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Title: Copper sorption by the edge surfaces of synthetic birnessite nanoparticles

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Journal Article: Publisher's Accepted Manuscript
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Chemical Geology
Additional Journal Information:
Journal Volume: 396; Journal Issue: C; Related Information: CHORUS Timestamp: 2017-06-22 23:12:09; Journal ID: ISSN 0009-2541
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Peña, Jasquelin, Bargar, John R., and Sposito, Garrison. Copper sorption by the edge surfaces of synthetic birnessite nanoparticles. Netherlands: N. p., 2015. Web. doi:10.1016/j.chemgeo.2014.12.021.
Peña, Jasquelin, Bargar, John R., & Sposito, Garrison. Copper sorption by the edge surfaces of synthetic birnessite nanoparticles. Netherlands. doi:10.1016/j.chemgeo.2014.12.021.
Peña, Jasquelin, Bargar, John R., and Sposito, Garrison. 2015. "Copper sorption by the edge surfaces of synthetic birnessite nanoparticles". Netherlands. doi:10.1016/j.chemgeo.2014.12.021.
title = {Copper sorption by the edge surfaces of synthetic birnessite nanoparticles},
author = {Peña, Jasquelin and Bargar, John R. and Sposito, Garrison},
abstractNote = {},
doi = {10.1016/j.chemgeo.2014.12.021},
journal = {Chemical Geology},
number = C,
volume = 396,
place = {Netherlands},
year = 2015,
month = 3

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Free Publicly Available Full Text
Publisher's Version of Record at 10.1016/j.chemgeo.2014.12.021

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Cited by: 16works
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  • Cited by 12
  • 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 ofmore » 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).« less
  • The sorption of divalent cadmium and copper ions from aqueous solutions on natural and synthetic hydroxyapatite was investigated by the batch method and under dynamic conditions in columns at 22 deg. C and pH 5. The effect of cadmium and copper concentration on sorption was studied. Both types of apatites are efficient, despite their different composition and morphology. The sorption mechanism involves an ion exchange for Cd(II), while Cu(II) leads to precipitation of a newly formed solid. Thus, the sorption efficiency depends on the experimental conditions and the specific physicochemical properties of the apatites used. The sorption isotherms were fittedmore » to the Langmuir equation.« less
  • An X-ray absorption spectroscopy study has been carried out at the Fe and Cu K-edges for two bridged molecular assemblies, both of which contain an Fe-X-Cu (X = O{sup 2{minus}}, OH{sup {minus}}) bridge unit, some of whose features are relevant to the binuclear site of cytochrome c oxidase. The two complexes [(OEP)Fe-O-Cu(Me{sub 6}tren)]{sup 1+} and [(OEP)-Fe-(OH)-Cu(Me{sub 5}tren)(OC1O{sub 3})]{sup 1+} have similar structural fragments around the metal centers except that they differ significantly in the bridge structure (the former contains a linear oxo bridge while the latter has a bent hydroxo bridge). The authors report a comparative study of these complexesmore » using multiple-scattering (MS) EXAFS analysis and the program package GNXAS. It is found that there is a dramatic increase in the amplitude of the Fe-X-Cu MS pathway as the bridge unit approaches linearity. Full EXAFS MS analysis enables accurate quantitation of bridge metrical details and geometry for both complexes. The accuracy of the structural determination for the bridge units is evaluated by a statistical analysis methodology in which correlations among fitting parameters are identified and contour plots are used to determine random error. The relevance of this study to the structural definition of binuclear bridged sites in cytochrome c oxidase and other metalloenzymes is considered.« less
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