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Title: Metal Adsorption Controls Stability of Layered Manganese Oxides

Abstract

Hexagonal birnessite, a typical layered Mn oxide (LMO), can adsorb and oxidize Mn(II) and thereby transform to Mn(III)-rich hexagonal birnessite, triclinic birnessite, and/or tunneled Mn oxides (TMOs), remarkably changing the environmental behavior of Mn oxides. We have determined the effects of co-existing cations on the transformation by incubating Mn(II)-bearing δ-MnO2 at pH 8 under anoxic conditions for 25 d (dissolved Mn < 11 μM). In the Li+, Na+ or K+ chloride solution, the Mn(II)-bearing δ-MnO2 first transforms to Mn(III)-rich δ-MnO2 and/or triclinic birnessite (T-bir) due to the Mn(II)-Mn(IV) comproportionation, most of which eventually transform to a 4 × 4 TMO. In contrast, Mn(III)-rich δ-MnO2 and T-bir form and persist in the Mg2+ or Ca2+ chloride solution. Yet, in the presence of surface adsorbed Cu(II), Mn(II)-bearing δ-MnO2 turns into Mn(III)-rich δ-MnO2 without forming T-bir or TMOs. The stabilizing power of the cations on the δ-MnO2 structure positively correlates with their binding strength to δ-MnO2 (Li+, Na+ or K+ < Mg2+ or Ca2+ < Cu(II)). Since metal adsorption decreases the surface energy of minerals, our result suggests that the surface energy largely controls the thermodynamic stability of LMOs. Our study implies that the adsorption of divalent metal cations, particularly transition metals, canmore » be a prime cause of the high abundance of LMOs, rather than the more stable TMO phases, in the environment.« less

Authors:
 [1];  [2];  [1];  [3];  [4];  [4]; ORCiD logo [1]
  1. Univ. of Wyoming, Laramie, WY (United States)
  2. Smithsonian Inst., Washington, DC (United States)
  3. Argonne National Lab. (ANL), Lemont, IL (United States)
  4. Colorado State Univ., Fort Collins, CO (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Wyoming, Laramie, WY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Experimental Program to Stimulate Competitive Research (EPSCoR)
OSTI Identifier:
1559537
Alternate Identifier(s):
OSTI ID: 1854156
Grant/Contract Number:  
AC02-06CH11357; SC0016272
Resource Type:
Accepted Manuscript
Journal Name:
Environmental Science and Technology
Additional Journal Information:
Journal Volume: 53; Journal Issue: 13; 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; 58 GEOSCIENCES

Citation Formats

Yang, Peng, Post, Jeffrey E., Wang, Qian, Xu, Wenqian, Geiss, Roy, McCurdy, Patrick R., and Zhu, Mengqiang. Metal Adsorption Controls Stability of Layered Manganese Oxides. United States: N. p., 2019. Web. doi:10.1021/acs.est.9b01242.
Yang, Peng, Post, Jeffrey E., Wang, Qian, Xu, Wenqian, Geiss, Roy, McCurdy, Patrick R., & Zhu, Mengqiang. Metal Adsorption Controls Stability of Layered Manganese Oxides. United States. https://doi.org/10.1021/acs.est.9b01242
Yang, Peng, Post, Jeffrey E., Wang, Qian, Xu, Wenqian, Geiss, Roy, McCurdy, Patrick R., and Zhu, Mengqiang. Wed . "Metal Adsorption Controls Stability of Layered Manganese Oxides". United States. https://doi.org/10.1021/acs.est.9b01242. https://www.osti.gov/servlets/purl/1559537.
@article{osti_1559537,
title = {Metal Adsorption Controls Stability of Layered Manganese Oxides},
author = {Yang, Peng and Post, Jeffrey E. and Wang, Qian and Xu, Wenqian and Geiss, Roy and McCurdy, Patrick R. and Zhu, Mengqiang},
abstractNote = {Hexagonal birnessite, a typical layered Mn oxide (LMO), can adsorb and oxidize Mn(II) and thereby transform to Mn(III)-rich hexagonal birnessite, triclinic birnessite, and/or tunneled Mn oxides (TMOs), remarkably changing the environmental behavior of Mn oxides. We have determined the effects of co-existing cations on the transformation by incubating Mn(II)-bearing δ-MnO2 at pH 8 under anoxic conditions for 25 d (dissolved Mn < 11 μM). In the Li+, Na+ or K+ chloride solution, the Mn(II)-bearing δ-MnO2 first transforms to Mn(III)-rich δ-MnO2 and/or triclinic birnessite (T-bir) due to the Mn(II)-Mn(IV) comproportionation, most of which eventually transform to a 4 × 4 TMO. In contrast, Mn(III)-rich δ-MnO2 and T-bir form and persist in the Mg2+ or Ca2+ chloride solution. Yet, in the presence of surface adsorbed Cu(II), Mn(II)-bearing δ-MnO2 turns into Mn(III)-rich δ-MnO2 without forming T-bir or TMOs. The stabilizing power of the cations on the δ-MnO2 structure positively correlates with their binding strength to δ-MnO2 (Li+, Na+ or K+ < Mg2+ or Ca2+ < Cu(II)). Since metal adsorption decreases the surface energy of minerals, our result suggests that the surface energy largely controls the thermodynamic stability of LMOs. Our study implies that the adsorption of divalent metal cations, particularly transition metals, can be a prime cause of the high abundance of LMOs, rather than the more stable TMO phases, in the environment.},
doi = {10.1021/acs.est.9b01242},
journal = {Environmental Science and Technology},
number = 13,
volume = 53,
place = {United States},
year = {Wed May 22 00:00:00 EDT 2019},
month = {Wed May 22 00:00:00 EDT 2019}
}

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Works referenced in this record:

Manganese oxide minerals: Crystal structures and economic and environmental significance
journal, March 1999


Arsenite Oxidation by a Poorly Crystalline Manganese-Oxide. 2. Results from X-ray Absorption Spectroscopy and X-ray Diffraction
journal, November 2010

  • Lafferty, Brandon J.; Ginder-Vogel, Matthew; Zhu, Mengqiang
  • Environmental Science & Technology, Vol. 44, Issue 22
  • DOI: 10.1021/es102016c

Mechanisms of nickel sorption by a bacteriogenic birnessite
journal, June 2010

  • Peña, Jasquelin; Kwon, Kideok D.; Refson, Keith
  • Geochimica et Cosmochimica Acta, Vol. 74, Issue 11
  • DOI: 10.1016/j.gca.2010.02.035

Mechanisms of Pb(II) Sorption on a Biogenic Manganese Oxide
journal, January 2005

  • Villalobos, Mario; Bargar, John; Sposito, Garrison
  • Environmental Science & Technology, Vol. 39, Issue 2
  • DOI: 10.1021/es049434a

Ni(II) Sorption on Biogenic Mn-Oxides with Varying Mn Octahedral Layer Structure
journal, June 2010

  • Zhu, Mengqiang; Ginder-Vogel, Matthew; Sparks, Donald L.
  • Environmental Science & Technology, Vol. 44, Issue 12
  • DOI: 10.1021/es9037066

Structural Transformation of Birnessite by Fulvic Acid under Anoxic Conditions
journal, January 2018

  • Wang, Qian; Yang, Peng; Zhu, Mengqiang
  • Environmental Science & Technology, Vol. 52, Issue 4
  • DOI: 10.1021/acs.est.7b04379

Key geochemical factors regulating Mn(IV)-catalyzed anaerobic nitrification in coastal marine sediments
journal, May 2014


Adsorption of Phosphate on Manganese Dioxide in Seawater
journal, January 1996

  • Yao, Wensheng; Millero, Frank J.
  • Environmental Science & Technology, Vol. 30, Issue 2
  • DOI: 10.1021/es950290x

Nucleation and growth of todorokite from birnessite: Implications for trace-metal cycling in marine sediments
journal, November 2014

  • Atkins, Amy L.; Shaw, Samuel; Peacock, Caroline L.
  • Geochimica et Cosmochimica Acta, Vol. 144
  • DOI: 10.1016/j.gca.2014.08.014

Mineralogy and crystal chemistry of Mn, Fe, Co, Ni, and Cu in a deep-sea Pacific polymetallic nodule
journal, October 2014

  • Manceau, A.; Lanson, M.; Takahashi, Y.
  • American Mineralogist, Vol. 99, Issue 10
  • DOI: 10.2138/am-2014-4742

Mn, Fe, Zn and As speciation in a fast-growing ferromanganese marine nodule
journal, July 2004

  • Marcus, Matthew A.; Manceau, Alain; Kersten, Michael
  • Geochimica et Cosmochimica Acta, Vol. 68, Issue 14
  • DOI: 10.1016/j.gca.2004.01.015

Surface complexation of Cu on birnessite (δ-MnO2): Controls on Cu in the deep ocean
journal, December 2010


Reductive transformations of layered manganese oxides by small organic acids and the fate of trace metals
journal, April 2019


Structure of synthetic monoclinic Na-rich birnessite and hexagonal birnessite; I, Results from X-ray diffraction and selected-area electron diffraction
journal, October 1997

  • Drits, Victor A.; Silvester, Ewen; Gorshkov, Anatoli I.
  • American Mineralogist, Vol. 82, Issue 9-10
  • DOI: 10.2138/am-1997-9-1012

Structure of synthetic monoclinic Na-rich birnessite and hexagonal birnessite; II, Results from chemical studies and EXAFS spectroscopy
journal, October 1997

  • Silvester, Ewen; Manceau, Alain; Drits, Victor A.
  • American Mineralogist, Vol. 82, Issue 9-10
  • DOI: 10.2138/am-1997-9-1013

Influence of Mn(III) Availability on the Phase Transformation From Layered Buserite to Tunnel-structured Todorokite
journal, August 2008


Birnessites with different average manganese oxidation states synthesized, characterized, and transformed to todorokite at atmospheric pressure
journal, December 2009


Synthesis of Birnessite in the Presence of Phosphate, Silicate, or Sulfate
journal, September 2016


Importance of Mn(III) Availability on the Rate of Cr(III) Oxidation on δ-MnO 2
journal, August 2000

  • Nico, Peter S.; Zasoski, Robert J.
  • Environmental Science & Technology, Vol. 34, Issue 16
  • DOI: 10.1021/es991462j

Chromium(III) Oxidation by Three Poorly-Crystalline Manganese(IV) Oxides. 1. Chromium(III)-Oxidizing Capacity
journal, October 2012

  • Landrot, Gautier; Ginder-Vogel, Matthew; Livi, Kenneth
  • Environmental Science & Technology, Vol. 46, Issue 21
  • DOI: 10.1021/es302383y

On the role of Mn(IV) vacancies in the photoreductive dissolution of hexagonal birnessite
journal, July 2009

  • Kwon, Kideok D.; Refson, Keith; Sposito, Garrison
  • Geochimica et Cosmochimica Acta, Vol. 73, Issue 14
  • DOI: 10.1016/j.gca.2009.04.031

Relationship between Pb<SUP>2+</SUP> adsorption and average Mn oxidation state in synthetic birnessites
journal, October 2009


Pb2+ adsorption on birnessite affected by Zn2+ and Mn2+ pretreatments
journal, April 2010


Photochemical Formation and Transformation of Birnessite: Effects of Cations on Micromorphology and Crystal Structure
journal, May 2018

  • Zhang, Tengfei; Liu, Lihu; Tan, Wenfeng
  • Environmental Science & Technology, Vol. 52, Issue 12
  • DOI: 10.1021/acs.est.7b06592

Geomicrobiology of manganese(II) oxidation
journal, September 2005

  • Tebo, Bradley M.; Johnson, Hope A.; McCarthy, James K.
  • Trends in Microbiology, Vol. 13, Issue 9
  • DOI: 10.1016/j.tim.2005.07.009

Remobilization of transition metals in surficial pelagic sediments from the eastern Pacific
journal, May 1984


New insights into the formation and burial of Fe/Mn accumulations in Lake Baikal sediments
journal, November 2012


Reductive Transformation of Birnessite by Aqueous Mn(II)
journal, August 2011

  • Elzinga, Evert J.
  • Environmental Science & Technology, Vol. 45, Issue 15
  • DOI: 10.1021/es2013038

A Mn-54 Radiotracer Study of Mn Isotope Solid–Liquid Exchange during Reductive Transformation of Vernadite (δ-MnO 2 ) by Aqueous Mn(II)
journal, March 2015

  • Elzinga, Evert J.; Kustka, Adam B.
  • Environmental Science & Technology, Vol. 49, Issue 7
  • DOI: 10.1021/acs.est.5b00022

Influence of pH on the Reductive Transformation of Birnessite by Aqueous Mn(II)
journal, September 2013

  • Lefkowitz, Joshua P.; Rouff, Ashaki A.; Elzinga, Evert J.
  • Environmental Science & Technology, Vol. 47, Issue 18
  • DOI: 10.1021/es402108d

Redox Reactions between Mn(II) and Hexagonal Birnessite Change Its Layer Symmetry
journal, January 2016

  • Zhao, Huaiyan; Zhu, Mengqiang; Li, Wei
  • Environmental Science & Technology, Vol. 50, Issue 4
  • DOI: 10.1021/acs.est.5b04436

Cation Effects on the Layer Structure of Biogenic Mn-Oxides
journal, June 2010

  • Zhu, Mengqiang; Ginder-Vogel, Matthew; Parikh, Sanjai J.
  • Environmental Science & Technology, Vol. 44, Issue 12
  • DOI: 10.1021/es1009955

Structural response of phyllomanganates to wet aging and aqueous Mn(II)
journal, November 2016

  • Hinkle, Margaret A. G.; Flynn, Elaine D.; Catalano, Jeffrey G.
  • Geochimica et Cosmochimica Acta, Vol. 192
  • DOI: 10.1016/j.gca.2016.07.035

Sorption of Ni by birnessite: Equilibrium controls on Ni in seawater
journal, March 2007


Impacts of Aqueous Mn(II) on the Sorption of Zn(II) by Hexagonal Birnessite
journal, April 2015

  • Lefkowitz, Joshua P.; Elzinga, Evert J.
  • Environmental Science & Technology, Vol. 49, Issue 8
  • DOI: 10.1021/es506019j

Copper sorption by the edge surfaces of synthetic birnessite nanoparticles
journal, March 2015


Structural alteration of hexagonal birnessite by aqueous Mn(II): Impacts on Ni(II) sorption
journal, September 2017


Effects of metal cations on coupled birnessite structural transformation and natural organic matter adsorption and oxidation
journal, April 2019


Impact of Mn(II)-Manganese Oxide Reactions on Ni and Zn Speciation
journal, March 2017

  • Hinkle, Margaret A. G.; Dye, Katherine G.; Catalano, Jeffrey G.
  • Environmental Science & Technology, Vol. 51, Issue 6
  • DOI: 10.1021/acs.est.6b04347

Manganese in the North Pacific
journal, August 1980


Temporal Changes in Manganese Concentrations in Water from the Fredericton Aquifer, New Brunswick
journal, July 1994


Rietveld refinement of a triclinic structure for synthetic Na-birnessite using synchrotron powder diffraction data
journal, September 2002

  • Post, Jeffrey E.; Heaney, Peter J.; Hanson, Jonathan
  • Powder Diffraction, Vol. 17, Issue 3
  • DOI: 10.1154/1.1498279

Time-resolved structural analysis of K- and Ba-exchange reactions with synthetic Na-birnessite using synchrotron X-ray diffraction
journal, February 2007

  • Lopano, C. L.; Heaney, P. J.; Post, J. E.
  • American Mineralogist, Vol. 92, Issue 2-3
  • DOI: 10.2138/am.2007.2242

Cation sorption on colloidal hydrous manganese dioxide
journal, December 1968

  • Posselt, Hans S.; Anderson, Frederick J.; Weber, Walter J.
  • Environmental Science & Technology, Vol. 2, Issue 12
  • DOI: 10.1021/es60023a005

Local structure of Cu2+ in Cu-doped hexagonal turbostratic birnessite and Cu2+ stability under acid treatment
journal, September 2017


Crystal structure of Ni-sorbed synthetic vernadite: a powder X-ray diffraction study
journal, December 2008


Comparison of three colorimetric methods for the determination of manganese in freshwaters
journal, June 1991


Birnessite polytype systematics and identification by powder X-ray diffraction
journal, May 2007

  • Drits, V. A.; Lanson, B.; Gaillot, A. -C.
  • American Mineralogist, Vol. 92, Issue 5-6
  • DOI: 10.2138/am.2007.2207

Crystal structures of synthetic 7 Å and 10 Å manganates substituted by mono- and divalent cations
journal, September 1994


Lattice vibrations of manganese oxides
journal, February 2004

  • Julien, C. M.; Massot, M.; Poinsignon, C.
  • Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 60, Issue 3
  • DOI: 10.1016/S1386-1425(03)00279-8

Study of structural defects in ?-MnO2 by Raman spectroscopy
journal, January 2002

  • Julien, C.; Massot, M.; Rangan, S.
  • Journal of Raman Spectroscopy, Vol. 33, Issue 4
  • DOI: 10.1002/jrs.838

Effect of Ionic Strength on the Kinetics of Crystal Growth by Oriented Aggregation
journal, September 2012

  • Burrows, Nathan D.; Hale, Christopher R. H.; Penn, R. Lee
  • Crystal Growth & Design, Vol. 12, Issue 10
  • DOI: 10.1021/cg3004849

Phenomenological Theory of Ion Solvation. Effective Radii of Hydrated Ions
journal, September 1959

  • Nightingale, E. R.
  • The Journal of Physical Chemistry, Vol. 63, Issue 9, p. 1381-1387
  • DOI: 10.1021/j150579a011

STUDIES ON THE PERIODIC SYSTEM. I. THE IONIC POTENTIAL AS A PERIODIC FUNCTION 1
journal, November 1928

  • Cartledge, G. H.
  • Journal of the American Chemical Society, Vol. 50, Issue 11
  • DOI: 10.1021/ja01398a001

Structural Transformation of MnO 2 during the Oxidation of Bisphenol A
journal, May 2017

  • Balgooyen, Sarah; Alaimo, Peter J.; Remucal, Christina K.
  • Environmental Science & Technology, Vol. 51, Issue 11
  • DOI: 10.1021/acs.est.6b05904

Modeling sorption of divalent metal cations on hydrous manganese oxide using the diffuse double layer model
journal, January 2004


Structure of synthetic Na-birnessite: Evidence for a triclinic one-layer unit cell
journal, November 2002

  • Lanson, Bruno; Drits, Victor A.; Feng, Qi
  • American Mineralogist, Vol. 87, Issue 11-12
  • DOI: 10.2138/am-2002-11-1215

Substructure and superstructure of four-layer Ca-exchanged birnessite
journal, February 1998

  • Drits, Victor A.; Lanson, Bruno; Gorshkov, Anatoli I.
  • American Mineralogist, Vol. 83, Issue 1-2
  • DOI: 10.2138/am-1998-1-210

Formation of todorokite from vernadite in Ni-rich hemipelagic sediments
journal, December 2007

  • Bodeï, Sabine; Manceau, Alain; Geoffroy, Nicolas
  • Geochimica et Cosmochimica Acta, Vol. 71, Issue 23
  • DOI: 10.1016/j.gca.2007.07.020

Release of Ni from birnessite during transformation of birnessite to todorokite: Implications for Ni cycling in marine sediments
journal, September 2016

  • Atkins, Amy L.; Shaw, Samuel; Peacock, Caroline L.
  • Geochimica et Cosmochimica Acta, Vol. 189
  • DOI: 10.1016/j.gca.2016.06.007

Structure of copper(II) hydroxide, Cu(OH)2
journal, December 1990

  • Oswald, H. R.; Reller, A.; Schmalle, H. W.
  • Acta Crystallographica Section C Crystal Structure Communications, Vol. 46, Issue 12
  • DOI: 10.1107/S0108270190006230

XAFS study of Cu model compounds and Cu 2+ sorption products on amorphous SiO 2 , γ-Al 2 O 3 , and anatase
journal, January 2000

  • Cheah, Sing-Foong; Brown, Gordon E.; Parks, George A.
  • American Mineralogist, Vol. 85, Issue 1
  • DOI: 10.2138/am-2000-0113

Comment on “Molecular controls on Cu and Zn isotopic fractionation in Fe–Mn crusts” by Little et al.
journal, February 2015


Size-Driven Structural and Thermodynamic Complexity in Iron Oxides
journal, March 2008


Size Effect on the Thermodynamic Properties of Silver Nanoparticles
journal, January 2008

  • Luo, Wenhua; Hu, Wangyu; Xiao, Shifang
  • The Journal of Physical Chemistry C, Vol. 112, Issue 7
  • DOI: 10.1021/jp0770155

Crystal growth and aggregation in suspensions of δ-MnO 2 nanoparticles: implications for surface reactivity
journal, January 2018

  • Marafatto, Francesco Femi; Lanson, Bruno; Peña, Jasquelin
  • Environmental Science: Nano, Vol. 5, Issue 2
  • DOI: 10.1039/C7EN00817A

Effect of Manganese Oxide Aging and Structure Transformation on the Kinetics of Thiol Oxidation
journal, October 2018

  • Eitel, Eryn M.; Zhao, Shiliang; Tang, Yuanzhi
  • Environmental Science & Technology, Vol. 52, Issue 22
  • DOI: 10.1021/acs.est.8b03993

Cryptomelane formation from nanocrystalline vernadite precursor: a high energy X-ray scattering and transmission electron microscopy perspective on reaction mechanisms
journal, September 2015

  • Grangeon, Sylvain; Fernandez-Martinez, Alejandro; Warmont, Fabienne
  • Geochemical Transactions, Vol. 16, Issue 1
  • DOI: 10.1186/s12932-015-0028-y

Synthesis of todorokite-type manganese oxide from Cu-buserite by controlling the pH at atmospheric pressure
journal, January 2009


Transformation of Co-containing birnessite to todorokite: Effect of Co on the transformation and implications for Co mobility
journal, February 2019

  • Wu, Zhongkuan; Peacock, Caroline L.; Lanson, Bruno
  • Geochimica et Cosmochimica Acta, Vol. 246
  • DOI: 10.1016/j.gca.2018.11.001

Structure of heavy metal sorbed birnessite. Part III: Results from powder and polarized extended X-ray absorption fine structure spectroscopy
journal, August 2002


Effect of Zn coprecipitation on the structure of layered Mn oxides
journal, August 2018


Zn sorption modifies dynamically the layer and interlayer structure of vernadite
journal, May 2012

  • Grangeon, Sylvain; Manceau, Alain; Guilhermet, Julien
  • Geochimica et Cosmochimica Acta, Vol. 85
  • DOI: 10.1016/j.gca.2012.02.019

Synthesis of Todorokite at Atmospheric Pressure
journal, November 2004

  • Feng, Xiong Han; Tan, Wen Feng; Liu, Fan
  • Chemistry of Materials, Vol. 16, Issue 22
  • DOI: 10.1021/cm0499545

Nanophase Transition Metal Oxides Show Large Thermodynamically Driven Shifts in Oxidation-Reduction Equilibria
journal, October 2010

  • Navrotsky, Alexandra; Ma, Chengcheng; Lilova, Kristina
  • Science, Vol. 330, Issue 6001
  • DOI: 10.1126/science.1195875

Adsorption and redox reactions of heavy metals on synthesized Mn oxide minerals
journal, May 2007