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Limited data are available for the occurrence of more recent per and polyfluorinated alkyl substances (PFAS) in marine mammals, especially from the St. Lawrence Estuary and Gulf. This study investigates the occurrence of PFAS in liver and muscle tissues of various marine mammals, including the harbor seal, gray seal, harp seal, hooded seal, harbor porpoise, white-sided dolphin, white-beaked dolphin, and True's beaked whale. Among the 80 target PFAS (including PFCAs, PFSAs, Cyclic PFSA, FASAs/FASAAs, FTCAs/FTUCAs, FTSAs, Ether-PFAS, diPAPs, and ESI + ECF precursors) perfluorooctanoic sulfonate (PFOS) dominates in all the marine mammal species and several other longchain PFCAs, such as PFNA, PFDA, PFUnA, PFTrDA, and PFHxDA, were detected at 100% frequency in both muscle and liver samples. PFDoA and 7:3 fluorotelomer carboxylic acid (7:3 acid) also showed a 100% detection frequency for liver samples. Harp seal tissues displayed notably low PFAS concentrations, with average total PFAS concentrations of 7 ng/g (ww: wet weight) in muscle and 44 ng/g (ww) in the liver. In contrast, the white-sided dolphin exhibited the highest average concentrations, reaching 39 ng/g (ww) in muscle and 334 ng/g (ww) in liver samples. The Pearson correlation analysis reveals a strong correlation between the concentration of PFOS, perfluoroalkyl carboxylic acids (PFCAs), and electrochemical fluorination (ECF) precursors. Species at the top of the marine food chain (harbor porpoise, white sided dolphin, and white beaked dolphin) presented the highest concentrations of PFAS, particularly PFOS and long-chain PFCAs, highlighting the need for an increased regulation of these persistent molecules in order to protect marine mammal's health. [ABSTRACT FROM AUTHOR]

Limited data are available for the occurrence of more recent per and polyfluorinated alkyl substances (PFAS) in marine mammals, especially from the St. Lawrence Estuary and Gulf. This study investigates the occurrence of PFAS in liver and muscle tissues of various marine mammals, including the harbor seal, gray seal, harp seal, hooded seal, harbor porpoise, white-sided dolphin, white-beaked dolphin, and True’s beaked whale. Among the 80 target PFAS (including PFCAs, PFSAs, Cyclic PFSA, FASAs/FASAAs, FTCAs/FTUCAs, FTSAs, Ether-PFAS, diPAPs, and ESI + ECF precursors) perfluorooctanoic sulfonate (PFOS) dominates in all the marine mammal species and several other long-chain PFCAs, such as PFNA, PFDA, PFUnA, PFTrDA, and PFHxDA, were detected at 100% frequency in both muscle and liver samples. PFDoA and 7:3 fluorotelomer carboxylic acid (7:3 acid) also showed a 100% detection frequency for liver samples. Harp seal tissues displayed notably low PFAS concentrations, with average total PFAS concentrations of 7 ng/g (ww: wet weight) in muscle and 44 ng/g (ww) in the liver. In contrast, the white-sided dolphin exhibited the highest average concentrations, reaching 39 ng/g (ww) in muscle and 334 ng/g (ww) in liver samples. The Pearson correlation analysis reveals a strong correlation between the concentration of PFOS, perfluoroalkyl carboxylic acids (PFCAs), and electrochemical fluorination (ECF) precursors. Species at the top of the marine food chain (harbor porpoise, white sided dolphin, and white beaked dolphin) presented the highest concentrations of PFAS, particularly PFOS and long-chain PFCAs, highlighting the need for an increased regulation of these persistent molecules in order to protect marine mammal’s health.

Abstract: We have characterized microsomal systems and measured the levels of microsomal cytochrome P450 1A1 (CYP1A1) and ethoxyresorufin-O-deethylase (EROD) activity in multiple internal organs of male and female white-sided dolphin (Lagenorhynchus acutus) from the northwest Atlantic Ocean. Internal organs were sampled within 24h of death, sometimes in a period of hours, collection times which are significantly less than usually seen for marine mammals. Tissue autolysis, as assessed by histological analysis of liver, was minimal to none in all individuals. Total P420 did not correlate with time from death to sampling, suggesting that it is a poor indicator of P450 degradation in cetacean tissues where perfusion is not practical. The total hepatic microsomal P450 content, cytochrome b5 content, and NADPH-cytochrome c (P450) reductase (CPR) activity averaged 0.29nmolmg−1, 0.12nmolmg−1, and 238nmolmg−1 min−1, respectively. Microsomal CPR activity in liver was higher than that in lung and kidney, and was higher than that reported in liver of most other cetacean species. Immunodetected CYP1A1 content was low in all organs, less than 3pmolesCYP1A equivalentsmg−1. EROD activity ranged from 9 to 376pmolesmg−1 min−1 and was greater in liver than in other tissues. Hepatic microsomal EROD activity and CYP1A1 content did not correlate. However, hepatic EROD activity, but not CYP1A1 protein content, was well correlated with both total PCB and Σmono-ortho PCB concentrations in blubber. Length, as a proxy for age, did not correlate with hepatic EROD activity or CYP1A1 protein levels, and sex did not influence the relationship between EROD and contaminant concentrations. We cannot easily control for the extent of tissue degradation in cetacean studies nor do we have a complete history of these animals. Therefore, other factors such as degradation or hormonal state may have a role in the observed relationships. Yet, as in other mammals, hepatic tissues appear to be a major site of CYP1A1 expression and probably of biotransformation of CYP1A substrates in white-sided dolphin. The expression of an EROD catalyst in liver likely reflects induction by PCBs, but the P450 enzyme catalyzing hepatic EROD activity in these whales may not be CYP1A1. [Copyright &y& Elsevier]

Metallothioneins (MTs) were characterised in the kidneys of a white-sided dolphin Lagenorhynchus acutus stranded along the Belgian coast, displaying high levels of cadmium (Cd) and mercury (Hg) in liver and kidney. The protein has two isoforms: MT-1 and MT-2. MT-1 binds Cu, Zn, Hg and Cd, while MT-2 only binds Zn, Hg and Cd. This suggests different metabolic functions for the two isoforms: MT-1 is mainly involved in Cu homeostasis; MT-2, which was four-fold more abundant than MT-1, detoxifies most of the accumulated cadmium. [Copyright &y& Elsevier]