Zinc sorption to biogenic hexagonal-birnessite particles within a hydrated bacterial biofilm

Toner, Brandy M.; Manceau, Alain; Webb, Samuel M.; Sposito, Garrison

doi:10.1016/j.gca.2005.08.029

Cited by 178 publications

(178 citation statements)

References 58 publications

(108 reference statements)

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“…The present study helps to explain the sorptive capacity of the Mn oxide coatings. Bacteriogenic and abiotic layered Mn oxides have impressive sorptive capacity for a range of metals, with edge sites and Mn(IV) vacancy sites being particularly important for contaminant metal binding (Nelson et al, 1999;Lanson et al, 2002b;O'Reilly and Hochella, 2003;Tebo et al, 2004;Villalobos et al, 2005a,b;Toner et al, 2006;Webb et al, 2006). The nanosheet morphology and abundant Mn(IV) vacancies of the Pinal Creek hyporheic zone Mn oxides should bequeath them with a great abundance of metal-binding sites.…”

Section: Comparison To Laboratory Bacteriogenic Mn Oxidesmentioning

confidence: 99%

Structural characterization of terrestrial microbial Mn oxides from Pinal Creek, AZ

Bargar

Fuller

Marcus

et al. 2009

Geochimica et Cosmochimica Acta

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The microbial catalysis of Mn(II) oxidation is believed to be a dominant source of abundant sorption-and redox-active Mn oxides in marine, freshwater, and subsurface aquatic environments. In spite of their importance, environmental oxides of known biogenic origin have generally not been characterized in detail from a structural perspective. Hyporheic zone Mn oxide grain coatings at Pinal Creek, Arizona, a metals-contaminated stream, have been identified as being dominantly microbial in origin and are well studied from bulk chemistry and contaminant hydrology perspectives. This site thus presents an excellent opportunity to study the structures of terrestrial microbial Mn oxides in detail. XRD and EXAFS measurements performed in this study indicate that the hydrated Pinal Creek Mn oxide grain coatings are layer-type Mn oxides with dominantly hexagonal or pseudo-hexagonal layer symmetry. XRD and TEM measurements suggest the oxides to be nanoparticulate plates with average dimensions on the order of 11 nm thick Â 35 nm diameter, but with individual particles exhibiting thickness as small as a single layer and sheets as wide as 500 nm. The hydrated oxides exhibit a 10-Å basal-plane spacing and turbostratic disorder. EXAFS analyses suggest the oxides contain layer Mn(IV) site vacancy defects, and layer Mn(III) is inferred to be present, as deduced from Jahn-Teller distortion of the local structure. The physical geometry and structural details of the coatings suggest formation within microbial biofilms. The biogenic Mn oxides are stable with respect to transformation into thermodynamically more stable phases over a time scale of at least 5 months. The nanoparticulate layered structural motif, also observed in pure culture laboratory studies, appears to be characteristic of biogenic Mn oxides and may explain the common occurrence of this mineral habit in soils and sediments.

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Section: Comparison To Laboratory Bacteriogenic Mn Oxidesmentioning

confidence: 99%

Structural characterization of terrestrial microbial Mn oxides from Pinal Creek, AZ

Bargar

Fuller

Marcus

et al. 2009

Geochimica et Cosmochimica Acta

Self Cite

109

106

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“…Birnessite (layer-type MnO 2 ), produced mainly by bacteria and fungi, is a ubiquitous environmental nanoparticle participating in important geochemical processes, particularly metal scavenging (Tebo et al, 2004;Tonkin et al, 2004;Toner et al, 2006, Manceau et al, 2007Miyata et al, 2007). Among the trace metals of major interest, Zn appears to be influenced strongly in its biogeochemical cycling by sorption on birnessite minerals found in soils, aquifers, streams, and wetlands .…”

Section: Introductionmentioning

confidence: 99%

“…Among the trace metals of major interest, Zn appears to be influenced strongly in its biogeochemical cycling by sorption on birnessite minerals found in soils, aquifers, streams, and wetlands . Detailed molecular-scale studies of sorbed Zn 2+ species have been published for chemically-and microbially-synthesized birnessite (Manceau et al, 2002;Toner et al, 2006), natural soil and marine birnessite (Marcus et al, 2004;Manceau et al, 2007), and Zn-Mn coprecipitates on plant roots (Lanson et al, 2008). These studies reveal that Zn 2+ binds to Mn(IV) vacancy sites in hexagonal birnessite, forming triple-corner-sharing (TCS) inner-sphere surface complexes with the three surface O surrounding a vacancy.…”

Section: Introductionmentioning

confidence: 99%

“…However, other birnessite samples shown to contain the Zn IV -TCS species comprise sheets of octahedra with only Mn(IV) present [sediment birnessite, Isaure et al (2005); bacteriogenic birnessite and δ-MnO 2 , Toner et al (2006); quartz-coating birnessite, Manceau et al (2007); plant-root Zn-Mn coprecipitate, Lanson et al (2008)]. Therefore, it does not seem necessary to connect the existence of Zn IV -TCS uniquely to the presence of Mn(III) substituted in the octahedral sheet and the fundamental basis for the occurrence of the four-coordinate surface species remains unclear.…”

Section: Introductionmentioning

confidence: 99%

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Zinc surface complexes on birnessite: A density functional theory study

Kwon

Refson

Sposito

2009

Geochimica et Cosmochimica Acta

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Biogeochemical cycling of zinc is strongly influenced by sorption on birnessite minerals (layertype MnO 2 ), which are found in diverse terrestrial and aquatic environments. Zinc has been observed to form both tetrahedral (Zn IV ) and octahedral (Zn VI ) triple-corner-sharing surface complexes (TCS) at Mn(IV) vacancy sites in hexagonal birnessite. The octahedral complex is expected to be similar to that of Zn in the Mn oxide mineral, chalcophanite (ZnMn 3 O 7 ·3H 2 O), but the reason for the occurrence of the four-coordinate Zn surface species remains unclear. We address this issue computationally using spin-polarized Density Functional Theory (DFT) to examine the Zn IV -TCS and Zn VI -TCS species. Structural parameters obtained by DFT geometry optimization were in excellent agreement with available experimental data on Zn-birnessites.Total energy, magnetic moments, and electron-overlap populations obtained by DFT for isolated Zn IV -TCS revealed that this species is stable in birnessite without a need for Mn(III) substitution in the octahedral sheet and that it is more effective in reducing undersaturation of surface O at a Mn vacancy than is Zn VI -TCS. Comparison between geometry-optimized ZnMn 3 O 7 ·3H 2 O (chalcophanite) and the hypothetical monohydrate mineral, ZnMn 3 O 7 ·H 2 O, which contains only tetrahedral Zn, showed that the hydration state of Zn significantly affects birnessite structural stability. Finally, our study also revealed that, relative to their positions in an ideal vacancy-free

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“…Biogenic Mn oxides are often poorly crystalline nano-sized particulates with many structural defects . Such biogenic Mn oxides are expected to be reactive with heavy metals effectively through adsorption ( (Nelson et al 1999); ; (Toner et al 2006); ); (Jin et al 2009)) and oxidation (Lee and Tebo 1994;; ; (Chinni et al 2008); (Ohnuki et al 2008)). …”

Section: Introductionmentioning

confidence: 99%