Comparative investigation of PFAS adsorption onto activated carbon and anion exchange resins during long-term operation of a pilot treatment plant

Widespread contamination of groundwater with per- and polyfluoroalkyl substances (PFAS) has required drinking water producers to quickly adopt practical and efficacious treatments to limit human exposure and deleterious health outcomes. This pilot-scale study comparatively investigated PFAS adsorption behaviors in granular activated carbon (GAC) and two strong-base gel anion exchange resin (AER) columns operated in parallel over a 441-day period to treat contaminated groundwater dominated by short-chain perfluorocarboxylic acids (PFCA). Highly-resolved breakthrough profiles of homologous series of 2–8 CF₂ PFCA and perfluorosulfonic acids (PFSA), including ultrashort-chain compounds and branched isomers, were measured to elucidate adsorption trends. Sample ports at intermediate bed depths could predict 50% breakthrough of compounds on an accelerated basis, but lower empty bed contact times led to conservative estimates of initial breakthrough. Homologous PFAS series displayed linear (GAC) and log-linear (AER) relationships between chain-length and breakthrough, independent of initial concentration. AERs generally outperformed GAC on a normalized bed volume basis, and this advantage widened with increasing PFAS chain-length. As designed, all treatments would have short full-scale service times (≤142 days for GAC; ≤61 days for AERs) before initial breakthrough of short-chain (2–4 CF₂) PFCA. However, AER displayed far longer breakthrough times for PFSA compared to GAC (>3× treatment time), and breakthrough was not observed for PFSA with >4 CF₂ in AERs. GAC had a finite molar adsorption capacity for total PFAS, leading to a stoichiometric replacement of short-chain PFCA by PFSA and longer-chain PFCA over time. AERs quickly reached a finite adsorption capacity for PFCA, but they showed substantially greater selectivity for PFSA whose capacity was not reached within the duration of the pilot. Breakthrough characteristics of keto- and unsaturated-PFSA, identified in the groundwater by suspect screening, were also evaluated in absence of reference standards. Modified PFAS structures (branched, keto-, unsaturated-) broke through faster than linear and unmodified perfluorinated structures with equal degrees of fluorination, and the effects were more pronounced in GAC compared to AERs. The results highlight that the design of robust PFAS treatment systems should consider facets beyond current PFAS targets including operational complexities and impacts of unregulated and unmonitored co-contaminants.