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Title: Structural response of phyllomanganates to wet aging and aqueous Mn(II)

Abstract

Naturally occurring Mn(IV/III) oxides are often formed through microbial Mn(II) oxidation, resulting in reactive phyllomanganates with varying Mn(IV), Mn(III), and vacancy contents. Residual aqueous Mn(II) may adsorb in the interlayer of phyllomanganates above vacancies in their octahedral sheets. The potential for interlayer Mn(II)-layer Mn(IV) comproportionation reactions and subsequent formation of structural Mn(III) suggests that aqueous Mn(II) may cause phyllomanganate structural changes that alters mineral reactivity or trace metal scavenging. Here we examine the effects of aging phyllomanganates with varying initial vacancy and Mn(III) content in the presence and absence of dissolved Mn(II) at pH 4 and 7. Three phyllomanganates were studied: two exhibiting turbostratic layer stacking (δ-MnO2 with high vacancy content and hexagonal birnessite with both vacancies and Mn(III) substitutions) and one with rotationally ordered layer stacking (triclinic birnessite containing predominantly Mn(III) substitutions). Structural analyses suggest that during aging at pH 4, Mn(II) adsorbs above vacancies and promotes the formation of phyllomanganates with rotationally ordered sheets and mixed symmetries arranged into supercells, while structural Mn(III) undergoes disproportionation. These structural changes at pH 4 correlate with reduced Mn(II) uptake onto triclinic and hexagonal birnessite after 25 days relative to 48 h of reaction, indicating that phyllomanganate reactivity decreases upon aging withmore » Mn(II), or that recrystallization processes involving Mn(II) uptake occur over 25 days. At pH 7, Mn(II) adsorbs and causes limited structural effects, primarily increasing sheet stacking in δ-MnO2. These results show that aging-induced structural changes in phyllomanganates are affected by aqueous Mn(II), pH, and initial solid-phase Mn(III) content. In conclusion, such restructuring likely alters manganese oxide reactions with other constituents in environmental and geologic systems, particularly trace metals and redox-active compounds.« less

Authors:
 [1];  [1];  [1]
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  1. Washington Univ., St. Louis, MO (United States)
Publication Date:
Research Org.:
Washington Univ., St. Louis, MO (United States). School of Medicine
Sponsoring Org.:
National Science Foundation (NSF); USDOE
OSTI Identifier:
1418531
Alternate Identifier(s):
OSTI ID: 1432896
Grant/Contract Number:  
AC02-06CH11357; EAR-1056480; DGE-1143954; ECS-0335765; EAR-1161543
Resource Type:
Accepted Manuscript
Journal Name:
Geochimica et Cosmochimica Acta
Additional Journal Information:
Journal Volume: 192; Journal Issue: C; Journal ID: ISSN 0016-7037
Publisher:
The Geochemical Society; The Meteoritical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Hinkle, Margaret A. G., Flynn, Elaine D., and Catalano, Jeffrey G. Structural response of phyllomanganates to wet aging and aqueous Mn(II). United States: N. p., 2016. Web. doi:10.1016/j.gca.2016.07.035.
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Hinkle, Margaret A. G., Flynn, Elaine D., & Catalano, Jeffrey G. Structural response of phyllomanganates to wet aging and aqueous Mn(II). United States. https://doi.org/10.1016/j.gca.2016.07.035
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Hinkle, Margaret A. G., Flynn, Elaine D., and Catalano, Jeffrey G. Sat . "Structural response of phyllomanganates to wet aging and aqueous Mn(II)". United States. https://doi.org/10.1016/j.gca.2016.07.035. https://www.osti.gov/servlets/purl/1418531.
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@article{osti_1418531,
title = {Structural response of phyllomanganates to wet aging and aqueous Mn(II)},
author = {Hinkle, Margaret A. G. and Flynn, Elaine D. and Catalano, Jeffrey G.},
abstractNote = {Naturally occurring Mn(IV/III) oxides are often formed through microbial Mn(II) oxidation, resulting in reactive phyllomanganates with varying Mn(IV), Mn(III), and vacancy contents. Residual aqueous Mn(II) may adsorb in the interlayer of phyllomanganates above vacancies in their octahedral sheets. The potential for interlayer Mn(II)-layer Mn(IV) comproportionation reactions and subsequent formation of structural Mn(III) suggests that aqueous Mn(II) may cause phyllomanganate structural changes that alters mineral reactivity or trace metal scavenging. Here we examine the effects of aging phyllomanganates with varying initial vacancy and Mn(III) content in the presence and absence of dissolved Mn(II) at pH 4 and 7. Three phyllomanganates were studied: two exhibiting turbostratic layer stacking (δ-MnO2 with high vacancy content and hexagonal birnessite with both vacancies and Mn(III) substitutions) and one with rotationally ordered layer stacking (triclinic birnessite containing predominantly Mn(III) substitutions). Structural analyses suggest that during aging at pH 4, Mn(II) adsorbs above vacancies and promotes the formation of phyllomanganates with rotationally ordered sheets and mixed symmetries arranged into supercells, while structural Mn(III) undergoes disproportionation. These structural changes at pH 4 correlate with reduced Mn(II) uptake onto triclinic and hexagonal birnessite after 25 days relative to 48 h of reaction, indicating that phyllomanganate reactivity decreases upon aging with Mn(II), or that recrystallization processes involving Mn(II) uptake occur over 25 days. At pH 7, Mn(II) adsorbs and causes limited structural effects, primarily increasing sheet stacking in δ-MnO2. These results show that aging-induced structural changes in phyllomanganates are affected by aqueous Mn(II), pH, and initial solid-phase Mn(III) content. In conclusion, such restructuring likely alters manganese oxide reactions with other constituents in environmental and geologic systems, particularly trace metals and redox-active compounds.},
doi = {10.1016/j.gca.2016.07.035},
journal = {Geochimica et Cosmochimica Acta},
number = C,
volume = 192,
place = {United States},
year = {Sat Aug 06 00:00:00 EDT 2016},
month = {Sat Aug 06 00:00:00 EDT 2016}
}
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https://doi.org/10.1016/j.gca.2016.07.035
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