Perfluorooctane sulfonate production

Perfluoroalkyl compounds have been manufactured since the 1950s.The total production of fluorinated surfactants (anionic, cationic and neutral) was 2001 in 1979, whereas in 2000 the total production of PFOS (perfluorooctane sulfonate) alone was nearly 3000t (Shoeib et al., 2004). Together with PFOA (perfluoroocta-noic acid), PFOS is used in refrigerants, surfactants, fire retardants, stain-resistant coatings for fabrics, carpets and paper and insecticides. Surface treatments, such as protection of clothing and carpets constitute the largest volume of PFOS production (Moriwaki, Takata and Arakawa, 2003). PFOA as well is present in several... 

OSHA PB PBB PBT PEC penta-BDE PFOS PNEC POP PPE PPORD PRODUCE European Agency for Safety and Health at Work Persistent and bioaccumulating Polybromobiphenyl(s) Persistent, bioaccumulative and toxic Predicted environmental concentration Pentabromodiphenyl ether Perfluorooctane sulfonate Predicted no-effect concentration Persistent organic pollutant Personal protective equipment Process/product-oriented research and development Piloting REACH on downstream use communication in Europe... 

Abstract In the past years, elucidation of transformation products of per- and polyfluorinated chemicals (PFC) has been a task frequently approached by analytical chemists. PCT, such as perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) are persistent and thus, the analytical quest to detect transformation products has failed so far. Their prominence as contaminants is mainly due to their extreme persistence, which is linked to their perfluoroalkyl chain length. Molecules that are less heavily fluorinated can show very complex metabolic behavior, as is the case for fluorotelomer alcohols. These compounds are degraded via different but simultaneous pathways, which produce different stable metabolites. Biotransformation processes of PFC may occur when these compounds enter the environment, and thus known and unknown PFC may be generated in these compartments. Therefore, it is essential to determine metabolic pathways of such compounds in order to entirely understand their fate in the environment. This chapter summarizes methodological approaches and instmmental setups which have been implemented in biotransformation studies of PFC and focuses on mass spectrometric methods and the separation techniques coupled to the mass spectrometer (MS). Valuable MS approaches that have not been frequently used in studies on PFC are presented as well. Since compounds carrying C-F bonds exhibit unique properties, these will be initially presented to address the meaning of these properties both for analytical tasks and for the setup of biotransformation experiments. 

In the past years, elucidation of transformation products of per- and polyfluorinated compounds (PFC) has been a task frequently approached by analytical chemists. It has been estimated that biotransformation contributes to approximately 0.1-5% with respect to perfluorocarboxylic acid (PFCA) historical global emissions [1]. For perfluorooctanesulfonyl fluoride (POSF)-based compounds such as perfluorooctane sulfonic acid (PFOS), biotransformation products probably affect environmental burden marginally, although no distinct estimations have been made so far [2]. 

Paul AG, Jones KC, Sweetman AJ (2008) A first global production, emission, and environmental inventory for perfluorooctane sulfonate. Environ Sci Technol 43 386-392... 

Chu S, Letcher RJ (2009) Linear and branched perfluorooctane sulfonate isomers in technical product and environmental samples by in-port derivatization-gas chromatography-mass spectrometry. Anal Chem 81 4256—4262... 

Recent actions taken by authorities in order to prevent further environmental contamination have led to several reductions in environmental emissions in the immediate past or near future. The voluntary initiative launched in 2006 by manufacturing industries to reduce emissions of perfluorooctanoic acid (PFOA) to the environment by 95% until 2010 (2000 as baseline year) is one example [19]. Although involved western industries aim at stopping PFOA emissions from products or facilities by 2015 [19], one should be aware that the phase-out of emissions does not entail global production stop. Recently, perfluorooctane sulfonate (PFOS) has been classified as a persistent organic pollutant (POP) by the Stockholm convention [20]. Also a restrictive regulation on the use of PFOS in Europe has been accepted by the European Parliament in 2006 [21]. According to the directive industries which cannot operate without PFOS are bound to use the best available techniques (BAT) to reduce emissions to the environment [21] and... 

FIGURE 18.1 Simplified production pathway of fluorinated surfactants derived from perfluorooctanesul-fonyl fluoride, (Adapted from Kissa, E., Fluorinated Surfactants and Repellents, Marcel Dekker, New York, 2001 Environment Directorate, OECD, Hazard assessment of perfluorooctane sulfonate (PEGS) and its salts. Report ENV/JM/RD(2002)17/FINAL, Organization for Economic Cooperation and Development, Paris, 2002 Schultz, M.M. et al., Environ. Eng. ScL, 20, 487, 2003.)... 

Gallo V, Leonard G, Genser B et al (2012) Serum perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS) concentrations and liver function biomarkers in a population with elevated PFOA exposure. Environ Health Perspect 120(5) 655-660 Gilliland FD, Mandel JS (1993) Mortality among employees of a perflucnooctanoic acid production plant. J Occup Med 35(9) 950-954... 

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