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

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; C-6, C-8, C-10 chain lengths) was dominated by PFOS (>90% of Sigma PFSA concentration) regardless of collection location. Concentrations of Sigma PFSA 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 C-8 to C-15 were detected in the eggs, with PFUnA and PFTrA being the dominant compounds. PFOA and PFNA were more abundant in the Sigma PFCA in eggs from Lake Superior and Michigan colonies, and PFUnA and longer chain PFCAs were more abundant in the Sigma PFCA in eggs from Lake Erie and Ontario colonies. In contrast to Sigma PFSA, the highest concentrations of Sigma PFCA 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.