Unrecognized Role of Organic Acid in Natural Attenuation of Pollutants by Mackinawite (FeS): The Significance of Carbon-Center Free Radicals

Organic acid is prevalent in underground environments and, against the backdrop of biogeochemical cycles on Earth, holds significant importance in the degradation of contaminants by redox-active minerals. While earlier studies on the role of organic acid in the generation of reactive oxygen species (ROS) primarily concentrated on electron shuttle or ligand effects, this study delves into the combined impacts of organic acid decomposition and Mackinawite (FeS) oxidation in contaminant transformation under dark aerobic conditions. Using bisphenol A (BPA) as a model, our findings showed that oxalic acid (OA) notably outperforms other acids in enhancing BPA removal, attaining a rate constant of 0.69 h-1. Mass spectrometry characterizations, coupled with anaerobic treatments, advocate for molecule-O2 activation as the principal mechanism behind pollutant transformation. Comprehensive results unveiled that carbon center radicals, initiated by hydroxyl radical (•OH) attack, serve as the primary agents in pollutant oxidation, accounting for at least 93.6% of the total •OH generation. This dynamic, driven by the decomposition of organic acids and the concurrent formation of carbon-centered radicals, ensures a steady supply of electrons for ROS generation. The obtained information highlights the importance of OA decomposition in the natural attenuation of pollutants and offers innovative strategies for FeS and organic acid-coupled decontamination.