I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[14793, 15903]
Abstract: Eudialyte group minerals (EGM) attract global interest as potential resources for High Field
Strength Elements (HFSE, e.g. Zr, Nb, Ta, and Rare Earth Elements, REE), i.e. critical
materials for modern technologies. They are particularly valued for their relative enrichment
in the most critical lanthanides, i.e. Nd and heavy REE (Gd-Lu). However, REE substitution
mechanisms into the EGM structure are still poorly understood. Light and heavy REE may
occupy different sites and there may be ordering and/or defect clustering in the structure. This
study uses X-ray Absorption Spectroscopy (XAS) to determine the structural state of REE in
EGM from prospective eudialyte-bearing complexes. Yttrium K-edge and Nd L3-edge spectra
were collected as proxies for heavy and light REE, respectively, and compared to natural and
synthetic REE-bearing standards. Extended X-ray Absorption Fine Structure (EXAFS) data
yield best fits for Y in six-fold coordination with Y-O distances of 2.24-2.32 Å, and a second
coordination sphere comprising Fe, Na, Ca, Si and O at radial distances of 3.6-3.8 Å. These
findings are consistent with dominant Y3+ substitution for Ca2+ on the octahedral M1 site in
all samples studied, and exclude preferential substitution of Y3+ onto the smaller octahedral Z
site or the large low-symmetry N4 site. Using lattice strain theory, we constructed relative partitioning models to predict site
preferences of lanthanides we have not directly measured. The models predict that all REE
are favoured on the Ca-dominant M1 site and that preferential partitioning of heavy over light
REE increases in EGM containing significant Mn in the M1-octahedral rings (oneillite
3
subgroup). Thus, the flat REE profiles that make EGM such attractive exploration targets are
not due to preferential partitioning of light and heavy REE onto different sites. Instead, local
ordering of Mn- and Ca-occupied M1 sites may influence the capacity of EGM to
accommodate heavy REE.
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Aug 2019
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I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[10070]
Abstract: The spinel group minerals, found in a range of igneous rocks, are resistant to weathering and can incorporate several multivalent elements, meaning they have the potential to provide insight into redox conditions of parental magmas. Naturally occurring spinel can contain varying quantities of Mn, an element which occurs terrestrially and extraterrestrially as Mn2+, Mn3+, Mn4+ and Mn5+. However, a lack of information on the effects of oxygen fugacity (fO2) on: (1) Mn valence state and cation distribution, and (2) on spinel-melt partitioning means that the potential for a Mn-in-spinel oxy-barometer remains largely untested. Here, we use electron probe microanalysis, micro-focus X-ray Absorption Near Edge Structure (XANES) spectroscopy and single crystal X-ray diffraction (SC-XRD) to investigate cation distribution and valence state in spinels in the Al-Mn-O and Fe-Mn-O systems synthesized at ambient pressure under varying fO2 conditions. In contrast to previous studies, we find that the spectral resolution of the Mn K edge XANES spectra is insufficient to provide quantitative data on Mn valence state and site occupancy, although it does verify that Mn is incorporated as both Mn2+ and Mn3+, distributed over tetrahedral and octahedral sites. Combination of data from XANES and SC-XRD refinements can, however, be used to model Mn, Al and Fe valence and site occupancy. It would be expected that Mn-Fe spinels have the potential to record fO2 conditions in parental melts due to changes to the octahedral site under more reducing conditions. However, decoupling the effects of temperature and oxygen fugacity on the TFe3+-TMn2+ exchange in the Mn-Fe spinels remains challenging. In contrast, little variation is noted in Mn-Al spinels as a function of fO2, implying that crystal chemistry and cation site geometry may significantly influence cation distribution, and by inference, crystal-melt partitioning, in spinel group minerals.
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May 2018
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I13-2-Diamond Manchester Imaging
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Diamond Proposal Number(s):
[12201]
Abstract: The ~492 Ma Shetland Ophiolite Complex (SOC) contains an extensive mantle section, within which numerous podiform chromitite bodies formed during melt percolation in a supra-subduction zone setting. One of the SOC chromitite localities has an unusual style of platinum-group element (PGE) mineralisation. Specifically, the Cliff chromitite suite has relatively high (>250 ppm) Pt plus Pd, compared to other SOC chromitites. In this study, we apply petrographic observation, mineral chemistry and novel X-ray microtomography data to elucidate the petrogenesis of PGE-bearing phases at Cliff. The combined datasets reveal that the PGE at Cliff have likely been fractionated by an As-rich fluid, concentrating Pt and Ir into visible (0.1-1 μm) platinum-group minerals (PGM) such as sperrylite and irarsite, respectively. The high (>1 ppm) bulk rock concentrations of the other PGE (e.g., Os) in the Cliff chromitites suggests the presence of abundant fine-grained unidentified PGM in the serpentinised groundmass. The spatial association of arsenide phases and PGM with alteration rims on Cr-spinel grains suggests that the high Pt and Pd abundances at Cliff result from a late-stage low-temperature (e.g., 200-300°C) hydrothermal event. This conclusion highlights the potential effects that secondary alteration processes can have on modifying and upgrading the tenor of PGE deposits.
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Apr 2018
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Abstract: Millsite, CuTeO3·2H2O, is a new mineral from Gråurdfjellet in Oppdal, Norway. It occurs as a minor secondary phase alongside teineite, other copper secondaries and relict primary tellurides in a boulder of quartz-rich granite, which is probably a glacial erratic. Millsite is bright cyan to royal blue in colour. The mineral is transparent to slightly translucent with a vitreous lustre and has a perfect (100) cleavage. It is brittle, has a conchoidal fracture and a pale green streak. Millsite is optically biaxial (+), α = 1.756(5), β = 1.794(5), γ = 1.925calc and 2Vmeas = 60(1)°; Millsite has monoclinic space group P21/c, with a = 7.4049(2) Å, b = 7.7873(2) Å, c = 8.5217(2) Å, β = 110.203(3)°, V = 461.17(2) Å3 and Z = 4. The empirical formula is Cu0.99(Te0.98Se0.02)O3(H2O)2. The five strongest reflections in the X-ray powder diffraction pattern are [dhkl in Å (hkl, Irel %)]: 6.954 (100, 100), 3.558 (012, 64), 2.838 (12¯2, 47), 2.675 (211, 43) and 3.175 (210, 39). The crystal structure has been determined to R1 = 0.016, wR2 = 0.036, GooF = 1.049. The diagnostic structural unit of millsite consists of a Cu2O6(H2O)4 dimer that is decorated with four TeO3 groups connecting adjacent dimers and defining (100) heteropolyhedral sheets. These heteropolyhedral sheets are only connected by layers of structurally significant hydrogen bonds and correlate with the (100) cleavage. Millsite is a polymorph of teineite with a unique configuration of the M2O6(H2O)4 dimer that leads to a sheet topology. No isostructural selenium or tellurium analogue exists. The monoclinic polymorph (P21/c) of chalcomenite “monoclinic-CuSeO3·2H2O” hereafter, ahlfeldite and MgSeO3·2H2O have M2O6(H2O)4 dimers, but their configuration differs significantly from that of millsite and leads to a framework topology rather than a sheet. Teineite does not have a dimeric structure and so is fundamentally different from millsite. The sheet topology of millsite appears to be unique among tellurites.
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Aug 2017
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Abstract: Synthesis of Ni and Zn substituted nano-greigite, Fe3S4, is achieved from single source diethyldithiocarbamato
precursor compounds, producing particles typically 50–100 nm in diameter with plate-like pseudohexagonal morphologies. Up to 12 wt.% Ni is incorporated into the greigite structure, and there is evidence that Zn is also incorporated but Co is not substituted into the lattice. The Fe L3 X-ray absorption spectra for these materials have a narrow single peak at 707.7 eV and the resulting main X-ray magnetic circular dichroism (XMCD) has the same sign at 708.75 eV. All XMCD spectra also have a broad positive feature at 711 eV, a characteristic of covalent mixing. The greigite XMCD spectra contrast with the three clearly defined XMCD site specific peaks found in the ferrite spinel, magnetite. The Fe L2,3 X-ray absorption spectra and XMCD spectra of the greigite reflect and reveal the high conductivity of greigite and the very strong covalency of the Fe–S bonding. The electron hopping between Fe3+ and Fe2+ on octahedral sites results in an intermediate oxidation state of the Fe in theOh site of Fe2.5+ producing an effective formula
of [Fe3þ "]A-site[2Fe2:5þ #]B-siteS24 ]. The Ni L2,3 X-ray absorption spectra and XMCD reveal substitution on the Oh site with a strongly covalent character and an oxidation state
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Aug 2016
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B18-Core EXAFS
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Diamond Proposal Number(s):
[4941]
Open Access
Abstract: Geological disposal facilities (GDF) are intended to isolate and contain radioactive waste within multiple protective barriers, deep underground, to ensure that no harmful quantities of radioactivity reach the surface environment. The last line of defense in a multi-barrier GDF is the geosphere, where iron is present in the
host rock mineralogy as either Fe(II) or Fe(III), and in groundwater as Fe(II) under reducing conditions. The mobility of risk-driving radionuclides, including uranium and technetium, in the environment is affected
significantly by their valence state. Due to its low redox potential, Fe(II) can mediate reduction of these radionuclides from their oxidized, highly mobile, soluble state to their reduced, insoluble state, preventing them from reaching the biosphere. Here a study of five types of potential host rocks, two granitoids, an andesite, a mudstone and a clay-rich carbonate, is reported. The bulk rocks and their minerals were analysed
for iron content, Fe(II/III) ratio, and for the speciation and fine-grained nature of alteration product minerals that might have important controls on groundwater interaction. Total iron content varies between 0.9% in clays to 5.6% in the andesite. X-ray absorption spectroscopy reveals that Fe in the granitoids and andesite is
predominantly Fe(II), and in mudstones, argillaceous limestone and terrestrial sandstone is predominantly Fe(III). The redox reactivity of the potential host rocks both in the presence and absence of Fe(II)-containing ‘model’ groundwater was investigated using an azo dye as a probe molecule. Reduction rates as determined by reactivity with the azo dye were correlated with the ability of the rocks to uptake Fe(II) from groundwater rather than with initial Fe(II) content. Potential GDF host rocks must be characterized in terms of mineralogy, texture, grain size and bulk geochemistry to assess how they might interact with groundwater. This study highlights the importance of redox reactivity, not just total iron and Fe(II)/(III) ratio, when considering the host rock performance as a barrier material to limit transport of radionuclides from the GDF.
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Dec 2015
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I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[6208, 9044]
Open Access
Abstract: A detailed understanding of the response of mineral phases to the radiation fields experienced in a geological disposal facility (GDF) is currently poorly constrained. Prolongued ion irradiation has the potential to affect both the physical integrity and oxidation state of materials and therefore may alter a structure's ability to react with radionuclides. Radiohalos (spheres of radiation damage in minerals surrounding radioactive (α-emitting) inclusions) provide useful analogues for studying long term α-particle damage accumulation. In this study, silicate minerals adjacent to Th- and U-rich monazite and zircon were probed for redox changes and long/short range disorder using microfocus X-ray absorption spectroscopy (XAS) and high resolution X-ray diffraction (XRD) at Beamline I18, Diamond Light Source. Fe3+→ Fe2+ reduction has been demonstrated in an amphibole sample containing structural OH− groups – a trend not observed in anhydrous phases such as garnet. Coincident with the findings of Pattrick et al. (2013), the radiolytic breakdown of OH− groups is postulated to liberate Fe3+ reducing electrons. Across all samples, high point defect densities and minor lattice aberrations are apparent adjacent to the radioactive inclusion, demonstrated by micro-XRD.
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Dec 2015
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B18-Core EXAFS
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Diamond Proposal Number(s):
[7367, 7593, 8070]
Open Access
Abstract: Uranium incorporation into magnetite and its behaviour during subsequent oxidation has been investigated at high pH to determine the uranium retention mechanism(s) on formation and oxidative perturbation of magnetite in systems relevant to radioactive waste disposal. Ferrihydrite was exposed to U(VI)aq
containing cement leachates (pH 10.5–13.1) and crystallization of magnetite was induced via addition of Fe(II)aq. A combination of XRD, chemical extraction and XAS techniques provided direct evidence that U(VI) was reduced and incorporated into the magnetite structure, possibly as U(V), with a significant fraction recalcitrant to oxidative remobilization. Immobilization of U(VI) by reduction and incorporation into
magnetite at high pH, and with significant stability upon reoxidation, has clear and important implications for limiting uranium migration in geological disposal of radioactive wastes.
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Dec 2015
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I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[9094]
Abstract: Manganese incorporation in synthetic hercynite, and partitioning between hercynite and silicate melt synthesized at 1.0 GPa, 1250°C, and at an fO2 buffered by Fe–FeO, has been studied by X-ray absorption spectroscopy and single-crystal X-ray structure refinement. Spectra indicate the presence of both Mn2+ and Mn3+ (and possibly also Mn4+) in synthetic hercynite and partitioning of Mn2+ into the melt phase, and Mn3+ into hercynite, respectively, under run conditions. X-ray refinement is consistent with partial disorder of Fe and Al across tetrahedral and octahedral sites. A higher than expected degree of Fe-Al disorder in the Mn-bearing hercynite can be explained by preferential incorporation of Mn2+ onto the tetrahedral site, and indicates that Fe-Al disorder in pure, stoichiometric hercynite cannot necessarily be used to determine closure temperatures in natural spinel. However, partitioning of Mn2+ and Mn3+ between melt and hercynite suggests that Mn incorporation in hercynite could be used as a measure of fO2 conditions in magmas during spinel crystallization.
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Jun 2015
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B18-Core EXAFS
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Diamond Proposal Number(s):
[7799]
Abstract: Iron oxides resulting from the corrosion of large quantities of steel that are planned to be installed throughout a deep geological disposal facility (GDF) are expected to be one of the key surfaces of interest for controlling radionuclide behaviour under disposal conditions. Over the lengthy timescales associated with a GDF, the system is expected to become anoxic so that reduced Fe(II) phases will dominate. Batch experiments have therefore been completed in order to investigate how a model reduced Fe-oxide surface (wüstite, Fe1xO) alters as a function of exposure to aqueous solutions with compositions representative of conditions expected within a GDF. Additional experiments were performed to constrain the effect that highly alkaline solutions (up to pH 13) have on the adsorption behaviour of the uranyl (Formula ) ion onto the surfaces of both wüstite and portlandite [Ca(OH)2; representative of the expected cementitious phases]. Surface co-ordination chemistry and speciation were determined by ex situ X-ray absorption spectroscopy measurements (both X-ray absorption near-edge structure analysis (XANES) and extended X-ray absorption fine structure analysis (EXAFS)). Diffraction, elemental analysis and XANES showed that the bulk solid composition and Fe oxidation state remained relatively unaltered over the time frame of these experiments (120 h), although under alkaline conditions possible surface hydroxylation is observed, due presumably to the formation of surface hydroxyl complexes. The surface morphology, however, is altered significantly with a large degree of roughening and an observed decrease in the average particle size. Reduction of U(VI) to U(IV) occurs during adsorption in almost all cases and this is interpreted to indicate that wüstite may be an effective reductant of U during surface adsorption. This work also shows that increasing the carbonate concentration in reactant solutions dramatically decreases the adsorption coefficients for U on both wüstite and portlandite, consistent with U speciation and surface reactivity determined in other studies. Finally, the EXAFS results include new details about exactly how U bonds to this metal oxide surface.
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Nov 2014
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