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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]
  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
Resource Type:
Journal Article: 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.
Hinkle, Margaret A. G., Flynn, Elaine D., & Catalano, Jeffrey G. Structural response of phyllomanganates to wet aging and aqueous Mn(II). United States. doi:10.1016/j.gca.2016.07.035.
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. doi:10.1016/j.gca.2016.07.035. https://www.osti.gov/servlets/purl/1418531.
@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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  • We studied the impacts of aqueous Mn(II) (1 mM) on the sorption of Ni(II) (200 μM) by hexagonal birnessite (0.1 g L- 1) at pH 6.5 and 7.5 with batch experiments and XRD, ATR-FTIR and Ni K-edge EXAFS analyses. In the absence of Mn(II)aq, sorbed Ni(II) was coordinated predominantly as triple corner-sharing complexes at layer vacancies at both pH values. Introduction of Mn(II)aq into Ni(II)-birnessite suspensions at pH 6.5 caused Ni(II) desorption and led to the formation of edge-sharing Ni(II) complexes. This was attributed to competitive displacement of Ni(II) from layer vacancies by either Mn(II) or by Mn(III) formed throughmore » interfacial Mn(II)-Mn(IV) comproportionation, and/or incorporation of Ni(II) into the birnessite lattice promoted by Mn(II)-catalyzed recrystallization of the sorbent. Similar to Mn(II)aq, the presence of HEPES or MES caused the formation of edge-sharing Ni(II) sorption complexes in Ni(II)-birnessite suspensions, which was attributed to partial reduction of the sorbent by the buffers. At pH 7.5, interaction with aqueous Mn(II) caused reductive transformation of birnessite into secondary feitknechtite that incorporated Ni(II), enhancing removal of Ni(II) from solution. These results demonstrate that reductive alteration of phyllomanganates may significantly affect the speciation and solubility of Ni(II) in anoxic and suboxic environments.« less
  • Caustic high level radioactive waste induces mineral weathering reactions that can influence the fate of radionuclides released in the vicinity of leaking storage tanks. The uptake and release of CsI and SrII were studied in batch reactors of 2:1 layer-type silicates?illite (Il), vermiculite (Vm) and montmorillonite (Mt)?under geochemical conditions characteristic of leaking tank waste at the Hanford Site in WA (0.05 mAlT, 2 m Na*, 1 m NO3 *, pH *14, Cs and Sr present as co-contaminants). Time series (0 to 369 d) experiments were conducted at 298 K, with initial [Cs]0 and [Sr]0 concentrations from 10*5 to 10*3 molmore » kg*1. Clay mineral type affected the rates of (1) hydroxide promoted dissolution of Si, Al and Fe, (2) precipitation of secondary solids and (3) uptake of Cs and Sr. Initial Si release to solution followed the order Mt * Vm * Il. An abrupt decrease in soluble Si and/or Al after 33 d for Mt and Vm systems, and after 190 d for Il suspensions was concurrent with accumulation of secondary aluminosilicate precipitates. Strontium uptake exceeded that of Cs in both rate and extent, although sorbed Cs was generally more recalcitrant to subsequent desorption and dissolution. After 369 d reaction time, reacted Il, Vm and Mt solids retained up to 17, 47 and 14 mmol kg*1 (0.18, 0.24 and 0.02 *mol m*2) of Cs, and 0, 27 and 22 mmol kg*1 (0, 0.14 and 0.03 *molm*2) Sr, respectively, which were not removed in subsequent Mg exchange or oxalic acid dissolution reactions. Solubility of Al and Si decreased with initial Cs and Sr concentration in Mt and Il, but not in Vm. High co-contaminant sorption to the Vm clay, therefore, appears to diminish the influence of those ions on mineral transformation rates.« less
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