Transformation of para arsanilic acid by manganese oxide: Adsorption, oxidation, and influencing factors.

Aromatic organoarsenic compounds tend to transform into more mobile toxic inorganic arsenic via several processes, and can inadvertently spread toxic inorganic arsenic through the environment to water sources. To gain insight into the transformation mechanisms, we herein investigated how the process of para arsanilic acid (p-ASA) transformation works in detail on the surface of adsorbents by comparing it with phenylarsonic acid (PA) and aniline, which have similar chemical structures. In contrast to the values of 0.23 mmol g-1 and 0.68 mmol g-1 for PA and aniline, the maximum adsorption capacity was determined to be 0.40 mmol g-1 for p-ASA at pH 4.0. The results of FTIR and XPS spectra supported the presence of a protonated amine, resulting in a suitable condition for the oxidation of p-ASA. Based on the combined results of UV-spectra and UPLC-Q-TOF-MS, we confirmed that the adsorbed p-ASA was first oxidized through the transfer of one electron from p-ASA on MnO2 surface to form a radical intermediate, which through further hydrolysis and coupling led to formation of benzoquinone and azophenylarsonic acid, which was identified as a major intermediate. After that, p-ASA radical intermediate was cleaved to form arsenite (III), and then further oxidized into arsenate (V) with the release of manganese (Mn) into solution, indicating a heterogeneous oxidation process.