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Title: Impact of Mn(II)-Manganese Oxide Reactions on Ni and Zn Speciation

Abstract

Layered Mn oxide minerals (phyllomanganates) often control trace metal fate in natural systems. The strong uptake of metals such as Ni and Zn by phyllomanganates results from adsorption on or incorporation into vacancy sites. Mn(II) also binds to vacancies and subsequent comproportionation with structural Mn(IV) may alter sheet structures by forming larger and distorted Mn(III)O6 octahedra. Such Mn(II)-phyllomanganate reactions may thus alter metal uptake by blocking key reactive sites. Here we investigate the effect of Mn(II) on Ni and Zn binding to phyllomanganates of varying initial vacancy content (δ-MnO2, hexagonal birnessite, and triclinic birnessite) at pH 4 and 7 under anaerobic conditions. Dissolved Mn(II) decreases macroscopic Ni and Zn uptake at pH 4 but not pH 7. Extended X-ray absorption fine structure spectroscopy demonstrates that decreased uptake at pH 4 corresponds with altered Ni and Zn adsorption mechanisms. These metals transition from binding in the interlayer to sheet edges, with Zn increasing its tetrahedrally coordinated fraction. These effects on metal uptake and binding correlate with Mn(II)-induced structural changes, which are more substantial at pH 4 than 7. Finally, through these structural effects and the pH-dependence of Mn(II)-metal competitive adsorption, system pH largely controls metal binding to phyllomanganates in the presencemore » of dissolved Mn(II).« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2]
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  1. Washington Univ., Saint Louis, MO (United States)
  2. Washington Univ., St. Louis, MO (United States)
Publication Date:
Research Org.:
Washington Univ., Saint Louis, MO (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC)
OSTI Identifier:
1418550
Grant/Contract Number:  
AC02-06CH11357; AC02-76SF00515; EAR-1056480
Resource Type:
Accepted Manuscript
Journal Name:
Environmental Science and Technology
Additional Journal Information:
Journal Volume: 51; Journal Issue: 6; 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; Physiology; Metals; Adsorption; Defects in solids; Vinyl

Citation Formats

Hinkle, Margaret G., Dye, Katherine G., and Catalano, Jeffrey G. Impact of Mn(II)-Manganese Oxide Reactions on Ni and Zn Speciation. United States: N. p., 2017. Web. doi:10.1021/acs.est.6b04347.
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Hinkle, Margaret G., Dye, Katherine G., & Catalano, Jeffrey G. Impact of Mn(II)-Manganese Oxide Reactions on Ni and Zn Speciation. United States. https://doi.org/10.1021/acs.est.6b04347
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Hinkle, Margaret G., Dye, Katherine G., and Catalano, Jeffrey G. Wed . "Impact of Mn(II)-Manganese Oxide Reactions on Ni and Zn Speciation". United States. https://doi.org/10.1021/acs.est.6b04347. https://www.osti.gov/servlets/purl/1418550.
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@article{osti_1418550,
title = {Impact of Mn(II)-Manganese Oxide Reactions on Ni and Zn Speciation},
author = {Hinkle, Margaret G. and Dye, Katherine G. and Catalano, Jeffrey G.},
abstractNote = {Layered Mn oxide minerals (phyllomanganates) often control trace metal fate in natural systems. The strong uptake of metals such as Ni and Zn by phyllomanganates results from adsorption on or incorporation into vacancy sites. Mn(II) also binds to vacancies and subsequent comproportionation with structural Mn(IV) may alter sheet structures by forming larger and distorted Mn(III)O6 octahedra. Such Mn(II)-phyllomanganate reactions may thus alter metal uptake by blocking key reactive sites. Here we investigate the effect of Mn(II) on Ni and Zn binding to phyllomanganates of varying initial vacancy content (δ-MnO2, hexagonal birnessite, and triclinic birnessite) at pH 4 and 7 under anaerobic conditions. Dissolved Mn(II) decreases macroscopic Ni and Zn uptake at pH 4 but not pH 7. Extended X-ray absorption fine structure spectroscopy demonstrates that decreased uptake at pH 4 corresponds with altered Ni and Zn adsorption mechanisms. These metals transition from binding in the interlayer to sheet edges, with Zn increasing its tetrahedrally coordinated fraction. These effects on metal uptake and binding correlate with Mn(II)-induced structural changes, which are more substantial at pH 4 than 7. Finally, through these structural effects and the pH-dependence of Mn(II)-metal competitive adsorption, system pH largely controls metal binding to phyllomanganates in the presence of dissolved Mn(II).},
doi = {10.1021/acs.est.6b04347},
journal = {Environmental Science and Technology},
number = 6,
volume = 51,
place = {United States},
year = {Wed Mar 01 00:00:00 EST 2017},
month = {Wed Mar 01 00:00:00 EST 2017}
}
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https://doi.org/10.1021/acs.est.6b04347
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