A ReaxFF-based molecular dynamics study of the destruction of PFAS due to ultrasound

Abstract

This work uses a computational approach to provide a mechanistic explanation for the experimentally observed destruction of per- and polyfluoroalkyl substances (PFAS) in water due to ultrasound. The PFAS compounds have caused a strong public and regulatory response due to their ubiquitous presence in the environment and toxicity to humans. In this research, ReaxFF -based Molecular Dynamics simulation under several temperatures ranging from 373 K to 5,000 K and different environments such as water vapor, O₂, N_2, and air were performed to understand the mechanism of PFAS destruction. The simulation results showed greater than 98% PFAS degradation was observed within 8 ns under a temperature of 5,000 K in a water vapor phase, replicating the observed micro/nano bubbles implosion and PFAS destruction during the application of ultrasound. Additionally, the manuscript discusses the reaction pathways and how PFAS degradation evolves providing a mechanistic basis for the destruction of PFAS in water due to ultrasound. The simulation showed that small chain molecules C₁ and C₂ fluoro-radical products are the most dominant species over the simulated period and are the impediment to an efficient degradation of PFAS. Furthermore, this research confirms the empirical findings observations that the mineralization of PFAS molecules occurs without the generation of byproducts. These findings highlight the potential of virtual experiments in complementing laboratory experiments and theoretical projections to enhance the understanding of PFAS mineralization during the application of ultrasound.

Keywords: Molecular dynamics simulation; Organic pollutants; PFAS mineralization; PFOA; Perfluorinated chemicals.