Environ. Sci. Technol. 2009, 43, 7443–7449
Perfluorinated Carboxylates and Sulfonates and Precursor Compounds in Herring Gull Eggs from Colonies Spanning the Laurentian Great Lakes of North America W O U T E R A . G E B B I N K , * ,†,‡ CRAIG E. HEBERT,† AND R O B E R T J . L E T C H E R * ,†,‡ National Wildlife Research Centre, Science and Technology Branch, Environment Canada, Carleton University, Ottawa, ON, K1A 0H3, Canada, and Department of Chemistry, Carleton University, Ottawa, Ontario, K1S 5B6, Canada
Received June 15, 2009. Revised manuscript received August 14, 2009. Accepted August 18, 2009.
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 ΣPFSA concentration) regardless of collection location. Concentrations of ΣPFSA 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 ΣPFCA in eggs from Lake Superior and Michigan colonies, and PFUnA and longer chain PFCAs were more abundant in the ΣPFCA in eggs from Lake Erie and Ontario colonies. In contrast to ΣPFSA, the highest concentrations of ΣPFCA 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 60% detection of individual PFCs in the eggs for a given colony, and a Shapiro-Wilk’s W test indicated a normal distribution for the majority of individual PFCAs and PFSAs. Differences in the pattern of
TABLE 1. Arithmetic Mean Concentrations of ΣPFSA and ΣPFCA (ng/g Wet Weight) in Individual Herring Gull Eggs Collected from 15 Colonies in the Great Lakes in 2007 (n = 13 Per Colony) colony
lake/river
ΣPFSAa ((SE)
ΣPFCAb ((SE)
Granite Is. Agawa Rocks Big Sister Is. Gull Is. Channel-Shelter Is. Double Is. Chantry Is. Fighting Is. Middle Is. Port Colborne Niagara River Hamilton Harbour Toronto Harbour Snake Is. Strachan Is.
L. Superior L. Superior L. Michigan L. Michigan L. Huron L. Huron L. Huron Detroit River L. Erie L. Erie Niagara River L. Ontario L. Ontario L. Ontario St. Lawrence River
127 ( 20 91 ( 13 212 ( 26 178 ( 18 227 ( 16 227 ( 24 160 ( 37 264 ( 47 507 ( 47 328 ( 32 301 ( 40 319 ( 32 484 ( 49 427 ( 67 486 ( 59
46 ( 6 72 ( 5 63 ( 9 30 ( 5 41 ( 4 113 ( 12 32 ( 7 58 ( 9 94 ( 9 51 ( 6 64 ( 8 56 ( 8 70 ( 6 73 ( 12 66 ( 9
correlations of ΣPFCA versus ΣPFSAc slope
r
p
2.47 0.89 2.52 2.86 3.06 0.40 5.07 5.06 5.30 5.47 4.94 3.43 6.71 5.32 6.12
0.744 0.335 0.834 0.845 0.808 0.197 0.959 0.972 0.959 0.949 0.965 0.832 0.849 0.985 0.956
0.001 0.22
