Collection of Airborne Fluorinated Organics and Analysis by Gas Chromatography/Chemical Ionization Mass Spectrometry

Department of Chemistry, University of Toronto, Toronto, Ontario, Canada
Analytical Chemistry (Impact Factor: 5.64). 03/2002; 74(3):584-90. DOI: 10.1021/ac015630d
Source: PubMed

ABSTRACT The ubiquitous detection of perfluorooctane sulfonate (PFOS) in humans and animals has produced a need for sensitive and compound-specific analytical methods to determine the environmental distribution of fluorinated organic contaminants. A suite of potential PFOS precursors (sulfonamides) and fluorotelomer alcohols (FTOHs) were separated by gas chromatography and detected by chemical ionization mass spectrometry (GC/CI-MS). Full-scan spectra were collected in both positive and negative chemical ionization (PCI and NCI, respectively) mode to determine retention time windows and fragmentation patterns. In selected ion monitoring (SIM) mode, instrumental detection limits ranged from 0.2 to 20 pg for individual analytes, depending on ionization mode. PCI mode was preferred for routine analysis because of the simple mass spectra produced, typified by the presence of a major molecular ion [M + H]+. High-volume air samplers collected gaseous and particle-bound fluoroorganics on composite media consisting of XAD-2, polyurethane foam (PUF), and quartz-fiber filters. The combined collection efficiency for individual analytes was 87 to 136% in breakthrough experiments. Application of the method to the analysis of ambient air from urban and rural sites confirmed the presence of six novel fluorinated atmospheric contaminants at picogram per meter3 concentrations. Low concentrations of fluoroorganics were consistently detected in blanks (<4 pg m(-3)); however, this did not prevent confirmation or quantification of environmental concentrations.

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    • "The latter method was later optimized to avoid solvent-induced response enhancements, which resulted in instrumental limits of detection of <0.2 pg [68]. In earlier work on determination of airborne fluorinated organics kit was shown that both positive and negative modes of chemical ionization were useful for the determination of all target analytes [69]. "
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    ABSTRACT: Perfluoroalkyl substances (PFASs) are proliferated into the environment on a global scale and present in the organisms of animals and humans even in remote locations. Persistent organic pollutants of that kind therefore have stimulated substantial improvement in analytical methods. The aim of this review is to present recent achievements in PFASs determination in various matrices with different methods and its comparison to measurements of Total Organic Fluorine (TOF). Analytical methods used for PFASs determinations are dominated by chromatography, mostly in combination with mass spectrometric detection. However, HPLC may be also hyphenated with conductivity or fluorimetric detection, and gas chromatography may be combined with flame ionization or electron capture detection. The presence of a large number of PFASs species in environmental and biological samples necessitates parallel attempts to develop a total PFASs index that reflects the total content of PFASs in various matrices. Increasing attention is currently paid to the determination of branched isomers of PFASs, and their determination in food. Figure The aim of this review is to present recent achievements in perfluoroalkyl substances (PFASs) determination in various matrices with different methods and its comparison to measurements of Total Organic Fluorine (TOF). Increasing attention is currently paid to the determination of branched isomers of PFASs, and their determination in food.
    Microchimica Acta 08/2013; 180(11-12):957-971. DOI:10.1007/s00604-013-1046-z · 3.74 Impact Factor
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    • "FTOHs are volatile, not very soluble in water (carbon chain-length dependent) in the absence of a sorbing medium (Liu and Lee, 2005) and have a tendency to be adsorbed strongly to solid matters such as household dusts (Strynar and Lindstrom, 2008), soils or activated sludge (Liu and Lee, 2005, 2007; Wang et al., 2005a). Field monitoring studies have detected FTOHs in the troposphere at concentrations ranging from 7 to 196 pg/m 3 (Martin et al., 2002) and averaged 87 pg/m 3 (Dreyer et al., 2009) with 6:2 and 8:2 FTOHs in majority. The major source of environmental FTOHs has been postulated to come from the residual unreacted FTOH present in commercial products (Ellis et al., 2003). "
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    ABSTRACT: Fluorotelomer alcohols [FTOHs, F(CF(2) )(n) CH(2) CH(2) OH, n = 4, 6, and 8] are emerging environmental contaminants. Biotransformation of FTOHs by mixed bacterial cultures has been reported; however, little is known about the microorganisms responsible for the biotransformation. Here we reported biotransformation of FTOHs by two well-studied Pseudomonas strains: Pseudomonas butanovora (butane oxidizer) and Pseudomonas oleovorans (octane oxidizer). Both strains could defluorinate 4:2, 6:2, and 8:2 FTOHs, with a higher degree of defluorination for 4:2 FTOH. According to the identified metabolites, P. oleovorans transformed FTOHs via two pathways I and II. The pathway I led to the production of x:2 ketone [dominant metabolite, F(CF(2) )(x) C(O)CH(3) ; x = n - 1, n = 6 or 8], x:2 sFTOH [F(CF(2) )(x) CH(OH)CH(3) ], and perfluorinated carboxylic acids (PFCAs, perfluorohexanoic, or perfluorooctanoic acid). The pathway II resulted in the formation of x:3 polyfluorinated acid [F(CF(2) )(x) CH(2) CH(2) COOH] and relatively minor shorter-chain PFCAs (perfluorobutyric or perfluorohexanoic acid). Conversely, P. butanovora transformed FTOHs by using the pathway I, leading to the production of x:2 ketone, x:2 sFTOH, and PFCAs. This is the first study to show that individual bacterium can bio-transform FTOHs via different or preferred transformation pathways to remove multiple CF(2)  groups from FTOHs to form shorter-chain PFCAs. Biotechnol. Bioeng. © 2012 Wiley Periodicals, Inc.
    Biotechnology and Bioengineering 12/2012; 109(12). DOI:10.1002/bit.24561 · 4.13 Impact Factor
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    • "Per-and polyfluoroalkyl compounds (PFCs) are persistent against the typical environmental degradation processes and have been found ubiquitously in water (Saito et al., 2003; Schultz et al., 2004; So et al., 2004; Yamashita et al., 2005; Ahrens et al., 2010a,b; Busch et al., 2010), air (Martin et al., 2002; Stock et al., 2004, 2007; Jahnke et al., 2007), sediment (Bao et al., 2009, 2010; Gómez et al., 2011; Yang et al., 2011), sludge (Higgins et al., 2005), precipitation (Liu et al., 2009), wildlife (Giesy and Kannan, 2001; Li et al., 2008a,b) and humans (Yeung et al., 2006, 2008; Jin et al., 2007) around the globe. Because of their chemical characteristics , including extraordinary stability, hydrophobicity, oleophobicity and surfactant characteristics, many PFCs have been broadly applied to industrial and domestic production in the past half-century (OECD, 2002; Prevedouros et al., 2006). "
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    ABSTRACT: The spatial distribution of per- and polyfluoroalkyl compounds (PFCs) were investigated in coastal waters collected onboard research vessel Snow Dragon from the East to South China Sea in 2010. All samples were prepared by solid-phase extraction and analyzed using high performance liquid chromatography/negative electrospray ionization-tandem mass spectrometry (HPLC/(-)ESI-MS/MS). Concentrations of 9 PFCs, including C(4) and C(8) (PFBS, PFOS) perfluoroalkyl sulfonate (PFSAs), C(5)-C(9) and C(13) (PFPA, PFHxA, PFHpA, PFOA, PFNA, PFTriDA) perfluoroalkyl carboxylates (PFCAs), and N-ethyl perfluorooctane sulfonamide (EtFOSA) were quantified. The ΣPFC concentrations ranged from 133 pg/L to 3320 pg/L, with PFOA (37.5-1541 pg/L), PFBS (23.0-941 pg/L) and PFHpA (0-422 pg/L) as dominant compounds. Concentrations of PFCs were greater in coastal waters along Shanghai, Ningbo, Taizhou, Xiamen and along coastal cities of the Guangdong province compared to less populated areas along the east Chinese coast. Additionally, the comparison with other seawater PFC measurements showed lower levels in this study.
    Environmental Pollution 02/2012; 161:162-9. DOI:10.1016/j.envpol.2011.09.045 · 4.14 Impact Factor
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