High stability and unusual chemical properties make perfluoroalkyl carboxylic acids (PFCAs) ideal for many stringent specific need applications. However, their widespread use has led to extensive environmental and biological contamination. The inert nature of PFCAs makes their remediation a great contemporary challenge. Oxidation by sulfate radical from activated peroxydisulfate (persulfate) provides the opportunity to degrade these recalcitrant molecules. Many studies using thermally activated persulfate for PFCA degradation have found that a low matrix pH is necessary, and this is a major hurdle for transferring the technology to the field. A description of the mechanistic role protons play in PFCA oxidation by sulfate radicals will provide insight into what conditions are actually amenable for activated persulfate PFCA remediation. Results from computational and empirical techniques used to study this pH effect will be presented. Density functional theory studies explored specific interactions that could influence kinetics, and transient absorption spectroscopy was used to evaluate rate constants under variable pH conditions.

Investigating the influence of pH on activated-persulfate oxidation of perfluoroalkyl carboxylic acids using DFT and transient absorption spectroscopy

ACS Spring Meeting 2021

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