Molecular-Scale Speciation of Zn and Ni in Soil Ferromanganese Nodules from Loess Soils of the Mississippi Basin

Manceau, Alain; Tamura, Nobumichi; Celestre, Richard; MacDowell, Alastair A.; Geoffroy, Nicolas; Sposito, Garrison; Padmore, H. A.

doi:10.1021/es025748r

Cited by 176 publications

(138 citation statements)

References 33 publications

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“…Since only the species present in the library of model compounds can be identified, this library ought to be as large as possible. We used the extended inorganic and organic Zn libraries described in Sarret (1998) and Manceau et al (2003), completed by ZnPhos and ZnTS samples. Finally, once Zn species were identified, their proportions in bulk samples and in the analyzed spots were determined by least-squares fitting (LSF) of experimental spectra to linear combinations of the reference spectra.…”

Section: Methodsmentioning

confidence: 99%

The effect of phytostabilization on Zn speciation in a dredged contaminated sediment using scanning electron microscopy, X-ray fluorescence, EXAFS spectroscopy, and principal components analysis

Panfili

Manceau

Sarret

et al. 2005

Geochimica et Cosmochimica Acta

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122

129

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Running Title: Effect of phytostabilzation on Zn speciation in dredged sediment 2 ABSTRACTThe maintenance of waterways generates large amounts of dredged sediments, which are deposited on adjacent land surfaces. These sediments are often rich in metal contaminants and present a risk to the local environment. Understanding how the metals are immobilized at the molecular level is critical for formulating effective metal containment strategies, such as phytoremediation. In the present work, the mineralogical transformations of Zn Seven Zn species were identified at the micrometer-scale : sphalerite, gahnite, franklinite, Zncontaining ferrihydrite and phosphate, (Zn-Al)-hydrotalcite, and Zn-substituted, kerolite-like, trioctahedral phyllosilicate. Bulk fractions of each species were quantified by LSF of the powder EXAFS spectra to linear combinations of the identified Zn species spectra.In the untreated and unvegetated sediment, Zn was distributed as ~50 % (mole ratio of total Zn) sphalerite, ~40 % Zn-ferrihydrite, and ~10-20 % (Zn-Al)-hydrotalcite plus Znphyllosilicate. In unvegetated but amended sediments (AP and TS), ZnS and Zn-ferrihydrite each decreased by 10 to 20 % and were replaced by Zn-phosphate (~30-40 %). In the presence of plants, ZnS was almost completely dissolved and the released Zn bound to phosphate (~40-60 %) and to Zn phyllosilicate plus (Zn,Al)-hydrotalcite (~20-40 %). Neither the plant species 3 nor the co-addition of mineral amendment affected the Zn speciation in the vegetated sediment.The sediment pore waters were supersaturated with respect to Zn-containing trioctahedral phyllosilicate, near-saturation with respect to Zn-phosphate, and strongly undersaturated with respect to (Zn,Al)-hydrotalcite. Therefore, the formation of (Zn,Al)-hydrotalcite in slightly alkaline conditions ought to result from heterogenous precipitation on mineral surface. 4

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Section: Methodsmentioning

confidence: 99%

The effect of phytostabilization on Zn speciation in a dredged contaminated sediment using scanning electron microscopy, X-ray fluorescence, EXAFS spectroscopy, and principal components analysis

Panfili

Manceau

Sarret

et al. 2005

Geochimica et Cosmochimica Acta

Self Cite

122

129

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“…In oceanic serpentines this value is slightly smaller, indicating that some of the Fe is relocated in other phases like maghemite, which is readily hydrated to goethite. Goethite is able to incorporate or attach Ni (Manceau et al, 2003). The nickel contained in the limonite horizon and in primary serpentines is transferred to percolating meteoric solutions, and moves downward through the profile, being concentrated with Si and Mg within the underlying saprolite horizon to form secondary Ni-enriched phyllosilicates.…”

Section: Introductionmentioning

confidence: 99%

Ni Enrichment and Stability of Al-Free Garnierite Solid-Solutions: A Thermodynamic Approach

Galí

Soler

Proenza

et al. 2012

Clays and clay miner.

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Abstract-Garnierites represent significant Ni ore minerals in the many Ni-laterite deposits worldwide. The occurrence of a variety of garnierite minerals with variable Ni content poses questions about the conditions of their formation. From an aqueous-solution equilibrium thermodynamic point of view, the present study examines the conditions that favor the precipitation of a particular garnierite phase and the mechanism of Ni-enrichment, and gives an explanation to the temporal and spatial succession of different garnierite minerals in Ni-laterite deposits. The chemical and structural characterization of garnierite minerals from many nickel laterite deposits around the world show that this group of minerals is formed essentially by an intimate intermixing of three Mg-Ni phyllosilicate solid solutions: serpentine-népouite, kerolite-pimelite, and sepiolite-falcondoite, without or with very small amounts of Al in their composition. The present study deals with garnierites which are essentially Al-free. The published experimental dissolution constants for Mg end-members of the above solid solutions and the calculated constants for pure Ni end-members were used to calculate Lippmann diagrams for the three solid solutions, on the assumption that they are ideal. With the help of these diagrams, congruent dissolution of Ni-poor primary minerals, followed by equilibrium precipitation of Ni-rich secondary phyllosilicates, is proposed as an efficient mechanism for Ni supergene enrichment in the laterite profile. The stability fields of the solid solutions were constructed using [log a SiO 2 (aq) , log ((a Mg 2+ + a Ni 2+)/(a H +) 2 )] (predominance) diagrams. These, combined with Lippmann diagrams, give an almost complete chemical characterization of the solution and the precipitating phase(s) in equilibrium. The temporal and spatial succession of hydrous MgNi phyllosilicates encountered in Ni-laterite deposits is explained by the small mobility of silica and the increase in its activity.

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“…In nodules from marine (Bodei et al, 2007;Peacock and Sherman, 2007a), freshwater (Manceau et al, 2007a), and soil environments (Manceau et al, 2002b;Manceau et al, 2003), Ni was present as a divalent cation incorporated (inc) into the octahedral sheets of layer-type Mn(IV) oxide minerals ( Fig. 1a).…”

Section: Introductionmentioning

confidence: 99%

Mechanisms of nickel sorption by a bacteriogenic birnessite

Peña

Kwon

Refson

et al. 2010

Geochimica et Cosmochimica Acta

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119

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Bacteriogenic birnessite nanoparticles have a large capacity to adsorb metal cations due to their high proportion of cation vacancy defects. In the current study, a synergistic experimental-computational approach was used to study the molecular-scale mechanisms of Ni sorption at varying loadings and at pH 6-8 using the hexagonal birnessite produced by Pseudomonas putida GB-1. We found that Ni is scavenged effectively by the biomass-

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Molecular-Scale Speciation of Zn and Ni in Soil Ferromanganese Nodules from Loess Soils of the Mississippi Basin

Cited by 176 publications

References 33 publications

The effect of phytostabilization on Zn speciation in a dredged contaminated sediment using scanning electron microscopy, X-ray fluorescence, EXAFS spectroscopy, and principal components analysis

The effect of phytostabilization on Zn speciation in a dredged contaminated sediment using scanning electron microscopy, X-ray fluorescence, EXAFS spectroscopy, and principal components analysis

Ni Enrichment and Stability of Al-Free Garnierite Solid-Solutions: A Thermodynamic Approach

Mechanisms of nickel sorption by a bacteriogenic birnessite

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