PFOS and PFOA in cereals and fish: Development and validation of a high performance liquid chromatography-tandem mass spectrometry method Valentina Ciccotelli, Maria Cesarina Abete, Stefania Squadrone * Istituto Zooprofilattico Sperimentale del Piemonte, Liguria e Valle D'Aosta, via Bologna 148,10154 Torino, Italy article info Article history: Received 9 March 2015 Received in revised form 30 April 2015 Accepted 2 May 2015 Available online 19 May 2015 Keywords: PFOS PFOA LC-MS/MS Fish Cereals Validation abstract Perfluorooctane sulfonate (PFOS) and Perfluorooctanoic acid (PFOA) are environmental contaminants belonging to a chemical group known as perfluoroalkyl substances (PFASs), which are very persistent in the environment. PFASs are potential reproductive and developmental toxicants and are considered to be endocrine disrupters. These compounds have been found with greater frequency in fish and other seafood compared to other food groups. In fact, aquatic ecosystems represent the final reservoir for PFASs due to their high affinity for sedimentary and living organic matter. Recommendation161/2010/EU stated that the Member States should carry out analysis of perfluoroalkylated substances in order to detect the presence of PFOS and PFOA by making use of an analytical method that has been proven to generate reliable results. The LC-MS/MS method described here has been developed for detecting PFOS and PFOA in fish and cereals. Validation of this method resulted in limits of quantification (LOQs) varying from 0.50 mg/kg for PFOA to 0.70 mg/kg for PFOS, fulfilling recoveries (95e109%), and showing a good linearity (R2 ¼ 0.99). Precision varied from 4.43% to 8.97% of repeatability for PFOA and from 6.30% to 12.33% of repeatability for PFOS. © 2015 Elsevier Ltd. All rights reserved. 1. Introduction Perfluoroalkyl substances (PFAS) have been widely used for more than 50 years in industry and in the household, and are widely distributed in the environment due to extensive usage in a wide variety of commercial applications (Lindstrom et al., 2011). These compounds show a global distribution worldwide and have been detected not only in environmental samples but also in hu- man blood and liver samples (USDA, 2009). Regarding all PFASs, perfluorooctanoic acid (PFOA) and per- fluorooctane sulfonate (PFOS) are the compounds which have been most extensively studied. PFOA and PFOS have both been found to be persistent, toxic and bioaccumulative in the environment and in wildlife (Andersen et al. 2008; Conder et al. 2010, Lau, Butenhoff, & Rogers, 2004). As a result of their excellent solubility in water, the predominant mode of PFAS distribution occurs via the aqueous pathway (Yamashita et al., 2008). Another potential point of entry is industrial sewage in communal water treatment plants which are incapable of breaking down or retaining PFAS as a result of their persistence (Sinclair & Kannan, 2006). Therefore, these compounds can enter into cultivated plants (Felizeter, McLachlan, & de Voogt, 2012; Stahl et al. 2009) and farm animals (Vestergren et al. 2012) in the terrestrial environment or they can accumulate through the marine food web and concentrate in edible fish species (Berger et al. 2009). PFAS exposure in humans primarily originates through inges- tion of contaminated food as well as drinking water (Ericson et al., 2008a; Fromme, Tittlemier, V€ olkel, Wilhelm, & Twardella, 2009; Takagi et al., 2008; Vestergren, Cousins, Trudel, Wormuth, & Scheringer, 2008; Vestergren, Berger, Glynn, & Cousins, 2012; Yamaguchi et al., 2013). However, exposure varies depending on the type of PFAS, geographical location, types of food and food consumption patterns (Ullah, 2013). A recent study regarding hu- man exposure (Gebbink, Berger, & Cousins, 2015) revealed that dust and air are also major exposure pathways for certain PFASs, e.g. PFOS. Sub-chronic exposure of rats and monkeys to PFOS may lead to significant weight loss, increased liver weight and reduction of serum cholesterol and thyroid hormones (Seacat et al., 2003). In * Corresponding author. E-mail address: stefania.squadrone@izsto.it (S. Squadrone). Contents lists available at ScienceDirect Food Control journal homepage: www.elsevier.com/locate/foodcont http://dx.doi.org/10.1016/j.foodcont.2015.05.023 0956-7135/© 2015 Elsevier Ltd. All rights reserved. Food Control 59 (2016) 46e52