Evaluating per- and polyfluoroalkyl substance (PFAS) prevalence and potential for biological effects in Lake Superior tributaries.

Several per- and polyfluoroalkyl substances (PFAS) are Great Lakes binational chemicals of mutual concern. Although known to be persistent, data gaps regarding PFAS prevalence and biological effects exist, especially within Lake Superior's watershed. In this 2022 study of 27 United States tributaries to Lake Superior, water samples were collected during spring runoff, summer baseflow, and fall baseflow, and streambed-sediment samples were collected during fall. Per- and polyfluoroalkyl substances (PFAS) were detected in 97% of water samples and 59% of sediment samples. Summed PFAS water sample concentrations (33 analytes) were generally low, relative to other environmental studies (median = 6.5 ng/L), except at Newton, Miller, and Sargent Creeks (up to 391 ng/L). Maximum water concentrations were from perfluorooctane sulfonic acid (PFOS) and perfluorohexane sulfonate (PFHxS); perfluorobutanoic acid had the greatest median concentration. Perfluorobutanoic acid (PFBA) and perfluorooctanoic acid (PFOA) were most frequently detected in water samples (>90%). Summed PFAS sediment sample concentrations (33 analytes) were also generally low (median = 19 ng/kg), except at Newton and Muggun Creeks (up to 797 ng/kg). In sediment, PFOS occurred most frequently and had the greatest concentrations. The most contaminated samples came from sites with documented aqueous film forming foam or wastewater contamination; summer baseflow samples exhibited elevated PFAS concentrations. Comparison of observed water concentrations to published and derived water-quality guidelines indicated PFOS and PFHxS pose the greatest potential ecological risks. Observed PFAS mixtures may affect lipid metabolism, growth, thyroid hormones, and survival of aquatic organisms. The observed concentrations and predicted biological effects are likely underestimates of the environmental impact of PFAS. Despite low anthropogenic influence in Lake Superior's watershed, PFAS were ubiquitous and occurred at potentially harmful concentrations.