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: 5.48). 10/2009; 43(19):7443-9. DOI: 10.1021/es901755q
Source: PubMed

ABSTRACT 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.

  • Source
    • "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. "
    [Show abstract] [Hide abstract]
    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
  • Source
    • "Recovery of reference materials was within the confidence interval of the certified values and the nominal detection limit for total Hg was 0.006 lg g À1 dry weight sample. Stable-nitrogen isotope assays were performed by continuousflow stable isotope ratio mass spectrometry according to method described in Chambellant et al. (2013) for the 2007 samples, and in Gebbink et al. (2011) for the 2008 and 2009 samples. Data were normalized using international standards for calibration, and quality control was maintained through sample duplicates. "
    [Show abstract] [Hide abstract]
    ABSTRACT: Twelve marine fish species collected from a thick-billed murre (Uria lomvia) breeding colony in northern Hudson Bay in the Canadian Arctic during 2007-2009 were analyzed for legacy organochlorines (e.g. PCBs, DDT), polybrominated diphenyl ethers (PBDEs), perfluorinated carboxylates (PFCAs) and sulfonates (PFSAs), and total mercury (Hg). No one species of prey fish had the highest levels across all contaminant groups analyzed. For the two pelagic fish species sampled, concentrations of the major organochlorine groups (e.g. Σ21PCB, ΣDDT, ΣCHL, ΣCBz), ΣPBDE, ΣPFCA and Hg were consistently higher in Arctic cod (Boreogadus saida) than in capelin (Mallotus villosus). Biomagnification factors from whole fish to thick-billed murre liver across all species were generally higher for Σ21PCB and ΣDDT. ΣPBDE did not biomagnify.
    Marine Pollution Bulletin 11/2013; 78(1-2). DOI:10.1016/j.marpolbul.2013.11.003 · 2.79 Impact Factor
  • Source
    • "The extraction and cleanup is described in detail in Gebbink et al. (2009) and Chu and Letcher (2008). Briefly, approximately 1 g of egg homogenate was spiked with labeled internal standards and extracted with 10 mM KOH acetonitrile/water (80/20 v/v). "
    [Show abstract] [Hide abstract]
    ABSTRACT: In the present study, we identified and examined the spatial trends, sources and dietary relationships of bioaccumulative perfluorinated sulfonate (PFSA; C(6), C(8), and C(10) chain lengths) and carboxylate (PFCA; C(6) to C(15) chain lengths) contaminants, as well as precursor compounds including several perfluorinated sulfonamides, and fluorotelomer acids and alcohols, in individual eggs (collected in 2008) from four gull species [glaucous-winged (Larus glaucescens), California (Larus californicus), ring-billed (Larus delawarensis) and herring (Larus argentatus) gulls] from 15 marine and freshwater colony sites in provinces across Canada. The pattern of PFSAs was dominated by perfluorooctane sulfonate (PFOS; >89% of ΣPFSA concentration) regardless of egg collection location. The highest ΣPFSA concentrations were found in the eggs collected in the urbanized areas in the Great Lakes and the St. Lawrence River area [Big Chicken Island 308 ng/g ww, Toronto Harbour 486 ng/g ww, and Ile Deslauriers (HG) 299 ng/g ww]. Also, eggs from all freshwater colony sites had higher ΣPFSA concentrations, which were significant (p<0.05) in many cases, compared to the marine sites with the exception of the Sable Island colony in Atlantic Canada off the coast of Nova Scotia. C(6) to C(15) chain length PFCAs were detected in the eggs, although the pattern was variable among the 15 sites, where PFUnA and PFTrA dominated the pattern for most colonies. Like the ΣPFSA, the highest concentrations of ΣPFCA were found in the eggs from Big Chicken Island, Toronto Harbour, Ile Deslauriers (HG), and Sable Island, although not all freshwater sites had higher concentrations compared to marine sites. Dietary tracers [δ(15)N and δ(13)C stable isotopes (SIs)] revealed that PFSA and PFCA exposure is colony dependent. SI signatures suggested that gulls from most marine colony sites were exposed to PFCs via marine prey. The exception was the Mandarte Island colony in Pacific British Columbia, where PFSA and PFCA exposure appeared to be via terrestrial and/or freshwater prey consumption. The same was true for the freshwater sites where egg SIs suggested both aquatic and terrestrial prey consumption as the source for PFC exposure depending on the colony. Both aquatic (marine and freshwater) and terrestrial prey are likely sources of PFC exposure to gulls but exposure scenarios are colony-specific.
    Environment international 04/2011; 37(7):1175-82. DOI:10.1016/j.envint.2011.04.003 · 5.66 Impact Factor
Show more