Transport of per- and polyfluoroalkyl
substances (PFAS) to the
Great Lakes is of great importance as this large freshwater system
provides drinking water to over 40 million people. Tributary PFAS
loading to the Great Lakes is poorly characterized, and the role of
sediments as a source or sink of PFAS is largely unknown. We quantified
10 perfluoroalkyl acids (PFAAs) in water (4–1310 ng/L) and
sediment (below detection to 3255 ng/kg) of 41 tributaries to Green
Bay of Lake Michigan. We demonstrate that tributary discharge plays
a major role in PFAS contribution to receiving waters. In this system,
three large rivers (i.e., Fox, Menominee, and Peshtigo Rivers) contribute
two-thirds of the total tributary PFAA loading to Green Bay despite
their relatively low concentrations. This circumvents the current
regulatory focus on sites with high concentrations. Tributary PFAA
composition is linked to likely sources, including a fire-fighting
foam manufacturer, other industrial activities, and airports. In addition
to tributary discharge, we show that tributary sediments can contribute
to PFAA transport via desorption. Perfluorooctanesulfonate rapidly
desorbs from contaminated riverbed sediments when equilibrated with
Lake Michigan water, indicating that sediments may act as a PFAS source
if water concentrations are reduced by pollution mitigation methods.