Twenty years of temporal change in perfluoroalkyl sulfonate and carboxylate contaminants in herring gull eggs from the Laurentian Great Lakes

Abstract

In this study, temporal trends and patterns of major C₄ to C₁₅ chain length PFCAs and PFSAs and some sulfonamide, fluorotelomer acid and alcohol precursors were determined in herring gull (Larus argentatus) egg pools. Samples were analyzed from fifteen collection years including 1990 and all years from 1997 to 2010, and from seven colonies located throughout the Great Lakes, ranging from remote to highly urbanized areas. Other than at the Toronto Harbour colony, the slopes of ∑PFSA concentrations (C₆, C₈, and C₁₀) versus time were negative indicating general declines between 1990 and 2010. PFOS was the dominant PFSA regardless of colony or year, ranging from 80 to 99% of ∑PFSA. For ∑PFCA (C₈–C₁₅), slopes of concentrations versus time were generally positive with 4 of 7 colonies showing statistically significant (p < 0.05) increases in levels through time. Individual PFCAs showed similar increasing trends except for PFOA. Regardless of colony, the PFCA pattern was dominated by the C₁₀ to C₁₃ PFCAs. Consistent with the PFOS declines, concentrations of the PFOS precursor, PFOSA, declined at most colonies between 1990 and 2006 and post-2006 concentrations were below detection limits. Declining concentrations of the C₈ PFCs, PFOS, PFOA and PFOSA, were consistent with the phase out in 2002 by the 3M Company in North America of all of C₈ PFC-related chemistry products. Increasing production volumes of fluorotelomer based compounds, and degradation of these compounds to PFCAs may explain increasing trends of PFCAs in gull eggs. Dietary changes as measured by carbon and nitrogen stable isotopes, showed minimal relationships to PFC levels in gull eggs, which indicates the complexity of aquatic and terrestrial food of gulls and sources of PFCs.