Per- and polyfluoroalkyl substances (PFAS) in final treated solids (Biosolids) from 190 Michigan wastewater treatment plants.

Trends in concentration, distribution, and variability of per- and polyfluoroalkyl substances (PFAS) in biosolids are characterized using an extensive dataset of 350 samples from 190 wastewater treatment plants (WWTPs) across Michigan. All samples are comprised of final treated solids generated at the end of the wastewater treatment process. Concentrations of both individual and Σ24 PFAS are lognormally distributed, with Σ24 PFAS concentrations ranging from 1-3200 ng/g and averaging 108 ± 277 ng/g dry wt. PFAS with carboxyl and sulfonic functional groups comprise 29% and 71% of Σ24 PFAS concentrations, respectively, on average. Primary sample variability in concentration is associated with long-chain PFAS with higher tendency for partitioning to biosolids. Short-chain carboxylic compounds, most notably PFHxA, are responsible for secondary concentration variability. Usage of FTSA and PFBS replacements to long-chain sulfonic compounds also contributes to variance in biosolids concentrations. Sulfonamide precursor compounds as a collective group are detected at a similar frequency as PFOS and often have higher concentrations. Trends in PFAS enrichment for individual PFAS vary at least 3 orders-of-magnitude and generally increase with compound hydrophobicity; however, partitioning of PFAS onto solids in WWTPs is a complex process not easily described nor constrained using experimentally-derived partitioning coefficients.

Long-duration monitoring and mass balance of PFAS at a wastewater treatment plant following the release of aqueous film-forming foam concentrate.

Approximately 760 liters (200 gallons) of first-generation, PFOS-dominant, Aqueous Film-Forming Foam (AFFF) concentrate entered the sanitary sewer after an accidental release at the Kalamazoo/Battle Creek International Airport and migrated 11.4 km to the Kalamazoo Water Reclamation Plant. Near-daily sampling of influent, effluent, and biosolids generated a high-frequency, long-duration dataset used to understand the transport and fate of accidental PFAS releases to wastewater treatment plants, identify AFFF concentrate composition, and perform a plant-wide PFOS mass balance. Monitored influent concentrations exhibited sharp PFOS declines after 7 days post-spill, yet effluent discharges remained elevated due to return activated sludge (RAS) recirculation, resulting in the exceedance of Michigan's Surface Water Quality Value for 46 days. Mass balance estimates indicate 1.292 kg PFOS entering the plant and 1.368 kg leaving. Effluent discharge and sorption to biosolids account for 55% and 45% of estimated PFOS outputs, respectively. Identification of AFFF formulation and reasonable agreement between computed influent mass and reported spill volume demonstrates effective isolation of the AFFF spill signal and increases confidence in the mass balance estimates. These findings and related considerations provide critical insight for performing PFAS mass balances and developing operational procedures for accidental spills that minimize PFAS releases to the environment.