Effect of heavy metal co-contaminants on the sorption of thirteen anionic per- and poly-fluoroalkyl substances (PFAS) in soils.

Understanding the sorption behavior of per- and poly-fluoroalkyl substances (PFAS) in soils are essential for assessing their mobility and risk in the environment. Heavy metals often coexist with PFAS depending on the source and history of contamination. In this study, we investigated the effect of heavy metal co-contaminants (Pb, Cu and Zn) on the sorption of 13 anionic PFAS with different perfluorocarbon chain length (C3-C9) in two soils with different properties. Results revealed that Pb, Cu and Zn had little effect on the sorption of most short-chain compounds, while the presence of these heavy metals enhanced the sorption of long-chain PFAS in two soils. The distribution coefficients (K) of several long-chain PFAS linearly increased with increasing concentrations of heavy metal, especially in the presence of Pb (ΔK/Δ [Pb] > 3 for PFOS and PFNA vs <1 for PFPeS and PFHxS). While several mechanisms may have contributed to the enhancement of sorption of PFAS, the heavy metals most likely contributed through enhanced hydrophobic interactions of PFAS by neutralizing the negative charge of adsorption surfaces in soils and thus making it more favorable for their partitioning onto the solid phase. Moreover, the increase in the concentrations of heavy metals led to a decrease in the pH of the system and promoted sorption of long-chain compounds, especially in soil with lower organic carbon content. Overall, this study provides evidence that the presence of co-existing heavy metal cations in soils can significantly enhance the sorption of long-chain PFAS onto soil, thereby potentially limiting their mobility in the environment.