Perfluorinated Carboxylates and Sulfonates and Precursor Compounds in Herring Gull Eggs from Colonies Spanning the Laurentian Great Lakes of North America

National Wildlife Research Centre, Science and Technology Branch, Environment Canada, Carleton University, Ottawa, ON K1A 0H3, Canada.
Environmental Science and Technology (Impact Factor: 5.33). 10/2009; 43(19):7443-9. DOI: 10.1021/es901755q
Source: PubMed


Environmentally important perfluorinated carboxylates and sulfonates, as well as per- and polyfluorinated precursor compounds including several sulfonamides, telomer acids, and alcohols were determined in individual herring gull (Larus argentatus) eggs collected (in 2007) from 15 colonies located at Canadian and some American sites across the Laurentian Great Lakes of North America. The pattern of perfluorosulfonates (PFSAs; C6, C8, C10 chain lengths) was dominated by PFOS (> 90% of sigmaPFSA concentration) regardless of collection location. Concentrations of sigmaPFSA were significantly (p < 0.03) higher in eggs from Middle Island (western Lake Erie; 507 +/- 47 ng/g ww), Toronto Harbour (484 +/- 49 ng/g ww), and Strachan Island (486 +/- 59 ng/g ww) (Lake Ontario) compared to eggs from colonies on Lakes Superior, Michigan, and Huron. Perfluorocarboxylic acids (PFCAs) ranging in chain length from C8 to C15 were detected in the eggs, with PFUnA and PFTrA being the dominant compounds. PFOA and PFNA were more abundant in the sigmaPFCA in eggs from Lake Superior and Michigan colonies, and PFUnA and longer chain PFCAs were more abundant in the sigmaPFCA in eggs from Lake Erie and Ontario colonies. In contrast to sigmaPFSA, the highest concentrations of sigmaPFCA were found in eggs from Double Island, Lake Huron (113 +/- 12 ng/g ww) followed by eggs from colonies on Lakes Erie and Ontario. Among the PFOS or PFCA precursor compounds assessed (6:2, 8:2, and 10:2 fluorotelomer alcohols and acids and PFOSA), none were detectable in eggs from any sampling location. The exception was PFOSA (average concentration < 1 ng/g ww), which suggests that PFOS in the gulls and subsequently in their eggs may be due, in part, to biotransformation of PFOSA to PFOS in the gull and/or in their diet and food web. The accumulation of PFSA and PFCA from mainly aquatic dietary sources was suggested, and were highly lake- and/ or colony-dependent especially showing a northwest and southeast spatial trend and with higher concentrations in eggs from colonies in close proximity to highly urbanized and industrialized sites in Lakes Erie and Ontario.

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    • "Detailed descriptions of sample extraction and instrumental analysis can be found elsewhere (Chu and Letcher, 2008; Gebbink et al., 2009, 2011a,b). In brief, approximately 1 g of homogenate was spiked with labeled internal standards and extracted with 3 mL of 0.2% (v/v) solution of formic acid in acetonitrile three times. "
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    ABSTRACT: Chemicals of emerging concern (CECs) in the basin of the Laurentian Great Lakes of North America include per- and poly-fluoroalkyl substances (PFASs) classified as perfluoroalkyl acids. We investigated several PFASs, and specifically 13 C4-C16 perfluorinated carboxylic acids (PFCAs), 4 (C4, C6, C8 and C10) perfluorinated sulfonates (PFSAs), perfluoro-4-ethylcyclohexane sulfonate (PFEtCHxS) and selected precursors (e.g. perfluorobutane sulfonamide and perfluorooctane sulfonamide) in herring gull (Larus argentatus) eggs collected in 2012-2013 from 19 Canadian and U.S. colony sites across the Great Lakes. C6, C8 and C10 PFSAs, PFEtCHxS, and C7-14 and C16 PFCAs were quantifiable at >97% of the 114 egg samples. PFEtCHxS concentrations ranged from n.d. to 3.1ng/g ww (highest in Lake Michigan eggs). Mean Σ4PFSA (92 to 97% perfluorooctane sulfonate (PFOS)) and Σ9PFCA concentration ranges were 44 to 740 and 4.8 to 118ng/g ww, respectively. Σ4PFSA showed a clear increasing concentration trend from the northwest to the southeast colonies. Also, Σ4PFCA to Σ9PFSA concentration ratios in gull eggs were greater in eggs from Lake Superior relative to colonies in the other lakes. PFOS concentrations in some egg samples were greater than some of the known lowest observed effect concentrations (LOECs) measured and reported in captive bird model studies. This study showed the increasing complexity of PFAS-CECs, and emphasized the importance of continuing monitoring of bioaccumulative PFAS in Great Lakes herring gulls. Copyright © 2015 Elsevier B.V. All rights reserved.
    Science of The Total Environment 12/2015; 538:468-477. DOI:10.1016/j.scitotenv.2015.08.083 · 4.10 Impact Factor
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    • "The extraction and clean-up of the samples was based on published methods (Gebbink et al., 2009, 2013). Briefly, homogenized food basket samples (2.5e5 g) were spiked with labeled internal standards (500 pg each) (see Table S1 for all internal standards used) and 6 mL acetonitrile were added. "
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    ABSTRACT: We analyzed food market basket samples obtained in Sweden from 1999, 2005, and 2010 for perfluoroalkyl acids (PFAAs) and a range of precursor compounds. Perfluorooctane sulfonic acid (PFOS) precursors were detected in all food year pools with the highest concentrations in 1999. Six polyfluoroalkyl phosphate diesters (diPAPs, 4:2/6:2, 6:2/6:2, 6:2/8:2, 8:2/8:2, 6:2/10:2, and 10:2/10:2) were detected in the year pools with the highest ∑diPAP concentrations in 1999 and 2005. All precursors were predominantly found in meat, fish, and/or eggs based on analysis of individual food groups from 1999. Based on year pools, PFOS precursors contributed between 4 and 1% as an indirect source to total dietary PFOS intakes between 1999 and 2010. Perfluorohexanoic acid (PFHxA) exposure originated entirely from diPAPs, whereas for perfluorooctanoic acid (PFOA) and perfluorodecanoic acid (PFDA), diPAPs contributed between 1 and 19% to total exposure. The lowest precursor contributions were generally seen in food samples from 2010.
    Environmental Pollution 03/2015; 198. DOI:10.1016/j.envpol.2014.12.022 · 4.14 Impact Factor
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    • "PFOA is different from other persistent organic pollutants in its hydrotrope property and can therefore aggregate in the liver and blood serum rather than in fatty tissues (Gebbink et al., 2009). Although the manufacture and use of PFOA are phasing out in some countries, PFOA has been frequently detected in drinking water (Post et al., 2009; Quinones and Snyder, 2009), biotas (Gebbink et al., 2009) and in people (Harada et al., 2007). However, PFOA is difficult to degrade using most conventional technologies (Vecitis et al., 2009). "
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    ABSTRACT: Perfluorooctanoic acid (PFOA) is recalcitrant to degrade and mineralize. Here, the effect of temperature on the photolytic decomposition of PFOA was investigated. The decomposition of PFOA was enhanced from 34% to 99% in 60 min of exposure when the temperature was increased from 25 to 85°C under UV light (201–600 nm). The limited degree of decomposition at 25°C was due to low quantum yield, which was increased by a factor of 12 at 85°C. Under the imposed conditions, the defluorination ratio increased from 8% at 25°C to 50% at 85°C in 60 min. Production of perfluorinated carboxylic acids (PFCAs, C7–C5), PFCAs (C4–C3) and TFA (trifluoroacetic acid, C2) accelerated and attained a maximum within 30 to 90 min at 85°C. However, these reactions did not occur at 25°C despite extended irradiation to 180 min. PFOA was decomposed in a step-wise process by surrendering one CF2 unit. In each cyclical process, increased temperature enhanced the quantum yields of irradiation and reactions between water molecules and intermediates radicals. The energy consumption for removing each μmol of PFOA was reduced from 82.5 kJ at 25°C to 10.9 kJ at 85°C using photolysis. Photolysis coupled with heat achieved high rates of PFOA degradation and defluorination.
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