Hydrophobic Sorption Properties of an Extended Series of Anionic Per- and Polyfluoroalkyl Substances Characterized by C₁₈ Chromatographic Retention Measurement

Abstract

Partitioning from water to nonaqueous phases is an important process that controls the behavior of contaminants in the environment and biota. However, for ionic chemicals including many perfluoroalkyl and polyfluoroalkyl substances (PFAS), environmentally relevant partition coefficients cannot be predicted using the octanol/water partition coefficient, which is commonly used as a hydrophobicity indicator for neutral compounds. As an alternative, this study measured C 18 liquid chromatography retention times of 39 anionic PFAS and 20 nonfluorinated surfactants using isocratic methanol/water eluent systems. By measuring a series of PFAS with different perfluoroalkyl chain lengths, retention factors at 100% water (k 0 ) were successfully extrapolated even for long-chain PFAS. Molecular size was the most important factor determining the k 0 of PFAS and non-PFAS, suggesting that the cavity formation process is the key driver for retention. Log k 0 showed a high correlation with the log of partition coefficients from water to the phospholipid membrane, air/water interface, and soil organic carbon. The results indicate the potential of C 18 retention factors as predictive descriptors for anionic PFAS partition coefficients and the possibility of developing a more comprehensive multiparameter model for the partitioning of anionic substances in general.