Contaminants of emerging concern in Caspian tern compared to herring gull eggs from Michigan colonies in the Great Lakes of North America

Abstract

A broad suite of 87 contaminants of emerging concern (CECs), including 26 polybrominated diphenyl ethers (PBDEs), 23 non-PBDEs halogenated FRs (NPHFRs), 16 organophosphate esters (OPEs), 4 perfluorinated sulfonates (PFSAs), 13 perfluorinated carboxylic acids (PFCAs) and 5 emerging perfluoroalkyl acids (PFAAs) or precursors, were determined in 30 individual Caspian tern (listed as a threatened species in the U.S. State of Michigan) eggs collected in 2013 and 2014 from Michigan nesting sites on Two Tree Island (St, Mary's River), Charity Reef (Saginaw Bay) and Channel-Shelter Island (a Confined Disposal Facility (CDF) in Saginaw Bay). The same CEC suite was determined in 10 herring gull eggs on the Pipe Island Twins in the lower St. Mary's River. In tern eggs, the order of concentrations were ΣPFSA (mean: 793 ng/g wet weight (ww); range: 116-4690 ng/g ww) > ΣPFCAs (131; 30.4-506 ng/g ww) ≈ ΣPBDEs (86.7; 32.4-189 ng/g ww) » ΣNPHFRs (0.67; ND-4.3 ng/g ww) ≈ ΣOPEs (0.46; ND-2.89 ng/g ww). Compared to gull eggs collected from the same area, tern egg exposure contained significantly lower concentrations of ΣPBDE, but with up to 10 times greater mean concentrations of ΣPFSAs and ΣPFCAs. This study highlights the importance of consistent monitoring in eggs of different Great Lakes birds of PBDEs, perfluorooctane sulfonate (PFOS) and perfluoro-4-ethylcyclohexane sulfonate (PFEtCHxS) given that: 1) PBDE concentrations in all analyzed avian eggs exceeded or approached a concentration of 29 ng/g ww, which for birds is the current Canadian FEQG (Federal Environmental Quality Guideline); 2) ΣPBDE concentrations were comparable to lowest observed effect concentration (LOEC) values reported in the literature; 3) PFOS concentrations in Caspian tern eggs were extremely high with many eggs across sites exceeding 1 ppm, and with the greatest being up to 4.7 ppm; and 4) PFEtCHxS, a potentially persistent and bioaccumulative substance, showed a detection frequency of 100% in 40 of the analyzed eggs.

Keywords: Caspian terns; Eggs; Flame retardants; Herring gulls; Laurentian Great Lakes; Perfluoroalkyl substances.