Development of extraction and cleanup approachesfor PFASs analysis in fish tissue by HPLC-MS/MS technique

A V Sorokin, V V Ovcharenko, K A Turbabina, A I Kozhushkevich, A M Kalantaenko, A A Komarov

The Russian State Center for Quality and Standardization of Veterinary Drugs and Feed (VGNKI), Moscow, Russia, 123022

Abstract. The history of PFASs emergence and current status in the context of the Stockholm Convention on POPs, their environmental distribution and toxicity are discussed. Various approaches to PFASs analysis in fish tissues are discussed. An original method of sample preparation is described, which allows quantitative PFASs determination at 0.2 – 100 ppb levels.

1.   Introduction

Perfluorinated compounds (PFASs), classified according to the recommended terminology [1], are a large family of technogenic contaminants. The family consist of different compound classes, such as carboxylates, sulfonates, sulfonamides, alcohols and etc., of which carboxylates and sulfonates are most often analysed in laboratories. PFASs started to emerge into the environment in the late 40s as by-products of Teflon development by DuPont. Teflon was approved by FDA for kitchenware coating in 1962, and Zonyl was approved for food packaging in 1967. At present, PFASs are used in textile industry, paper production, as components in various resins, foams, etc. Accordingly, perfluorooctanoic acid (PFOA) (Fig. 1) was first detected in the blood samples of factory personnel in 1978, and in the ground water in 1984. Due to toxicity concerns, some companies stopped producing 8-carbon PFAS since 2000.

PFASs are stable contaminants capable of bioaccumulation, they are detected in animal tissues. At present, the worldwide production of PFASs has been reduced due to information about their potential health risks, including risks of cancer promotion. According to the European Union data on PFAS in food collected in 2006 – 2012, perfluoroalkanesulfonates (PFSAs) and perfluoroalkylcarboxylicacids (PFCAs) are the most widespread food contaminants. PFSAs were mostly found in fish, meat, drinking water and fruits. The highest levels were detected in liver samples.

High levels of PFCAs and PFSAs were found in marine mammals feeding on fish in such industrially developed areas as the Baltic Sea, Mediterranean, the Great Lakes, and along the South East Asia coast, but also in such remote areas as Alaska and the Antarctic (Table 1).

Most common approaches to PFASs extraction and cleanup involve methanol, acetonitrile, and their mixtures with acidic or alkaline modifications followed by SPE cleanup on commercial sorbents.  Here we report on the determination of perfluorinated carboxylates and sulfonates in medium-fat fish tissues using an alternative method of lipids removal described below.

2.  Materials and Methods

2.1.  Chemicals and Standards

All chemicals were of analytical grade and obtained from Sigma-Aldrich, Fluka and Merck companies. The PFASs standards (PFPeA, PFHxA, PFHpA, PFOA, PFNA, PFDA, PFUdA, PFDoA, PFTrDA, PFTeDa, PFHxDA, PFODA, PFBS, PFPeS, PFHxS, PFHpS, PFOS, PFNS, PFDS, PFDoS) and labeled standards were obtained from Wellington Laboratories. Blank fish samples were obtained from a local commercial source. Oasis WAX cartridges (3 cc, 60 mg) were obtained from Waters. The Reacti-Therm (heating and stirring module, Thermo) was used for concentration step.

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Acknowledgement for publication to: 

A V Sorokin, V V Ovcharenko, K A Turbabina, A I Kozhushkevich, A M Kalantaenko, A A Komarov

The Russian State Center for Quality and Standardization of Veterinary Drugs and Feed (VGNKI), Moscow, Russia, 123022

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