Occurrence of triclocarban and benzotriazole ultraviolet stabilizers in water, sediment, and fish from Indian rivers

Occurrence of triclocarban and benzotriazole ultraviolet stabilizers in water, sediment, and fish from Indian rivers

Science of the Total Environment 625 (2018) 1351–1360 Contents lists available at ScienceDirect Science of the Total Environment journal homepage: w...

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Science of the Total Environment 625 (2018) 1351–1360

Contents lists available at ScienceDirect

Science of the Total Environment journal homepage: www.elsevier.com/locate/scitotenv

Occurrence of triclocarban and benzotriazole ultraviolet stabilizers in water, sediment, and fish from Indian rivers Krishnamoorthi Vimalkumar, Elaiyaraja Arun, Selvaraj Krishna-Kumar, Rama Krishnan Poopal, Nishikant Patil Nikhil, Annamalai Subramanian, Ramaswamy Babu-Rajendran ⁎ Ecotoxicology and Toxicogenomics Lab, Department of Environmental Biotechnology, School of Environmental Sciences, Bharathidasan University, Tiruchirappalli 620024, 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

• This study is the first report on emerging contaminants and its risk in Indian environment. • We determined the concentrations of Triclocarban and BUVSs in surfacewater, sediment and fish. • We established a single fraction method to extract multi-residues of PCPs. • A measurable amount of Triclocarban and BUVSs was detected in all the study matrices. • Triclocarban and UV-9 were found predominant in the study matrices during wet and dry season.

a r t i c l e

i n f o

Article history: Received 13 September 2017 Received in revised form 5 January 2018 Accepted 5 January 2018 Available online xxxx Editor: Kevin V. Thomas Keywords: Micro pollutants GC–MS Indian river Environmental compartment LLE

a b s t r a c t Triclocarban and benzotriazole ultraviolet stabilizers (BUVSs) are listed as high production volume synthetic chemicals, used extensively in personal care products. Many of these chemicals persist in the aquatic environment as micropollutants. Knowledge on their fate in freshwater ecosystems is still lacking, especially in the Indian Rivers. Our intention is to study the seasonal distribution, hazard quotient, risk assessment, and bioaccumulation of triclocarban and BUVSs (UV-9, UV-P, UV-326, UV-327, UV-328, and UV-329) during wet and dry seasons in water, sediment and fish from the Kaveri, Vellar, and Thamiraparani rivers in Tamil Nadu State, India. Triclocarban and BUVSs were identified in all matrices analysed. Triclocarban was found in water, sediment, and fish up to 1119 ng/L, 26.3 ng/g (dry wt.), and 692 ng/g (wet wt.), respectively. Among BUVSs, UV-329 was found up to 31.3 ng/L (water samples), UV-327 up to 7.3 ng/g (sediment samples), and UV-9 up to 79.4 ng/g (fish samples). The hazard quotient (HQenv.) for triclocarban in surface water was found to be at risk level (HQenv. N1) in the Kaveri, and Thamiraparani rivers during dry season. Bioaccumulation factors indicate that target compounds (triclocarban and BUVSs) could bio-accumulate in organisms. © 2018 Elsevier B.V. All rights reserved.

1. Introduction The current lifestyle allows daily exposure to a variety of new chemicals through diet, environmental media (air, water, etc.) and use ⁎ Corresponding author. E-mail address: [email protected] (R. Babu-Rajendran).

https://doi.org/10.1016/j.scitotenv.2018.01.042 0048-9697/© 2018 Elsevier B.V. All rights reserved.

of consumer products including, pharmaceuticals and personal care products. During the past decade, there is an increasing public concern for the environmental contamination, exposure and harmful effect of persistent emerging chemicals such as triclocarban and benzotriazole ultraviolet stabilizers (BUVSs) (Horii et al., 2007; Nakata et al., 2012a). Although, there exist a number of studies on persistent organochlorine contamination levels in Indian rivers (Patil et al., 2015; Sinha and

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Loganathan, 2015), publications regarding the environmental levels, bioconcentration and toxicity profiles of these new persistent chemicals are still scare. In this study, we attempted to investigate occurrence of triclocarban and BUVSs residues in water, sediment, and fish from selected rivers in southern India. To our knowledge, this is the first study dealing with triclocarban and BUVSs in Kaveri, Vellar, and Thamairaparani rivers. Triclocarban (3-(4-chlorophenyl)-1-(3,4-dichlorophenyl)urea) is one of the major organic constituents of personal care products since 1957 (Halden, 2014), comprising a chemical structure of two benzene rings with chlorine attachments. It has a high sorption capacity with a log octanol-water partition coefficient (log Kow) of 4.9, a pH b 7, and water solubility of 0.65–1.55 mg/L (Venkatesan et al., 2012). Because of its germicidal (bacterial and fungal) property, triclocarban is used as an active ingredient in many consumer products, including kitchen detergents, textiles, plastics, cosmetics, and children's toys (Gago et al., 2015; Souchier et al., 2016). Triclocarban is detected in surface water, wastewater, sludge, biosolids, amended soils, sediments, fish (bile and muscle tissues), and human samples (plasma, urine, and milk) (Klein et al., 2010; Hinther et al., 2011; Gago et al., 2015; Souchier et al., 2016). In the environment, triclocarban degrades to di and monochlorinated secondary products, which persist for up to 540 days (Venkatesan et al., 2012; Pycke et al., 2014). Overexposure of skin to ultraviolet (UV) light causes dermal anomalies and sometimes cancer (Orazio et al., 2013). To avoid this phenomenon various organic UV absorbents have been employed. Among them Tinuvins or benzotriazoles are 2-hydroxyphenyl benzotriazole derivatives (heterocyclic with nitrogen atom combination) having a molecular structure of C6H5N3 (Montesdeoca-Esponda et al., 2013) and, a log Kow of 4.31–8.28, are widely in use. Different types of benzotriazole ultraviolet stabilizers (BUVSs) are available in the market such as UV-P, UV-234, UV-326, UV-327, UV-328, and UV-329 (Nakata et al., 2012b). BUVSs are extensively used as additions in antifogging products, polymeric surfaces, medical materials (dental restorative components and contact lenses), construction materials, corrosion inhibitors, and in consumer products (film, shoes, glasses, and some sports equipment). BUVSs are incorporated in the PCPs (sunscreen, soap, shampoo, toothpaste, scrubs, hair dye, nail polish, moisturizing cream, lipstick, makeup, and after-shave lotion) up to 25% (by weight) (Kim et al., 2011a; Montesdeoca-Esponda et al., 2013). BUVSs are detected in environmental (surface water, sediment, wastewater, sewage sludge, ground water etc.) and biological samples (fish muscle, liver and in human samples (blood and urine)) (Kim et al., 2011b; Tangtian et al., 2012; Montesdeoca-Esponda et al., 2013; Avagyan et al., 2015). According to Lai et al. (2014), BUVSs have a dissipation rate of 218 days in the environment. When considering the lifespan of these chemicals, the first half is very short as an ingredient in consumer products and the second half is mostly in the environment as micro-pollutants (Halden, 2014). The European Chemical Agency and British Environment Agency proposed triclocarban and BUVSs as substances of potential concern (Avagyan et al., 2015; Brandt et al., 2016). Triclocarban is also classified as an endocrine disruptor (steroid hormone enhancer) (Mulla et al., 2016), having hematotoxic and carcinogenic potential (Hinther et al., 2011). BUVSs are capable of accumulating in organisms and causing toxic effects (Nakata et al., 2012b), and have mutagenic, genotoxic, and hormonal disruptive properties (Fent et al., 2008; Montesdeoca-Esponda et al., 2013; Avagyan et al., 2015). Hazard quotients (HQs) developed by USEPA were used to predict the potential health risks based on the EC50 or LC50 of chemical pollutants in aquatic organisms. If the calculated HQ is b1, say what “it” is here is not treated as a health risk: however, a value N 1 indicates a potential adverse health risk (Zhao et al., 2010). Environmental screening of organic micro-pollutants is a challenging task; hence it is necessary to develop a sensitive technique for trace level detection (Bisceglia et al., 2010). Among the various

analytical techniques, liquid-liquid extraction (LLE) has gained preference and is considered a convenient method in analysing micro-pollutants. Quantification of organic compounds of the extracted sample by a typical hyphenated instrument like gas chromatography mass spectrometry (GC–MS) is advantageous for accuracy, easy handling, and wide dynamic range (Pitarch et al., 2007; Ramaswamy et al., 2011). Kaveri, Vellar, and Thamiraparani are the major rivers in Tamil Nadu state, India which have an imperative role in fulfilling drinking and agricultural demands. These peninsular rivers reach the Bay of Bengal with 19 tributaries. In our previous studies, we have detected carbamazepine, triclosan, parabens, diclofenac, ketoprofen, naproxen, ibuprofen, phthalates, and acetylsalicylic acid in all these three rivers (Ramaswamy et al., 2011; Shanmugam et al., 2014b; Selvaraj et al., 2014). Very little is known on contamination levels of triclocarban and BUVSs in these rivers. Considering the harmful effect of these micropollutants reported elsewhere (Fent et al., 2008; Hinther et al., 2011; Nakata et al., 2012a; Mulla et al., 2016), and the need for baseline data on these pollutants in our regional rivers, we aimed at fulfilling this research gap by analysing the contamination levels of triclocarban and BUVSs in the three rivers during wet and dry seasons. 2. Material and methods 2.1. Chemicals Triclocarban (CAS 101-20-2), UV-P (CAS 2440-22-4), UV-326 (CAS 3896-11-5), UV-328 (CAS 25973-55-1), and UV-329 (CAS 3147-75-9) were procured from Wako Pure Chemical (Osaka, Japan). UV-9 (CAS 2170-39-0), and UV-327 (CAS 3864-99-1) were procured from SigmaAldrich (St. Louis, MO, USA). Acetone, hexane, dichloromethane, methanol, and silica gel were purchased from MERCK Specialties Private Limited (Mumbai, India). 2.2. Sampling area Grab sampling was done during wet (November 2015) and dry (May 2016) seasons. Surface water, sediment, and fish (Labeo rohita, Oreochromis mossambicus, Wallago attu, Etroplus suratensis, Puntius filamentosus, and Gibelion catla) were sampled from 29 locations from three major rivers Kaveri, Vellar, and Thamiraparani of Tamil Nadu, India. Water samples were immediately processed for analysis, whereas, sediment and fish samples were kept in a deep freezer (− 20 °C) (Blue Star, India) until further chemical analysis. The sampling area and the number of samples (N = 131) are illustrated in Fig. 1 and Table S1, respectively. 2.3. Cleaning of glassware All the glassware used in this study were rinsed thoroughly with HCl (50%), then in double distilled water, and finally with acetone. After drying, all the glassware were wrapped with aluminium foil and kept in a hot air oven at 200 °C for about 8 h. 2.4. Chemical extraction 2.4.1. Water samples Liquid-liquid extraction was performed by following the method described by Nakata et al. (2010) with slight modifications. 500 ml of water sample and 50 ml of hexane were taken in a 2000 ml separating funnel and shaken vigorously for 15 min, and kept undisturbed until the hexane layer got separated. After collecting the hexane layer, the same water sample was extracted again with 50 ml hexane and the hexane layer was collected. The moisture content from the hexane extract was removed by adding 10 g of anhydrous sodium sulphate. Then the hexane extract was condensed using a rotary vacuum evaporator

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Fig. 1. Map illustrating the sampling sites in the Kaveri (K1–K15), Vellar (V1–V4), and Thamiraparani (T1–T11) rivers, India.

(BUCHI R-210). Further, the extract was condensed to 1 ml under nitrogen stream and transferred to a glass vial for GC–MS analysis. 2.4.2. Sediment and fish tissue samples Both sediment (5 g dry wt.) and fish (muscle tissue: 2 g wet wt.) samples were extracted following the method of Nakata et al. (2010) with some modifications. The samples were mixed with 25 ml of hexane and dichloromethane at 1:1 ratio in a glass tube and extracted using ultrasonication (for 15 min.). Next, the solvent layer was collected and transferred into a pear shape flask (Borosil, India) for condensation and the extraction was repeated once again. After condensing the combined extracts to 1 ml it was transferred into a glass vial for GC–MS analysis. 2.5. Method validation 2.5.1. Analytical measurements The concentrations of triclocarban and BUVSs in water, sediment, and fish muscle tissue samples were measured by using GC (GC2010)-MS (QP-2010) (Shimadzu Corporation, Japan). The analytical separation was done with HP-5MS column (30 m, 0.25 mm i.d., 0.25μm film thickness) with the following conditions. Initially, GC oven temperature was held at 120 °C for 3 min and then the temperature was gradually increased to 260 °C at the rate of 6 °C/min. Finally, the column temperature was increased to 320 °C at a rate of 8 °C/min and held for 5 min. Sample injection (1 μl) was performed using an autosampler (AOC-20i) in the split-less mode. Helium (99.999% purity) was used as a carrier gas at a flow rate of 1.50 ml/min. The injector port, interface, and ion source temperatures were set at 280 °C, 300 °C, and 230 °C, respectively. The mass spectrometer was operated in electron ionization (EI) mode at 70 eV and at an emission current of 60 μA. Full scan data was obtained in a mass range of m/z 50–500. Scanning interval and selected ion monitoring (SIM) sampling rate were 0.2 s. The mass selective detector was operated in SIM mode. 2.5.2. Quality assurance and quality control (QA/QC) Analyte recovery for the surface water, sediment, and fish tissue samples was determined using spiked samples with triclocarban and BUVSs (50 ng/g). Net recovery of these compounds was calculated by subtracting the analyte concentrations in un-spiked samples from the concentrations in the corresponding spiked samples. The recovery of all the compounds in water, sediment, and biota ranged as 54–122%, 76– 118%, and 79–120%, respectively (Table S2). The limit of detection

(LOD), and limit of quantification (LOQ) for target compounds were estimated based on signal-to noise ratio of 3, and 10 times, respectively. Further, the method detection limit (MDL) and method quantification limit (MQL) of the samples were calculated by using the formula (1) and (2), given by Souchier et al. (2015) and the values are given in Table S3. MDL ¼ LOD=ARR ðabsolute recovery rateÞ

ð1Þ

MQL ¼ LOQ =ARR

ð2Þ

2.5.3. Bioaccumulation factor (BAF) The BAF of fish was calculated based on the formula (3 and 4) formulated by Higgins et al. (2009). Bioaccumulation factor ðwaterÞ ðBAFw Þ ¼ C f =Cw

ð3Þ

Accumulation factor ðsedimentÞ ðAFs Þ ¼ C f =Cs

ð4Þ

where, Cf and Cw are the concentration of triclocarban and BUVSs in fish tissue (ng/g ww), and in water (ng/L), respectively; Cs is the concentration of triclocarban and BUVSs in sediment (ng/g dry wt.). 2.6. Risk assessment 2.6.1. Environmental risk Risk of environmental chemicals is expressed as hazard quotient (HQenv.) which was calculated based on formula (5) (as cited in Ramaswamy et al., 2011). HQ env: ¼ MEC=PNEC

ð5Þ

where, MEC is the measured environmental concentration and PNEC is predicted no-effect concentration. 2.6.2. Human dietary risk It is calculated as HQhuman using fish intake and admissible intake of chemical residues as given in formula (6) and (7) (as cited in Shanmugam et al., 2014a). HQ human ¼ AE=ADI

ð6Þ

AE ¼ ðC f  FCÞ=BW

ð7Þ

NA NA NA NA NA 2.83.1 3.0 ± 0.2 3.0 100 0.628 7.4 ± 3.6 2.0 100 NA NA NA NA NA ND0.2 0.2 ± ND 0.2 50 ND6.1 1.6 ± 1.8 1.1 91.7 NA NA NA NA NA 0.61.3 1.0 ± 0.5 1.0 100 ND13.4 3.2 ± 3.9 1.5 91.7 NA NA NA NA NA 0.30.1 0.6 ± 0.4 0.6 100 ND6.9 1.6 ± 2.5 0.5 83.3 NA NA NA NA NA 0.44.0 2.2 ± 2.6 2.2 100 0.3341.2 6.9 ± 11.5 2.4 100 NA NA NA NA NA 1.21.5 1.3 ± 0.2 1.3 100

ND4.4 1.4 ± 1.2 0.9 95 0.22.7 0.9 ± 0.8 0.6 100 ND6.59 1.41 ± 1.7 0.71 93.3 ND4.3 0.9 ± 1.4 0.2 80 ND0.8 0.2 ± 0.3 0.1 87.5 ND3.76 0.35 ± 0.8 0.11 83.3 ND4.4 0.6 ± 1.1 0.3 70 0.17.3 2.0 ± 2.7 0.4 100 ND3.46 0.88 ± 1.5 0.26 83.3 ND4.6 0.5 ± 1.1 0.2 80 ND0.5 0.2 ± 0.2 0.1 75 ND1.94 0.32 ± 0.4 0.16 60 ND2.1 0.3 ± 0.5 0.1 75 ND0.2 0.1 ± 0.1 0.1 62.5 ND1.41 0.21 ± 0.3 0.13 53.3

3.915.9 8.1 ± 3.8 7.0 100 1.729.3 13.7 ± 8.1 12.3 100 ND0.7 0.5 ± 0.2 0.6 30 ND1.0 0.8 ± 0.3 0.9 37.5 ND5.2 3.4 ± 1.7 2.9 36.7 ND6.4 3.3 ± 1.3 2.9 70 ND5.1 3.6 ± 1.0 3.4 75 ND9.5 4.3 ± 2.0 3.9 70 ND3.8 1.5 ± 0.9 1.5 65 ND2.1 1.5 ± 0.5 1.4 75 ND5.7 3.7 ± 1.1 3.6 56.7 ND1.6 0.8 ± 0.4 0.6 25 ND0.9 0.6 ± 0.3 0.6 37.5 ND2.7 2.3 ± 0.3 2.2 63.3

VR KR VR

TR

KR

VR

TR

KR

VR

TR

UV-328 UV-327 UV-326

KR – Kaveri River, VR- Vellar River, TR – Thamiraparani River, ND – not detected, NA - Not Applicable, SD – standard deviation.

NA-not applicable, ND-not detected, SD – standard deviation.

0.6979.4 14 ± 22.8 2.4 100

NA NA NA NA

Fish (n = 14) Concentration range (ng/g) Mean ± SD Median Detection (%)

0.8–11.1 5.9 ± 7 5.9 100

ND0.8 0.2 ± 0.2 0.1 85

1.4–692 73.4 ± 196 8.2 100

ND0.3 0.1 ± 0.1 0.1 87.5

Fish (ng/g) Concentration range Mean ± S.D. Median Detection frequency (%)

ND1.07 0.32 ± 0.3 0.19 96.7

ND-9.2 1.9 ± 2.3 1.3 70

Sediment (n = 58) Concentration range (ng/g) Mean ± SD Median Detection (%)

ND-4.3 2.6 ± 1.4 1.9 38

ND28.1 4.4 ± 6.3 2.0 95

ND-26.3 4.9 ± 6 3.2 83

ND3.7 1.8 ± 1.3 1.5 75

Sediment (ng/g) Concentration range Mean ± S.D. Median Detection frequency (%)

KR

3.3–168 55.6 ± 45 57.1 100

TR

2.2–103 25.3 ± 33 14.6 100

VR

8–1119 123.6 ± 253 49.2 100

KR

Thamiraparani

UV-P

Vellar

Water (ng/L) Concentration range Mean ± S.D. Median Detection frequency (%)

UV-9

Rivers Kaveri

BUVSs

Samples

Environmental matrices

Table 1 Concentration range, mean, median, and detection (%) of triclocarban in environmental matrices from the rivers in India.

Table 2 Concentration range, mean, median, and detection (%) of BUVSs in environmental matrices from the rivers in India.

A measurable amount of triclocarban was found in most of the water, sediment, and fish tissue samples showing the wide distribution of triclocarban in all the three rivers. The concentration (range, mean, and median) and detection frequency of triclocarban were given in Tables 1 and S1. The maximum concentrations of triclocarban was found in water (1119 ng/L), sediment (26.3 ng/g), and fish tissue (692 ng/g) sampled from Kaveri river with 100% frequency of detection in water and fish samples, and N 82% in sediment. This is an indication of habitual and ample usage of triclocarban in India. In the present study, triclocarban concentration in water was higher than the sediment and fish samples from Kaveri river. This could be due to the surface runoff of triclocarban from its potential sources, i.e. leaching from land, and treated/non-treated domestic wastewater. Senthil Kumar et al. (2010) reported higher concentrations of triclocarban in the particulate phase than in the dissolved phase of wastewater from Savannah, Georgia, USA. In water, triclocarban and suspended particulate matter (SPM) relate with each other and accumulate in the sediment and this could elevate the concentration of triclocarban in water and sediment (Zhao et al., 2013). Higgins et al. (2011) and Wang et al. (2014) stated that personal care products (PCPs) persist in the sediment because of their high affinity towards organic carbon. Moreover, triclocarban has a low solubility and high noctanol-water partition coefficient; this could be a possible reason for its accumulation in matrices like sediment (Lv et al., 2014). Triclocarban has high affinity to organic carbon (Gautam et al., 2014) and this could be used as a reliable indicator for organic contamination in the aquatic ecosystem. Here the concern is about the capacity of resistance of triclocarban to chemical and biological degradation. Further, it is opined that, in the environment triclocarban disintegrates through photolytic and biodegradation processes (anaerobic) and results into chlorinated anilines which are highly carcinogenic in nature (Pycke et al., 2014). Fish spend their entire life in water and are constantly exposed to PCPs, which are continuously released through wastewater into the

TR

3.1. Triclocarban occurrence in environmental samples

KR

UV-329

3. Results and discussion

ND26.5 5.7 ± 4.8 4.2 93.3

VR

TR

where, AE-Adult exposure (μg/kg bw); Cf-concentration of target compounds (Ctriclocarban & BUVSs) in fish; FC per diem- fish consumption by Indian population (27 g per diem); BW-body weight (60 kg); and ADIacceptable daily intake (50 μg/kg bw). HQ indicates the negligible/no risk at b1 and feasible risk at N 1.

ND31.3 12.3 ± 6.6 10.4 95

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Water (n = 59) Concentration range (ng/L) Mean ± SD Median Detection (%)

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Fig. 2. Seasonal variation of triclocarban levels in water, sediment, and fish from the rivers in India.

aquatic systems, further, PCPs have high hydrologic retention times, and pseudo-persistent in water (Ramirez et al., 2009). Triclocarban accumulation in fish tissue fully depends on the concentration in water or sediment or by both.

Bioaccumulation values in this study positively relate with the triclocarban concentration in sediment and water samples and this finding corroborates with the report of Keith et al. (2001), Nakata (2005), Venkatesan et al. (2012), Pycke et al. (2014), and Shanmugam

Fig. 3. Seasonal variation (wet and dry) of BUVSs levels in water, sediment, and fish tissue samples from rivers in India.

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Table 3 HQenv. of triclocarban and BUVSs in water from the rivers in India. Rivers

KR VR TR

Triclocarban

UV-9

Wet

Dry

Wet

Dry

Wet

UV-P Dry

Wet

UV-326 Dry

Wet

UV-327 Dry

Wet

UV-328 Dry

Wet

UV-329 Dry

0.62 0.65 0.58

3.6 0.3 1.2

0.0002 0.0001 0.00026

0.0002 0.00003 0.00002

– – –

0.05 0.01348 0.00007

0.0029 0.0018 0.0026

0.005 0.0011 0.0011

0.0109 0.0131 0.011

0.017 0.011 0.011

0.023 ND 0.002

0.048 0.011 0.0071

0.021 0.018 0.037

0.048 0.022 0.023

KR – Kaveri River, VR- Vellar River, TR – Thamiraparani River, ND – not detected.

et al. (2014a). In one of our previous studies, we measured the concentration of triclosan (TCS), another antimicrobial compounds in fish at 0.73–50 ng/g with 100% detection frequency in all the sampling sites of Kaveri river (Shanmugam et al., 2014a).

3.2. Benzotriazole ultraviolet stabilizers occurrence in environmental samples The concentration of BUVSs such as UV-9, UV-P, UV-326, UV-327, UV-328, and UV-329 were detected at nanogram (ng) level in water, sediment, and fish from Kaveri, Vellar, and Thamiraparani rivers (no fish was sampled) and are summarised in Table 2. This shows the ubiquitous distribution of BUVSs in environmental matrices in all the three rivers. Concentrations of BUVSs ranged from ND-31.3 ng/L in water, ND-7.3 ng/g in sediment, and ND-79.4 ng/g in fish. The BUVSs concentration in all the matrices were high in Kaveri river followed by Thamiraparani river, and Vellar river, and their detection frequency ranged from 37 to 100% (Kaveri river), 25 to 100% (Thamiraparani river), and 37.5 to 100% (Vellar river). Among BUVSs, UV-329, UV-327, and UV-9 were found predominant in water (Thamiraparani river), sediment (Vellar river), and fish (Kaveri river) samples. This reveals the high production/utility of BUVSs in customer products in the study area. The habit of using sun creams has phenomenally increasing among the Indian population; this could be the potential source of occurrence of BUVSs in Indian rivers. This is the first report on the occurrence of BUVSs in the Indian freshwater environment. BUVSs are ubiquitous in the environmental compartments and biota as shown in the reports of Nakata et al. (2010) and Brandt et al. (2016). The detected BUVSs concentration in the water samples of the present study is lower than in River Glatt (6.3 μg/L), Switzerland (Giger et al., 2006). Our value on BUVSs concentration in sediment samples is much lower than in Pawtuxet river, USA (10 mg/g) (Reddy et al., 2000), and

Songhua river, China (9.93 ng/g), Saginaw river, USA (22.5 ng/g), and Detroit, USA (389 ng/g) (Zhang et al., 2011). BUVSs, especially UV-326, UV-327, and UV-328 were detected in different environmental matrices from Saitama Prefecture, Japan and their concentrations ranged from ND to 4928 ng/L in water samples and 2.0 to 3422 μg/kg in sediment samples (Kameda et al., 2011). However, BUVSs in fish tissue samples (79.4 ng/g) corroborate the existing reports. Nakata et al. (2009, 2010) reported the occurrence of BUVSs (UV-326, UV-327, and UV-328) in biota (0.10–55 ng/g; wet wt.), and sediment (1.5–320 ng/g; dry wt.) around Ariake Sea, Japan. Nakata et al. (2012b) reported UV-326, UV327, and UV-328 up to 450, 150, and 220 ng/g lipid wt., respectively in mussels collected from Asia-Pacific coastal waters. Kim et al. (2011a) reported the BUVSs in fish samples collected from Manila Bay, the Philippines. The removal efficiency of benzotriazoles in WWTPs is b62%, and the biological degradation rate of aerobic and anaerobic conditions is also slow showing their persistent behaviour (Liu et al., 2011). Compounds with high octanol-water partition coefficients such as benzotriazoles, have high affinity towards suspended particulate matter in water, and ultimately accumulate in the sediments (Nakata et al., 2012b). Sediment acts as a pertinent sink and potential source of BUVSs in aquatic organisms (Ruan et al., 2012; Lu et al., 2016). Concentrations of BUVSs in environmental matrices are due to different potential sources, such as direct discharge of wastewater, human/domestic cattle bathing, wastewater from chemical plants, etc. (Kiss and Fries, 2009; Brandt et al., 2016).

3.3. Seasonal variations of triclocarban and benzotriazole ultraviolet stabilizers Bu et al. (2013) insisted in their review that the seasonal distribution data is essential to know the contamination of chemicals and their hot

Fig. 4. Human health risk levels of triclocarban during wet (A) and dry (B) seasons.

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spots. Further, the data could act as a starting point in mitigating the risk of water contaminants. During both wet and dry seasons high concentration of triclocarban was found in water, sediment, and biota samples sampled from Kaveri river (Fig. 2). Peng et al. (2017) reported that the

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concentrations of environmental contaminants were higher during the dry season in six urban rivers in Guangzhou, China, when compared to the wet season which could be due to differences in river flow rate during dry season.

Fig. 5. BAFw and AFs of triclocarban and BUVSs for the rivers in India during wet (A) and dry (B) seasons.

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Lv et al. (2014) studied the temporal variation of triclocarban and noted an elevated concentration in the city side area of River Jiulong, Southeast China. They concluded that the continued use of consumer products containing triclocarban may increase its load in the aquatic ecosystem. Moreover, natural attenuation (e.g. due to rain) especially rain could load/disperse aquatic contaminants by flooding. This could result in the decrease of triclocarban concentration during the wet season. Zhao et al. (2010) examined the seasonal distribution of triclocarban in Shujiang, Zhujiang, and Liuxi rivers in China during wet and dry seasons. They concluded that the seasonal variation in the water samples may be due to dilution by rainwater during the wet season compared to the dry season. The seasonal distributional data of BUVSs (except UV-329) in water, sediment, and fish from the Kaveri, Vellar, and Thamiraparani rivers were ≤ 10 ng/L (Fig. 3). The seasonal distribution in this study shows that Kaveri river is highly loaded with UV-9, UV-P, UV-326, UV-327, UV-328, and UV-329 when compared to the other two rivers. The inconsistency in the concentrations of triclocarban and BUVSs during wet and dry seasons depends on the influencing factors such as rainfall, temperature, and photo degradation; our finding matches with the statement of Sui et al. (2015). Triclocarban and BUVSs in wastewater may gather in flood water and ultimately reach surface water during the wet season. But during dry season, due to direct discharge of domestic wastewater into the surface water, triclocarban and BUVSs may attach with suspended particulate matters and settle in the bottom sediment. The report of the present study indicates that triclocarban and BUVSs could persist in the environmental matrices of Kaveri, Vellar, and Thamiraparani rivers.

3.4. Risk assessment 3.4.1. Hazard quotientenvironment The HQsenv. of triclocarban and BUVSs for Kaveri, Vellar, and Thamiraparani rivers during the wet and dry seasons are shown in Table 3. The predicted no effect concentration (PNEC) based on EC50 or LC50 values of fish for triclocarban was calculated as 58 ng/L, by adopting the safety factor 10. HQenv. calculated for triclocarban during wet season was b 1 in all the three rivers, whereas it was found to be 3.6, and 1.2 during dry season at Kaveri river, and Thamiraparani river water samples, respectively. Triclocarban creates less risk during the wet season in all the three rivers and high risk in Kaveri river, and Thamiraparani river during the dry season. Zhao et al. (2010) measured the risk for triclocarban in Pearl river and reported the condition as “worst case scenario”. The HQ in Shijing River water was N1 with a value of 9.55 in dry season, and 5.15 during the wet season. They also suggested the need for more attention on the fate of triclocarban in environmental matrices. The HQenv. of BUVSs in Kaveri, Vellar, and Thamiraparani rivers water samples during both wet and dry seasons showed a low level of risk with a value b 0.1.

3.4.2. Hazard quotientshuman Fish is an important protein source for humans and also supplies rich nutrients. Triclocarban could accumulate in fish tissue and the metabolites of triclocarban readily bind covalently with the protein molecules. Triclocarban is oxidised by cytochrome P450 to form monohydroxylated metabolites (2-OH, 3-OH, and 6-OH triclocarbans) and then conjugates to form sulphate and glucuronate and finally excreted. Triclocarban is known to cause endocrine disruption by enhancing the activity of steroids similar to other chemicals (Schebb et al., 2011). Fig. 4 shows the human health risk of triclocarban through fish intake during wet and dry seasons. In wet and dry seasons HQshuman for triclocarban was b 1 in Kaveri river and Vellar river, the possibility of human risk through fish consumption is very low.

Table 4 Contribution (%) of triclocarban and BUVSs in water from rivers in India. Season

Triclocarban

UV-9

UV-P

UV-326

UV-327

UV-328

UV-329

Wet KR VR TR

62 67 56

10 7 12

0 0 0

5 4 4

6 8 5

3 0 0

14 14 23

Dry KR VR TR

84 52 82

2 3 1

1 2 1

2 3 1

2 10 4

1 2 0

8 28 11

KR – Kaveri River, VR- Vellar River, TR – Thamiraparani River.

3.5. BAFw and AFs of triclocarban and BUVSs The lipophilicity of triclocarban and BUVSs could enhance accumulation in sediment. Through diet these lipophilic compounds reaches the biota and accumulate in it. Thus BAF data could be used as a reliable method to compare the contamination level of different matrices (Brandt et al., 2016; Schebb et al., 2011; Nakata et al., 2012b). Bioaccumulation factors (BAFw and AFs) for triclocarban and BUVSs during wet and dry seasons in Kaveri river and Vellar river are shown in Fig. 5. The BAFw of triclocarban in wet, and dry seasons ranged between 0.05–15.4, and 0.02–0.08, respectively, and the AFs ranged as 4.4–238, and 0.17–42.85 for wet, and dry seasons, respectively. Coogan et al. (2007) and Coogan and La Point (2008) reported BAF for triclocarban in algae (2700) and snail (1600), respectively. In our previous work (Shanmugam et al., 2014a) we reported the BAFw and AFs for TCS as 820 and 2.12 in Kaveri river, indicating the bioaccumulation in fish ‘Gibelion catla’. Similar to triclocarban, BAFw and AFs for BUVSs was found higher in wet season when compared to dry season, further, UV-9 was found to be higher (BAFw range - 3.6-34.8; AFs range - ND166.2) than other BUVSs in this study. When comparing BAFw and AFs for triclocarban and BUVSs, a higher range was found for sediment. Nakata et al. (2009) reported the BAF of UV-327 as 2400 and 14,000 for sole and mullet fish from Ariake Sea, Japan, respectively.

3.6. Contribution of triclocarban and BUVSs The overall percentage contributions of triclocarban and BUVSs in the rivers Kaveri, Vellar, and Thamiraparani rivers were given in the Table 4. In the wet season, triclocarban contribution was N 60% in Kaveri river and Vellar river. Among BUVSs, UV-329 was found predominant with a percentage of 23, 14, and 14 in Thamiraparani, Kaveri, and Vellar rivers, respectively. During the dry season, triclocarban percentage was N80% in Kaveri river and Vellar river. Among BUVSs, UV-329 had contributed high with 28%, 11%, and 8% in Vellar, Thamiraparani, and Kaveri rivers, respectively. In all the three rivers bathing and direct discharge of domestic wastewater are witnessed, hence, these activities may contribute to triclocarban and BUVSs load in these rivers.

4. Conclusions This study shows the occurrence of triclocarban and BUVSs during both dry and wet seasons in all the three rivers evaluated in Tamil Nadu state, India. Further, wastewater discharge may contribute these anthropogenic chemicals into the rivers. As a micro-pollutant, triclocarban HQenv. in Kaveri river and Thamiraparani river water was N1 in dry season. The study revealed that Kaveri river elicits slightly higher levels of triclocarban and BUVSs than the other two rivers. The health status of Indian fresh water ecosystems and potential sources of emerging pollutants is a matter of serious concern, and this is the first study reports the fate of triclocarban and BUVSs in Indian freshwater ecosystems and provides a baseline data for future research.

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Conflict of interest There are no conflicts of interest to declare. Acknowledgements The authors thank United Nations University, Tokyo, Japan and SHIMADZU Corporation, Japan, for the GC/MS facility at Bharathidasan University, and the funding agencies UGC-SAP, UGC-MRP (F.No.- 43313/2014(SR)), DST-FIST, DST-SERB (NPDF), DST-PURSE, and DBT New Delhi, India for providing funding for research facilities to carry out the research. The authors also thank Dr. Brianna Cassidy, Chief Science Officer, at CDX Analytics, Salem, MA., USA, for her constructive criticism and valuable suggestions on the manuscript. Appendix A. Supplementary data Supplementary data to this article can be found online at https://doi. org/10.1016/j.scitotenv.2018.01.042. References Avagyan, R., Luongo, G., Thorsén, G., Östman, C., 2015. Benzothiazole, benzotriazole, and their derivates in clothing textiles-a potential source of environmental pollutants and human exposure. Environ. Sci. Pollut. Res. Int. 22 (8):5842–5849. https:// doi.org/10.1007/s11356-014-3691-0. Bisceglia, K.J., Yu, J.T., Coelhan, M., Bouwer, E.J., Roberts, A.L., 2010. Trace determination of pharmaceuticals and other wastewater-derived micropollutants by solid phase extraction and gas chromatography/mass spectrometry. J. Chromatogr. A 1217 (4): 558–564. https://doi.org/10.1016/j.chroma.2009.11.062. Brandt, M., Becker, E., Jöhncke, U., Sättler, D., Schulte, C.A., 2016. Weight-of-evidence approach to assess chemicals: case study on the assessment of persistence of 4,6substituted phenolic benzotriazoles in the environment. Environ. Sci. Eur. 28 (1):4. https://doi.org/10.1186/s12302-016-0072-y. Bu, Q., Wang, B., Huang, J., Deng, S., Yu, G., 2013. Pharmaceuticals and personal care products in the aquatic environment in China: a review. J. Hazard. Mater. 262:189–211. https://doi.org/10.1016/j.jhazmat.2013.08.040. Coogan, M.A., La Point, T.W., 2008. Snail bioaccumulation of triclocarban, triclosan, and methyltriclosan in a North Texas, USA, stream affected by wastewater treatment plant runoff. Environ. Toxicol. Chem. 27 (8):1788–1793. https://doi.org/10.1897/07374.1. Coogan, M.A., Edziyie, R.E., La Point, T.W., Venables, B.J., 2007. Algal bioaccumulation of triclocarban, triclosan, and methyl-triclosan in a North Texas wastewater treatment plant receiving stream. Chemosphere 67 (10):1911–1918. https://doi.org/10.1016/ j.chemosphere.2006.12.027. Fent, K., Kunz, P.Y., Gomez, E., 2008. UV filters in the aquatic environment induce hormonal effects and affect fertility and reproduction in fish. Chimia 62:368–375. https://doi.org/10.2533/chimia.2008.368. Gago, F.P., Díaz-Cruz, M.S., Barceló, D., 2015. UV filters bioaccumulation in fish from Iberian river basins. Sci. Total Environ. 518–519:518–525. https://doi.org/10.1016/ j.scitotenv.2015.03.026. Gautam, P., Carsella, J.S., Kinney, C.A., 2014. Presence and transport of the antimicrobials triclocarban and triclosan in a wastewater-dominated stream and freshwater environment. Water Res. 48:247–256. https://doi.org/10.1016/j.watres.2013.09.032. Giger, W., Schaffner, C., Kohler, H.P.E., 2006. Benzotriazole and tolyltriazole as aquatic contaminants. 1. Input and occurrence in rivers and lakes. Environ. Sci. Technol. 40 (23):7186–7192. https://doi.org/10.1021/es061565j. Halden, R.U., 2014. On the need and speed of regulating triclosan and triclocarban in the United States. Environ. Sci. Technol. 48 (7):3603–3611. https://doi.org/10.1021/ es500495p. Higgins, C.P., Paesani, Z.J., Abbott Chalew, T.E., Halden, R.U., 2009. Accumulation of triclocarban in Lumbriculus variegates. Environ. Toxicol. Chem. 28 (12):2580–2586. https://doi.org/10.1897/09-013.1. Higgins, C.P., Paesani, Z.J., Chalew, T.E.A., Halden, R.U., Hundal, L.S., 2011. Persistence of triclocarban and triclosan in soils after land application of biosolids and bioaccumulation in Eisenia foetida. Environ. Toxicol. Chem. 30 (3):556–563. https://doi.org/ 10.1002/etc.416. Hinther, A., Bromba, C.M., Wulff, J.E., Helbing, C.C., 2011. Effects of triclocarban, triclosan, and methyl triclosan on thyroid hormone action and stress in frog and mammalian culture systems. Environ. Sci. Technol. 45 (12):5395–5402. https://doi.org/10.1021/ es1041942. Horii, Y., Reiner, J.L., Loganathan, B.G., Kumar, K.S., Sajwan, K., Kannan, K., 2007. Occurrence and fate of polycyclic musks in wastewater treatment plants in Kentucky and Georgia, USA. Chemosphere 68, 2011–2020. Kameda, Y., Kimura, K., Miyazaki, M., 2011. Occurrence and profiles of organic sunblocking agents in surface waters and sediments in Japanese rivers and lakes. Environ. Pollut. 159 (6):1570–1576. https://doi.org/10.1016/j.envpol.2011.02.055. Keith, T.L., Snyder, S.A., Nayler, C.G., Staples, C.A., Summer, C., Kannan, K., Giesy, J.P., 2001. Identification and quantitation of nonylphenol ethoxylates and nonylphenol in fish

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