Vanadium K edge XANES of synthetic and natural basaltic glasses and application to microscale oxygen barometry

Sutton, S. R.; Karner, J. M.; Papike, J. J.; Delaney, J. S.; Shearer, C. K.; Newville, Matt; Eng, Peter J.; Rivers, Mark L.; Dyar, M. D.

doi:10.1016/j.gca.2004.10.013

Cited by 159 publications

(114 citation statements)

References 74 publications

(106 reference statements)

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“…The spectra of the measured standards were in accordance with the literature [29,36] showing an increase in pre-edge peak intensity and E 1/2 with increasing oxidation state (Table S1). When the pre-edge peak intensity and the E 1/2 of the XANES spectra of the two BF slags were compared to those of the standards, it was possible to estimate the predominating valence state, which was +3 (Figure 1).…”

Section: Vanadium Concentrations and Speciation In Slags And Soilssupporting

confidence: 83%

“…Hence, the occurrence of low vanadium valence states in the blast furnace slag is expected. As the E 1/2 and the pre-edge peak intensity of the vanadium K-edge XANES spectra are positively correlated [29], they are commonly compared to vanadium standards to establish vanadium valence states [36,37]. Vanadium(II) lacks a pre-edge peak [29] and the intensities of the pre-edge peaks in the BF slag spectra were half of the intensity measured in the V 2 O 3 standard.…”

Section: Vanadium Concentrations and Speciation In Slags And Soilsmentioning

confidence: 99%

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Vanadium bioavailability in soils amended with blast furnace slag

Larsson

Baken

Smolders

et al. 2015

Journal of Hazardous Materials

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Blast furnace (BF) slags are commonly applied as soil amendments and in road fill material. In Sweden they are also naturally high in vanadium. The aim of this study was to assess the vanadium bioavailability in BF slags when applied to soil. Two soils were amended with up to 29 % BF slag (containing 800 mg V kg -1 ) and equilibrated outdoors for 10 months before conducting a barley shoot growth assay. Additional soil samples were spiked with dissolved vanadate(V) for which assays were conducted two weeks (freshly spiked) and 10 months (aged) after spiking. The BF slag vanadium was dominated by vanadium(III) as shown by V K-edge XANES spectroscopy. In contrast, results obtained by HPLC-ICP-MS showed that vanadium(V), the most toxic vanadium species, was predominant in the soil solution. Barley shoot growth was not affected by the BF slag additions. This was likely due to limited dissolution of vanadium from the BF slag, preventing an increase of dissolved vanadium above toxic thresholds. The difference in vanadium bioavailability among treatments was explained by the vanadium concentration in the soil solution. It was concluded that the vanadium in BF slag is sparingly available. These findings should be of importance in environmental risk assessment.

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Section: Vanadium Concentrations and Speciation In Slags And Soilssupporting

confidence: 83%

Section: Vanadium Concentrations and Speciation In Slags And Soilsmentioning

confidence: 99%

Vanadium bioavailability in soils amended with blast furnace slag

Larsson

Baken

Smolders

et al. 2015

Journal of Hazardous Materials

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“…These features are related to dipole and quadruple transitions from the metal 1s core state to metal 3d with some contribution from 4p depending on the local symmetry. Their intensity and energy therefore depend on the valence state and site symmetry of the metal cation (Calas and Petiau 1983;Farges et al 2001;Giuli et al 2003Giuli et al , 2004Sutton et al 2005;Westre et al 1997;Wilke et al 2001).…”

Section: Resultsmentioning

confidence: 99%

“…We focused on pre-edge features, which strongly depend on the valence state and coordination number of transition elements (Calas and Petiau 1983;Farges et al 2001;Giuli et al 2003Giuli et al , 2004Sutton et al 2005;Westre et al 1997;Wilke et al 2001). Additional 57 Fe Mössbauer spectra were performed on the Fe-containing samples to examine the relationship between the oxidation state of Cr and Fe.…”

Section: Introductionmentioning

confidence: 99%

XANES study of the oxidation state of Cr in lower mantle phases: Periclase and magnesium silicate perovskite

Eeckhout

Bolfan-Casanova

McCammon

et al. 2007

American Mineralogist

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“…While advances in the past ten years have laid the general framework for our understanding of the role of iron within the Earth's interior, new developments are underway in many areas of the research field that will likely reshape some of our current beliefs. Mantle oxygen fugacity measurements of natural samples are expanding through development of new oxybarometers based on V (Canil, 1997;Lee et al, 2003;Papike et al, 2004;Sutton et al, 2005) and potential new redox proxies based on platinum group element concentrations (Siebert et al, 2005) and iron isotopic compositions (Williams et al, 2004). Methods to measure oxidation states with higher spatial resolution continue to develop, with recent reported advances in XANES (Berry et al, 2003), the "flank method" using the electron microprobe (Höfer, 2002) and EELS (van Aken and Liebscher, 2002).…”

Section: Discussionmentioning

confidence: 99%

Microscopic properties to macroscopic behaviour: The influence of iron electronic state

McCammon

2006

Journal of Mineralogical and Petrological Sciences

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Iron is the only major element in the Earth with multiple electronic configurations (oxidation and spin state). In the upper mantle and transition zone iron is predominantly Fe 2+ , but the small amount of Fe 3+ that is present significantly affects properties that are sensitive to defect chemistry, including electrical conductivity, diffusivity and hydrogen solubility. Fe 3+ also determines the oxygen fugacity, where the upper mantle is relatively oxidised due to the high Fe 3+ /ΣFe ratio in spinel, even though the overall Fe 3+ concentration in the upper mantle is low due to its concentration in modally minor phases. The transition zone contains a similar amount of Fe 3+ , but its distribution among all the major phases results in a significantly lower oxygen fugacity, near metal saturation. In the lower mantle the transition to (Mg,Fe)(Si,Al)O 3 perovskite involves the creation of significant Fe 3+(approximately 50% of available iron), even at reducing conditions, which is likely balanced in the bulk lower mantle by disproportionation of Fe 2+ to form Fe 3+ and metallic iron, and potentially in subducting slabs through reduction of oxidised species in the slab. The nature of Fe 3+ charge balance in (Mg,Fe)(Si,Al)O 3 perovskite largely determines the influence on physical and chemical properties, where electrical conductivity is enhanced, diffusivity is reduced, and elasticity and hydrogen solubility vary depending on the substitution mechanism. If Fe 2+ is more stable in the post perovskite phase relative to (Mg,Fe)(Si,Al)O 3 perovskite as suggested by experiments, both Fe 3+ /ΣFe and the nature of its influence on physical and chemical properties may be different in the post perovskite phase. The influence of spin crossover on mantle properties remains unclear. Recent models show that the growth of an (Mg,Fe)(Si,Al)O 3 perovskite rich lower mantle during core formation would progressively oxidise the mantle to present levels as a portion of the disproportionated iron rich metal phase became incorporated into the core, and the increase in oxygen fugacity during the later stages of Earth accretion would alter the partitioning behaviour of elements between mantle and core, resolving puzzles such as the siderophile element anomaly and the discrepancy between U-Pb and Hf-W systematics in the early Earth. Redox reactions involved in the movement of material across the lower mantle boundary could be related to the formation of deep diamonds, and potentially the rise of atmospheric oxygen through a mantle avalanche in the late Archean that disturbed the balance of volatile element cycles.

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Vanadium K edge XANES of synthetic and natural basaltic glasses and application to microscale oxygen barometry

Cited by 159 publications

References 74 publications

Vanadium bioavailability in soils amended with blast furnace slag

Vanadium bioavailability in soils amended with blast furnace slag

XANES study of the oxidation state of Cr in lower mantle phases: Periclase and magnesium silicate perovskite

Microscopic properties to macroscopic behaviour: The influence of iron electronic state

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