India (Zuloaga et al., Considering that the individual contaminants might be a po- 2013). tential cause for environment degradationP and toxicP effects,P individual PAH compounds, DDT isomers, 16PAHs, 7PCBs, 6DDTs 3.5. Human health aspect and g-HCH were compared with two sets of SQGs: ERL/ERM and TEL/PEL depending on the available values of the individual com- In order to estimate the health risks for humans associated with e pounds (Tables 2 3). Further the mERMq was estimated to char- the exposition to the studied carcinogenic organic pollutants, CR acterize theP integratedP ecotoxicological riskP due to the combined through three exposure routes was calculated (Table 4). Total CR impact of 6DDTs, 16PAHs, g-HCH and 7PCBs. Moreover, it is ranged between 1.04 10 6 and 2.09 10 3 with the highest and assumed that: (i) PAHs, DDTs, PCBs and g-HCH contributed addi- lowest contribution of PAHs and g-HCH, respectively. Following the tively to the overall toxicity, rather than antagonistically or syner- quantiﬁcation of CR by Man et al. (2013), the obtained total CR was gistically, and (ii) samples with the same mERMq pose similar in the range of low to moderate risk and the contribution of the ecotoxicological risks (Long et al., 2006;PBotwe et al.,P 2017). pollutants showed the following decreasing trend: The concentration of each PAHs and 16PAHs, 7PCBs, and g- PAHs > DDTs > PCBs > g-HCH. Our results suggested that, out of the HCH did not exceed the ERL as well as TEL values indicating a three exposure routes, the CR through ingestion process would be negligible impact of these POPsP and PAHs in the studied area. prevalent on the other input routes, followed by dermal and However, the concentration of 6DDTs at stations Barrackpore inhalation process. Similar order of exposure routes was also re- (S1), Dakhineswar (S3), Diamond Harbor (S7) and Caning (S10) ported in the sediments of Cau Bay River, Vietnam (Toan and Quy, along with p,p'-DDE at Barrackpore (S1) lied between ERL and ERM 2015). The higher exposure through ingestion may suggest suggesting that more attention should be given to these pollutants greater risk for benthic species and sediment feeders and conse- in the environmental protection practices, as adverse effects might quently for predators due to biomagniﬁcation. occasional occur on the sediment dwelling organisms. While considering the cumulative impact of the studied contaminants, 3.6. Statistical output the spatial mERMq ranged between 0.01 and 0.16 with highest concentration at Barrackpore (S1) (Fig. 4), where the POPs might Principal Component Analysis (PCA) was performed to charac- pose 21% probability of toxicity to the biota. Values in the residual terize the individual loading of 35 variables in the sediments and < stations were 0.1, indicating a minimal risk. the results of the analysis are reported in Table S3 and Fig. 5. The Among the PAHs, only BaA, BbF and Chry are carcinogenic in Kaiser-Meyer-Olkin (KMO) test of sampling adequacy and nature (Wang et al., 2015); their carcinogenicity was determined by the TEQcarc (Savinov et al., 2003; Chen and Chen, 2011). The TEQcarc concentrations ranged 0.32e40.36 ng/g dry wt with a mean value Table 4 of 9.97 ± 16.31 ng/g dry wt (Table S2). Dhakhineswar (S3) showed Cancer risk (CR) probability to the human population due to the carcinogenic POPs. P P P the highest TEQcarc value (40.36 ng/g dry wt), followed by Dha- Average 7PCBs 16PAHs 6DDTs g-HCH makhali (S11) (36.87 ng/g dry wt); these carcinogenic PAHs were < 06 4 05 07 CRder 8.68 10 7.14 10 1.35 10 3.55 10 05 3 05 07 PLOD at Gangasagar (S9) and Caning (S10). The contribution to the CRing 1.67 10 1.38 10 2.60 10 6.85 10 08 07 08 10 TEQscarc was BaA (65%) > BbF (31%) > Chry (4%). The TEQscarc PCRinhale 1.06 10 8.74 10 1.65 10 4.34 10 05 3 05 06 concentrations in the Hooghly estuary studied stations were much CRs 2.54 10 2.09 10 3.95 10 1.04 10

Fig. 4. Mean ERM Quotient (mERMq) of each station. S. Mitra et al. / Chemosphere 221 (2019) 154e165 163

runoff and oil spills. Local people, in particular those living on the shore of the estuary, spend a good period of time throughout the year to maintain their livelihood: for bathing, ﬁshing, maintenance and cleaning of country and mechanized boats, for catching organisms they consume habitually (macrozoobenthos organisms like crabs (Decapoda), detritus-feeder gastropod and bivalve mol- luscs, the mud skippers Boleopthalmus sp.). In addition, a section of people intakes 'holy' estuarine water (enriched with suspended particles) as a part of traditional ritual practices. All these behaviors directly affect their health status as these sediments are enriched with POPs and PAHs and for these reasons it would be important to keep systematic and continuous POP and PAH monitoring.

Acknowledgments

This research was partially supported (laboratory analyses) by the RECETOX Research Infrastructure (LM2015051 and CZ.02.1.01/ 0.0/0.0/16_013/0001761).

Appendix A. Supplementary data

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