A re-assessment of archived (1989–2006) beluga liver from the North American Arctic with non-targeted analysis reveals brominated chemicals of emerging concern

Abstract

In 2011, 68 archived beluga whale (Delphinapterus leucas) liver samples collected from Cook Inlet and the eastern Chukchi Sea from 1989 to 2006 were characterized for 12 per- and polyfluoroalkyl substances (PFAS) using targeted mass spectroscopy (MS) methods; however, at the time of the original analysis, high resolution MS (HRMS) methods were not readily available. This follow-up study utilizes both targeted as well as cutting-edge HRMS non-targeted analysis (NTA) techniques to screen for additional PFAS as well as potential contaminants of emerging concern (CECs) in the chemical space under investigation. Targeted analysis detected perfluorodecanesulfonic acid (PFDS) and perfluoroheptane sulfonic acid (PFHpS) in 10 % and 9 % of liver samples, respectively. PFDS detections were observed only in Cook Inlet whales while PFHpS was detected in whales from both locations. In addition, NTA identified four dibrominated pyrrole ring structures two with a sulfate (C₈H₁₁NBr₂SO₃, and C₉H₁₃NBr₂SO₃, Schymanski level 3), and two with either a sulfonate or a sulfate and hydroxy group (C₈H₁₁NBr₂SO₄, C₉H₁₃NBr₂SO₄, Schymanski level 4) in whales from the eastern Chukchi Sea. Literature search reveals similar brominated metabolites from marine bacteria, sponges, and other marine organisms, suggesting the brominated CECs are of marine origin.