Molecular transformation of petroleum compounds by hydroxyl radicals produced upon oxidation of reduced nontronite

At redox interfaces, the interaction between oxygen and structural Fe(II) in minerals produces hydroxyl radicals (●OH); however, the specific reactivity and mechanisms of oxidation of complex petroleum compounds by ●OH remain poorly understood. This study investigates the interaction mechanisms between ●OH generated from reduced nontronite, an Fe-rich clay mineral (NAu-2), and petroleum compounds by employing a suite of wet chemistry, gas chromatography mass spectrometry and Fourier transform-ion cyclotron resonance-mass spectrometry, as well as theoretical calculations. The results showed that the intrinsic structure, composition, solubility, and adsorption of petroleum molecules onto reduced NAu-2 significantly influenced their reactivity with ●OH. Specifically, the aromatic fraction of a crude oil sample exerted a minimal influence on the oxidation rate of structural Fe(II) in reduced NAu-2, but enhanced the production of ●OH by generating environmentally persistent free radicals. ●OH reacted more with water-soluble dissolved organic matter from oil compared to polar compounds. The newly generated molecules by ●OH exhibited a preference for the insoluble (polar) phase. The oxidation of petroleum hydrocarbons by ●OH was mediated through hydrogen atom abstraction and radical adduct formation, followed by dehydrogenation, hydroxylation, and carboxylation reactions. Consequently, the abundance of oxygen-containing compounds in polar compounds increased. However, specific oxidation pathways differed depending on the nature of petroleum compounds. Our results provide insights that oxidation of petroleum compounds by ●OH is vital for mitigating the negative impacts from hydrocarbon contamination and for evaluating the role of these processes in the carbon cycle in redox-active environments.