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Title: Structural Transformation of Birnessite by Fulvic Acid under Anoxic Conditions

Abstract

The structure and Mn(III) concentration of birnessite dictate its reactivity and can be changed by birnessite partial reduction, but effects of pH and reductant/birnessite ratios on the changes by reduction remain unclear. We found that the two factors strongly affect the structure of birnessite (δ-MnO2) and its Mn(III) content during its reduction by fulvic acid (FA) at pH 4–8 and FA/solid mass ratios of 0.01–10 under anoxic conditions over 600 h. During the reduction, the structure of δ-MnO2 is increasingly accumulated with both Mn(III) and Mn(II) but much more with Mn(III) at pH 8, whereas the accumulated Mn is mainly Mn(II) with little Mn(III) at pH 4 and 6. Mn(III) accumulation, either in layers or over vacancies, is stronger at higher FA/solid ratios. At FA/solid ratios ≥1 and pH 6 and 8, additional hausmannite and MnOOH phases form. The altered birnessite favorably adsorbs FA because of the structural accumulation of Mn(II, III). Like during microbially mediated oxidative precipitation of birnessite, the dynamic changes during its reduction are ascribed to the birnessite-Mn(II) redox reactions. Here, our work suggests low reactivity of birnessite coexisting with organic matter and severe decline of its reactivity by partial reduction in alkaline environment.

Authors:
 [1];  [1]; ORCiD logo [1]
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  1. Univ. of Wyoming, Laramie, WY (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1424770
Grant/Contract Number:  
AC02-06CH11357; EAR-1529937
Resource Type:
Accepted Manuscript
Journal Name:
Environmental Science and Technology
Additional Journal Information:
Journal Volume: 52; Journal Issue: 4; Journal ID: ISSN 0013-936X
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; redox reactions; adsorption; layers; pH; transition metals

Citation Formats

Wang, Qian, Yang, Peng, and Zhu, Mengqiang. Structural Transformation of Birnessite by Fulvic Acid under Anoxic Conditions. United States: N. p., 2018. Web. doi:10.1021/acs.est.7b04379.
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Wang, Qian, Yang, Peng, & Zhu, Mengqiang. Structural Transformation of Birnessite by Fulvic Acid under Anoxic Conditions. United States. https://doi.org/10.1021/acs.est.7b04379
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Wang, Qian, Yang, Peng, and Zhu, Mengqiang. Mon . "Structural Transformation of Birnessite by Fulvic Acid under Anoxic Conditions". United States. https://doi.org/10.1021/acs.est.7b04379. https://www.osti.gov/servlets/purl/1424770.
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@article{osti_1424770,
title = {Structural Transformation of Birnessite by Fulvic Acid under Anoxic Conditions},
author = {Wang, Qian and Yang, Peng and Zhu, Mengqiang},
abstractNote = {The structure and Mn(III) concentration of birnessite dictate its reactivity and can be changed by birnessite partial reduction, but effects of pH and reductant/birnessite ratios on the changes by reduction remain unclear. We found that the two factors strongly affect the structure of birnessite (δ-MnO2) and its Mn(III) content during its reduction by fulvic acid (FA) at pH 4–8 and FA/solid mass ratios of 0.01–10 under anoxic conditions over 600 h. During the reduction, the structure of δ-MnO2 is increasingly accumulated with both Mn(III) and Mn(II) but much more with Mn(III) at pH 8, whereas the accumulated Mn is mainly Mn(II) with little Mn(III) at pH 4 and 6. Mn(III) accumulation, either in layers or over vacancies, is stronger at higher FA/solid ratios. At FA/solid ratios ≥1 and pH 6 and 8, additional hausmannite and MnOOH phases form. The altered birnessite favorably adsorbs FA because of the structural accumulation of Mn(II, III). Like during microbially mediated oxidative precipitation of birnessite, the dynamic changes during its reduction are ascribed to the birnessite-Mn(II) redox reactions. Here, our work suggests low reactivity of birnessite coexisting with organic matter and severe decline of its reactivity by partial reduction in alkaline environment.},
doi = {10.1021/acs.est.7b04379},
journal = {Environmental Science and Technology},
number = 4,
volume = 52,
place = {United States},
year = {Mon Jan 22 00:00:00 EST 2018},
month = {Mon Jan 22 00:00:00 EST 2018}
}
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https://doi.org/10.1021/acs.est.7b04379
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