Tunable Mn Oxidation State and Redox Potential of Birnessite Coexisting with Aqueous Mn(II) in Mildly Acidic Environments

As the dominant manganese oxide mineral phase in terrestrial and aquatic environments, birnessite plays an important role in many biogeochemical processes. The coexistence of birnessite with aqueous Mn<sup>2+</sup> is commonly found in the subsurface environments undergoing Mn redox cycl...

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Bibliographic Details
Main Authors: Juan Liu, Yixiao Zhang, Qian Gu, Anxu Sheng, Baogang Zhang
Format: Article
Language:English
Published: MDPI AG 2020-08-01
Series:Minerals
Subjects:
Online Access:https://www.mdpi.com/2075-163X/10/8/690
Description
Summary:As the dominant manganese oxide mineral phase in terrestrial and aquatic environments, birnessite plays an important role in many biogeochemical processes. The coexistence of birnessite with aqueous Mn<sup>2+</sup> is commonly found in the subsurface environments undergoing Mn redox cycling. This study investigates the change in Mn average oxidation state (AOS) of birnessite after reaction with 0.1–0.4 mM Mn<sup>2+</sup> at pH 4.5–6.5, under conditions in which phase transformation of birnessite by Mn<sup>2+</sup> was not detectable. The amount of Mn<sup>2+</sup> uptake by birnessite and the equilibrium concentration of Mn(III) proportionally increased with the initial concentration of Mn<sup>2+</sup>. The Mn AOS of birnessite particles became 3.87, 3.75, 3.64, and 3.53, respectively, after reaction with 0.1, 0.2, 0.3, and 0.4 mM Mn<sup>2+</sup> at pH 5.5. Oxidation potentials (<i>E<sub>h</sub></i>) of birnessite with different AOS values were estimated using the equilibrium concentrations of hydroquinone oxidized by the birnessite samples, indicating that <i>E<sub>h</sub></i> was linearly proportional to AOS. The oxidation kinetics of bisphenol A (BPA), a model organic pollutant, by birnessite suggest that the logarithms of surface area-normalized pseudo-first-order initial rate constants (log <i>k<sub>SA</sub></i>) for BPA degradation by birnessite were linearly correlated with the <i>E<sub>h</sub></i> or AOS values of birnessite with AOS greater than 3.64.
ISSN:2075-163X