Increasing levels of long-chain perfluorocarboxylic acids (PFCAs) in Arctic and North Atlantic marine mammals, 1984–2009 Anna Rotander a,⇑ , Anna Kärrman a , Bert van Bavel a , Anuschka Polder b , Frank Rigét c , Guðjón Atli Auðunsson d , Gísli Víkingsson e , Geir Wing Gabrielsen f , Dorete Bloch g , Maria Dam h a Man-Technology-Environment (MTM) Research Centre, Örebro University, SE-701 82 Örebro, Sweden b Norwegian School of Veterinary Science, Department of Food Safety and Environment, P.O. Box 8146 Dep, 0033 Oslo, Norway c Department of Arctic Environment, National Environmental Research Institute, University of Aarhus, Box 358, DK-4000 Roskilde, Denmark d Innovation Center Iceland, Dept. of Analytical Chemistry, Keldnaholti, 112 Reykjavik, Iceland e Marine Research Institute, Skúlagata 4, 101 Reykjavík, Iceland f Norwegian Polar Institute, FRAM Centre, NO-9296 Tromsø, Norway g Museum of Natural History, Fútalág 40, FO-100 Torshavn, Faroe Islands h Environment Agency, Pob, 2048, FO-165 Argir, Faroe Islands article info Article history: Received 22 June 2011 Received in revised form 22 September 2011 Accepted 29 September 2011 Available online 1 November 2011 Keywords: Marine mammals PFSAs PFCAs Structural isomers Temporal variations abstract Temporal variations in concentrations of perfluorinated carboxylic acids (PFCAs) and sulfonic acids (PFSAs), including perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) structural isomers, were examined in livers of pilot whale (Globicephala melas), ringed seal (Phoca hisida), minke whale (Bal- aenoptera acutorostrata), harbor porpoise (Phocoena phocoena), hooded seal (Cystophora cristata), Atlantic white-sided dolphin (Lagenorhynchus acutus) and in muscle tissue of fin whales (Balaenoptera physalus). The sampling spanned over 20 years (1984–2009) and covered a large geographical area of the North Atlantic and West Greenland. Liver and muscle samples were homogenized, extracted with acetonitrile, cleaned up using hexane and solid phase extraction (SPE), and analyzed by liquid chromatography with negative electrospray tandem mass spectrometry (LC-MS/MS). In general, the levels of the long-chained PFCAs (C9–C12) increased whereas the levels of PFOS remained steady over the studied period. The PFOS isomer pattern in pilot whale liver was relatively constant over the sampling years. However, in ringed seals there seemed to be a decrease in linear PFOS (L-PFOS) with time, going from 91% in 1984 to 83% in 2006. Ó 2011 Elsevier Ltd. All rights reserved. 1. Introduction Organofluorine compounds have been released into the envi- ronment since the 1950s from fluoropolymer manufacturing processes and disposal of products containing fluorochemicals (Prevedouros et al., 2006; Paul et al., 2009). In addition to direct discharge, precursor compounds have been identified as an indi- rect source of perfluorinated carboxylic acids (PFCAs) and sulfonic acids (PFSAs) found in environmental matrices. PFCAs and PFSAs are globally distributed and have been detected in wildlife as well as in humans (Giesy and Kannan, 2001; Kannan et al., 2002; Kärr- man et al., 2007; Kelly et al., 2009). The most studied compounds are perfluorooctane sulfonate (PFOS), which was recently added to the list of persistent organic pollutants (POPs) under the Stock- holm convention in 2009, and perfluorooctanoate (PFOA). How- ever, longer-chain PFCAs (>9 carbons) are commonly found in higher concentrations compared to PFOA in wildlife due to a higher accumulation potential and have been detected in Arctic bird and mammal species from high latitudes of the Northern hemisphere at considerable levels, even though they have not been produced intentionally on a large-scale (Martin et al., 2004; Butt et al., 2010). Because bioaccumulation increases with increasing perfluo- roalkyl chain length, and because no environmental degradation is known, long-chain PFCAs are chemicals of environmental concern (Martin et al., 2003; Conder et al., 2008). Temporal trends of levels of environmental contaminants over longer periods are important in order to monitor their occurrence and behaviour. During the last decades, a general trend has been that the legacy POPs have declined in biota whereas the perflu- oroalkylated substances (PFASs) have increased (Bossi et al., 2005; Braune et al., 2007; Helgason et al., 2008; Holmström et al., 2010; Rigét et al., 2010). Marine mammals have often been used in long-term exposure studies of persistent bioaccumulative substances since many species mainly feed at the top of the aquatic food chain as well as have a relatively long life-span. 0045-6535/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.chemosphere.2011.09.054 ⇑ Corresponding author. Tel.: +46 19 303078; fax: +46 19 303666. E-mail address: anna.rotander@oru.se (A. Rotander). Chemosphere 86 (2012) 278–285 Contents lists available at SciVerse ScienceDirect Chemosphere journal homepage: www.elsevier.com/locate/chemosphere