Volatility and Nonspecific van der Waals Interaction Properties of Per- and Polyfluoroalkyl Substances (PFAS): Evaluation Using Hexadecane/Air Partition Coefficients

摘要

Per- and polyfluoroalkyl substances (PFAS) form weak van der Waals (vdW) interactions, which render this class of chemicals more volatile than nonfluorinated analogues. Here, the hexadecane/air partition coefficient (K_(Hxd/air)) values at 25 °C, as an index of vdW interaction strength and volatility, were determined for 64 neutral PFAS using the variable phase ratio headspace and gas chromatographic retention methods. Log K_(Hxd/air) values increased linearly with increasing number of CF2 units, and the increase in log K_(Hxd/air) value per CF2 was smaller than that per CH2. Comparison of PFAS sharing the same perfluoroalkyl chain length but with different functional groups demonstrated that K_(Hxd/air) was highest for the W-alkyl perfluoroalkanesulfonamidethanols and lowest for the perfluoroalkanes and that the size of the nonfluorinated structure determines the difference in K_(Hxd/air) between PFAS groups. Two models, the quantum chemistry-based COSMO therm model and an iterative fragment selection quantitative structure-property relationship (IFS-QSPR) model, accurately predicted the log K_(Hxd/air) values of the PFAS with root-mean-square errors of 0.55 and 0.35, respectively. COSMOtherm showed minor systematic errors for all PFAS, whereas IFS-QSPR exhibited large errors for a few PFAS groups that were outside the model applicability domain. The present data set will be useful as a benchmark of the volatilities of the various PFAS and for predicting other partition coefficient values of PFAS.