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Title: Sorption selectivity of birnessite particle edges: a d-PDF analysis of Cd( ii ) and Pb( ii ) sorption by δ-MnO 2 and ferrihydrite

Abstract

Birnessite minerals (layer-type MnO2), which bear both internal (cation vacancies) and external (particle edges) metal sorption sites, are important sinks of contaminants in soils and sediments. Although the particle edges of birnessite minerals often dominate the total reactive surface area, especially in the case of nanoscale crystallites, the metal sorption reactivity of birnessite particle edges remains elusive. In this study, we investigated the sorption selectivity of birnessite particle edges by combining Cd(II) and Pb(II) adsorption isotherms at pH 5.5 with surface structural characterization by differential pair distribution function (d-PDF) analysis. We compared the sorption reactivity of δ-MnO2 to that of the nanomineral, 2-line ferrihydrite, which exhibits only external surface sites. Our results show that, whereas Cd(II) and Pb(II) both bind to birnessite layer vacancies, only Pb(II) binds extensively to birnessite particle edges. For ferrihydrite, significant Pb(II) adsorption to external sites was observed (roughly 20 mol%), whereas Cd(II) sorption was negligible. These results are supported by bond valence calculations that show comparable degrees of saturation of oxygen atoms on birnessite and ferrihydrite particle edges. Therefore, we propose that the sorption selectivity of birnessite edges follows the same order of that reported previously for ferrihydrite: Ca(II) < Cd(II) < Ni(II) < Zn(II)more » < Cu(II) < Pb(II).« less

Authors:
;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
DOE - BASIC ENERGY SCIENCES
OSTI Identifier:
1377910
Resource Type:
Journal Article
Journal Name:
Environmental Science: Processes & Impacts
Additional Journal Information:
Journal Volume: 18; Journal Issue: 8; Journal ID: ISSN 2050-7887
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
ENGLISH
Subject:
54 ENVIRONMENTAL SCIENCES

Citation Formats

van Genuchten, Case M., and Peña, Jasquelin. Sorption selectivity of birnessite particle edges: a d-PDF analysis of Cd( ii ) and Pb( ii ) sorption by δ-MnO 2 and ferrihydrite. United States: N. p., 2016. Web. doi:10.1039/C6EM00136J.
van Genuchten, Case M., & Peña, Jasquelin. Sorption selectivity of birnessite particle edges: a d-PDF analysis of Cd( ii ) and Pb( ii ) sorption by δ-MnO 2 and ferrihydrite. United States. https://doi.org/10.1039/C6EM00136J
van Genuchten, Case M., and Peña, Jasquelin. 2016. "Sorption selectivity of birnessite particle edges: a d-PDF analysis of Cd( ii ) and Pb( ii ) sorption by δ-MnO 2 and ferrihydrite". United States. https://doi.org/10.1039/C6EM00136J.
@article{osti_1377910,
title = {Sorption selectivity of birnessite particle edges: a d-PDF analysis of Cd( ii ) and Pb( ii ) sorption by δ-MnO 2 and ferrihydrite},
author = {van Genuchten, Case M. and Peña, Jasquelin},
abstractNote = {Birnessite minerals (layer-type MnO2), which bear both internal (cation vacancies) and external (particle edges) metal sorption sites, are important sinks of contaminants in soils and sediments. Although the particle edges of birnessite minerals often dominate the total reactive surface area, especially in the case of nanoscale crystallites, the metal sorption reactivity of birnessite particle edges remains elusive. In this study, we investigated the sorption selectivity of birnessite particle edges by combining Cd(II) and Pb(II) adsorption isotherms at pH 5.5 with surface structural characterization by differential pair distribution function (d-PDF) analysis. We compared the sorption reactivity of δ-MnO2 to that of the nanomineral, 2-line ferrihydrite, which exhibits only external surface sites. Our results show that, whereas Cd(II) and Pb(II) both bind to birnessite layer vacancies, only Pb(II) binds extensively to birnessite particle edges. For ferrihydrite, significant Pb(II) adsorption to external sites was observed (roughly 20 mol%), whereas Cd(II) sorption was negligible. These results are supported by bond valence calculations that show comparable degrees of saturation of oxygen atoms on birnessite and ferrihydrite particle edges. Therefore, we propose that the sorption selectivity of birnessite edges follows the same order of that reported previously for ferrihydrite: Ca(II) < Cd(II) < Ni(II) < Zn(II) < Cu(II) < Pb(II).},
doi = {10.1039/C6EM00136J},
url = {https://www.osti.gov/biblio/1377910}, journal = {Environmental Science: Processes & Impacts},
issn = {2050-7887},
number = 8,
volume = 18,
place = {United States},
year = {Fri Jan 01 00:00:00 EST 2016},
month = {Fri Jan 01 00:00:00 EST 2016}
}

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