Assessment of perfluorohexane sulfonic acid (PFHxS)-related compounds degradation potential: Computational and experimental approaches

Abstract

Perfluorohexane sulfonic acid (PFHxS) and PFHxS-related compounds are listed in Annex A of the Stockholm Convention without specific exemptions. Substances that potentially degrade to PFHxS are considered as their related compounds. Unfortunately, the degradation behavior of PFHxS precursors, an important basis for the corresponding chemical regulation, remains unclear. Herein, based on the hypothesis that bond dissociation enthalpy (BDE) is the determining factor for the degradation of PFHxS precursors, the BDE of PFHxS-related precursors to produceC6F13SO2-groups was calculated. In addition, quantitative structure-activity relationship models based on partial least squares, partial least squares discrimination analysis, and support vector machine algorithms were developed to predict the BDE of 48 PFHxS precursors and distinguish the precursors with different degradation potential. Subsequent photodegradation experiments demonstrated that the order of degradation rates was consistent with that predicted by theoretical models. Importantly, perfluorohexanoic acid (PFHxA) and perfluorobutanoic acid, and not PFHxS, were detected as the degradation products of potential PFHxS precursors. Sulfonamides, phenyl unit, and other radicals in the non-nucleus part of PFHxS precursors were identified as the critical molecular segments that affect their degradation potential. Ultimately, by comparing BDE values, it was theoretically speculated that PFHxS related compounds exhibit a greater potential to generate PFHxA than PFHxS. Results in this study indicated for the first time that not all the compounds containing C6F13SO2- groups were guaranteed to degrade into PFHxS under natural conditions.

Keywords: Bond dissociation enthalpy; Degradation potential; Machine learning; Perfluorohexane sulfonic acid; Photodegradation.