Differential Sorption of Short-Chain versus Long-Chain Anionic Per- and Poly-Fluoroalkyl Substances by Soils

Abstract

The impact of chain length on the sorption of anionic PFAS by soils and sediments was investigated by aggregating and synthesizing data sets from the literature. Quantitative structure/property relationship (QSPR) analysis was applied to characterize the influence of molecular size and soil properties on sorption. The log of the organic carbon-normalized equilibrium sorption coefficient (Koc) exhibited a biphasic relationship with molar volume, wherein the log Koc values for the short-chain PFAS were generally greater than would be predicted using the QSPR correlation determined for the long-chain PFAS. This enhanced differential sorption is observed to different degrees for all studies, which are compiled and synthesized for the first time. The results reveal remarkable congruency across a wide array of soils comprising a large range of properties and indicate that the observed enhanced differential sorption of short-chain PFAS is a prevalent phenomenon. Aggregating the long-chain PFAS data for all soils and sediments with organic carbon contents > 1% produced a strong correlation, indicating that the resultant QSPR model can produce representative log Koc values irrespective of the other properties of the medium. Silt+clay content was shown to be an important soil component for the short-chain PFAS for most soils, as well as the long-chain PFAS for soils with organic carbon contents < 1%. The results indicate that while the simple Koc-foc approach may produce reasonable estimates of Kd values for long-chain anionic PFAS, particularly for soils and sediments with larger organic carbon contents, it is unlikely to do so for short-chain anionic PFAS.