Isomer-specific biotransformation of perfluoroalkyl sulfonamide compounds in aerobic soil

Abstract

As an important reservoir of pollutants, soil may play a critical role in altering isomer ratios of perfluorooctane sulfonate (PFOS) or PFOS precursors (PrePFOS) via microbial processes, but this possibility has not yet been investigated, as well as the feasibility of using PFOS isomer ratio for source tracking in PFOS contaminated sites. In the present study, N‑ethyl perfluorooctane sulfonamide ethanol (EtFOSE) of the technical grade was incubated in soil microcosms for 105 days to examine isomer-specific transformation processes. Experimental data combined with a mathematical model suggest new biotransformation pathways leading to PFOS, including a direct pathway to produce PFOS via hydrolysis of the sulfonamide bond. A similar rate of biotransformation was observed for EtFOSE with an estimated half-life of 8.7 and 9.6 days for the branched and linear isomers, respectively, without statistical difference. Two transformation intermediates, N‑ethyl perfluorooctanoic acid (EtFOSAA) and perfluorooctane sulfonamide (FOSA), also showed preferential biotransformation of branched isomers. On the contrary, one intermediate N‑ethyl perfluorooctane sulfonamide (EtFOSA) showed the preferred transformation of the linear isomer with an estimated half-life of 80.8 and 11.2 days for the branched and linear isomers, respectively. As PFOS is likely to be generated through more than one pathway or one precursor, its final isomer ratio is collectively determined by several upstream reactions, each having specific isomer-specific transformation kinetics. Though the soil showed enrichment of branched PFOS isomers during the 4-month incubation, compared to PFOS standards, some uncertainty arises in concluding preferential generation of branched PFOS from its precursors, due to the lack of standards for branched PreFOS. The complexity of isomer-specific biotransformation only reinforced the challenge of applying the PFOS isomer ratio for source tracking in environmental microbial systems.

Keywords: Biotransformation; Environmental fate; Isomer-specific; PFOS; PFOS precursor; Soil.