Transformation of m-aminophenol by birnessite (δ-MnO2) mediated oxidative processes: Reaction kinetics, pathways and toxicity assessment

Huang, Wenqian; Wu, Guowei; Xiao, Hong; Song, Haiyan; Gan, Shuzhao; Ruan, Shuhong; Gao, Zhihong; Song, Jianzhong

Transformation of m-aminophenol by birnessite (δ-MnO2) mediated oxidative processes: Reaction kinetics, pathways and toxicity assessment

2020

The m-aminophenol (m-AP) is a widely used industrial chemical, which enters water, soils, and sediments with waste emissions. A common soil metal oxide, birnessite (δ-MnO2), was found to mediate the transformation of m-AP with fast rates under acidic conditions. Because of the highly complexity of the m-AP transformation, mechanism-based models were taken to fit the transformation kinetic process of m-AP. The results indicated that the transformation of m-AP with δ-MnO2 could be described by precursor complex formation rate-limiting model. The oxidative transformation of m-AP on the surface of δ-MnO2 was highly dependent on reactant concentrations, pH, temperature, and other co-solutes. The UV-VIS absorbance and mass spectra analysis indicated that the pathway leading to m-AP transformation may be the polymerization through the coupling reaction. The m-AP radicals were likely to be coupled by the covalent bonding between unsubstituted C2, C4 or C6 atoms in the m-AP aromatic rings to form oligomers as revealed by the results of activation energy and mass spectra. Furthermore, the toxicity assessment of the transformation productions indicated that the toxicity of m-AP to the E. coli K-12 could be reduced by MnO2 mediated transformation. The results are helpful for understanding the environmental behavior and potential risk of m-AP in natural environment.

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