Tamil Nadu, India

Marine Pollution Bulletin 109 (2016) 612–618

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Marine Pollution Bulletin

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Baseline Assessment of perﬂuorooctanoic acid and perﬂuorooctane sulfonate in surface water - Tamil Nadu, India

Ganesan Sunantha ⁎, Namasivayam Vasudevan Center for Environmental Studies, Anna University, Chennai, Tamil Nadu, India article info abstract

Article history: As an emerging class of environmentally persistent organic pollutants, perfluorinated compounds (PFCs), partic- Received 12 March 2016 ularly perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS); have been universally found in the Received in revised form 1 May 2016 environment. Wastewater and untreated effluents are likely the major causes for the accumulation of PFCs in sur- Accepted 3 May 2016 face water. There are very few reports on the contamination of PFCs in the developing countries, particularly in Available online 20 May 2016 India. This study reports the quantitative analysis of PFOA and PFOS in Noyyal, Cauvery, and also lakes in and Keywords: around Chennai, using Ultra-Fast liquid chromatograph. The concentration of PFOA and PFOS ranged from 4 to PFCs 93 ng/L and 3 to 29 ng/L, respectively. The concentration of PFOS was below detectable limit in Cauvery River. PFOA A reliable concentration of PFOA was recorded at all sites of River Cauvery (5 ng/L). The present study could be PFOS useful for the assessment of future monitoring programs of PFOA and PFOS in the surface water. LC-MS © 2016 Elsevier Ltd. All rights reserved. Surface water Tamil Nadu

Perfluorinated compounds (PFCs) have emerged as a new class of estimated at 3.8 and 5.4 years (Senthilkumar, 2005; Olsen et al., persistent organic pollutants. Among PFCs, perfluorooctanoic acid 2007), respectively. (PFOA) and perfluorooctane sulfonates (PFOS) have attracted much at- There are concerns regarding the increasing toxic chemical contam- tention in recent years. Their physicochemical characteristics such as ination in Tamil Nadu, India due to the rapid industrial development, thermal and chemical stability, surface tension-lowering properties, lack of effective toxic chemical control, and solid waste management. and the ability to create stable foams have led to widespread use of The important rivers in southern India including Cauvery River and these compounds in textile, plastic, electronics and upholstery industry Noyyal River are known to serve humanity for centuries. Due to indus- (Giesy and Kannan, 2001; Paul et al., 2009; Xavier et al., 2012; Van trial, agricultural, and urbanization activities, contaminants such as Asselt et al., 2013). The discharge of PFOA and PFOS from industries to polyaromatic hydrocarbons, pesticides, heavy metals, and various our environment resulted in contamination of surface and ground other organic pollutants have already been addressed in this river water (Wang et al., 2012; Lin et al., 2015). Several studies have reported (Ramaswamy et al., 2011; Shanmugam et al., 2014). Recently, the pres- the occurrence of PFOA and PFOS in environmental samples ence of Phthalate esters in the River Cauvery was recorded by Selvaraj et (Senthilkumar et al., 2007; Ahrens et al., 2009; Zushi et al., 2011). Con- al. (2015). To our knowledge, the studies of PFOA and PFOS in India are taminated water could be the source of human exposure pathway for limited (Yeung et al., 2009; Michio et al., 2010; Corsolini et al., 2012). In PFOA and PFOS. The exposure of PFOA and PFOS could cause adverse ef- this regard, the study was aimed to determine the occurrence of PFOA fects on living forms. The toxicological studies of PFOA and PFOS have and PFOS in surface water collected from various locations of Cauvery demonstrated that the compounds may induce adverse effects, namely River in Erode, Noyyal River in Tiruppur, and lakes in and around Chen- immunotoxicity, reproductive toxicity, hepatotoxicity, developmental nai. The main goal of this work is to evaluate the baseline data of PFOA toxicity, and endocrine disruptors, (Post et al., 2012). Moreover, these and PFOS in Tamil Nadu. compounds have been associated with negative human health effects In the present study, surface water were collected from Velachery such as low birth weight and thyroid diseases (Melzer et al., 2010). Lake, Porur Lake, Chitlapakkam Lake, Pallavaram Lake, Korattur Lake, Both the substances are persistent in human because they are poorly Ambattur Lake (Chennai), Cauvery River (Erode), and Noyyal River metabolized. The average half-life of PFOA and PFOS in humans is (Tiruppur) during 2014 and the sampling points are shown in Fig. 1a, b & c. The surface water (3 L) were collected in polypropylene bottles − ⁎ Corresponding author. and stored in freezer at 20 °C. The reference standards of PFOA E-mail address: [email protected] (G. Sunantha). (96%) and PFOS (98%) were bought from Sigma-Aldrich, Bangalore,

Fig. 1. Map showing the sampling sites of (a) Tiruppur district, (b) Erode district, and (c) Chennai.

India. All the chemicals and solvents were purchased from Merck, India 0.2 mL/min. The mass spectrometer used for the detection was and the solvents were of HPLC grade filtered through 0.2 μm nylon Shimadzu 2010EV equipped with electro spray ionization source and a membrane filter. The solid-phase extractor and plexa bond elute car- nitrogen generator (Peak Scientific, Japan). The column and sample tridges (200 mg, 6 cm3) were purchased from Varian Technologies, tray temperature were kept at 200 °C. The capillary voltage was held India. at 3.0 kV for PFOA and 1.5 kV for PFOS and the nebulizer gas flow was The PFOA and PFOS were extracted from surface water using plexa set as 1.5 mL/min. Mode of detection was set to selective ion monitoring cartridge. Cartridges were preconditioned by eluting with 5 mL of at m/z 413.00 for PFOA and 499.15 for PFOS. Quantification of PFOA and 100% methanol followed by 5 mL of milli-Q water. Approximately PFOS were performed using purchased standard. A five point calibration 100 mL of the surface water samples were loaded in the cartridge at a curve was constructed for PFOA and PFOS compounds. The coefficients rate of 2 drops per second. The cartridge was prevented from drying of determinants (R2) were of 0.998 for both PFOA and PFOS. The sam- by instant loading of water sample. Cartridges were then washed with ples were analyzed with a procedural blank, obtained by extracting 5 mL of 40% methanol in water and allowed to run dry and elute was 100 mL of Milli-Q water stored in polypropylene bottles. Blanks were again discarded. Finally, the target compounds were eluted with analyzed with samples as a check for possible laboratory contamination 10 mL methanol at a rate of 1 drop per second and collected in a and interferences, and the blanks were free from contamination. The 20 mL sample vial. The extracts were reduced to 1 mL by evaporation limit of quantification is less than1.5 ng/L for both PFOA and PFOS. under gentle stream of nitrogen gas and reconstituted in 1 mL of meth- The spatial analysis of PFOA and PFOS was carried out using the anol, filter through 0.2 μm syringe filter, and transferred into sample vial ArcGIS®10.1 software. In order to interpolate the data spatially and to for UFLC-MS analysis. calculate values between measurements, an inverse distance weighed The extract samples were analyzed using Shimadzu UFLC 2020 (IDW) method was used. Each value estimated in an IDW interpolation (Ultra-fast liquid chromatograph/mass spectrometer) equipped with is a weighted average of the surrounding sample points. The different binary LC20AD pumps, Shimadzu SIL-HTc auto sampler and PDA-visible locations of the sampling site were imported into GIS software through detector. Phenomenex Gemini C18 column (diameter of 50 mm × 2.0 point layer. Each sample point was assigned by a unique code and ID × 5 μm pore size) equipped with compatible guard column stored in the point attribute table. The database file contains values of (Phenomenex) was used for the separation. An aliquot of 50 μL PFOA PFOA and PFOS in separate columns along with a sample code for each and 20 μL of PFOS were injected. The mobile phase used for the analysis sampling location, the database was used to generate the spatial distri- was 2 mM ammonium acetate/methanol (80:20 v/v) with a flow rate of bution maps of selected compound namely, PFOA and PFOS. The general Download English Version: https://daneshyari.com/en/article/4476442

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