B22-Multimode InfraRed imaging And Microspectroscopy
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Diamond Proposal Number(s):
[11425]
Abstract: In this work, we address the kinetics of dehydrogenation occurring at high temperatures (HT) in riebeckite, a sodic amphibole with the ideal composition Na2Fe3+2 Fe2+3Si8O22(OH)2. We did isothermal experiments on both powders and single-crystals up to 560 °C and monitored the O-H stretching signal by Fourier Transform Infrared (FTIR) spectroscopy. Single-crystals show an initial increase in IR absorption intensity due to increasing vibrational amplitudes of the O-H bond stretching, not observed for powders. The OH-intensities vs. time were fitted using the formalism for first-order reactions. The calculated activation energies for H+ diffusion in riebeckite are 159 ± 15 kJ/mol for powders and 216 ± 20 kJ/mol for single crystals, respectively. The exponential factor m in the Avrami-Erofeev equation obtained for crystals ranges between 1.02 and 1.31, suggesting that, unlike powders, the dehydration process in crystals is not a purely first-order reaction. This implies that a second energy barrier must be considered, i.e., diffusion of H+ through the crystal. FTIR imaging showed that H+ diffusion occurs mainly perpendicular to the silicate double-chain. Our results confirm that the release of H+ from riebeckite occurs after the irreversible Fe2+-to-Fe3+ exchange, thus at temperatures > 550 °C. To be effective, the process needs the presence of external oxygen that, by interacting with H+ at the crystal surface, triggers the release of H2O molecules. This implies that oxidizing conditions are required for the amphibole to be an efficient water source at depth.
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May 2021
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I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[9914, 18747]
Abstract: Magmatic systems are dominated by five volatiles, namely H2O, CO2, F, Cl, and S (the igneous quintet). Multiple studies have measured partitioning of four out of these five volatiles (H2O, CO2, F, and Cl) between nominally volatile-free minerals and melts, whereas the partitioning of sulfur is poorly known. To better constrain the behavior of sulfur in igneous systems we measured the partitioning of sulfur between clinopyroxene and silicate melts over a range of pressure, temperature, and melt composition from 0.8 to 1.2 GPa, 1000 to 1240 °C, and 49 to 66 wt% SiO2 (13 measurements). Additionally, we determined the crystal-melt partitioning of sulfur for plagioclase (6 measurements), orthopyroxene (2 measurements), amphibole (2 measurements), and olivine (1 measurement) in some of these same run products. Experiments were performed at high and low oxygen fugacities, where sulfur in the melt is expected to be dominantly present as an S6+ or an S2– species, respectively. When the partition coefficient is calculated as the total sulfur in the crystal divided by the total sulfur in the melt, the partition coefficient varies from 0.017 to 0.075 for clinopyroxene, from 0.036 to 0.229 for plagioclase, and is a maximum of 0.001 for olivine and of 0.003 for orthopyroxene. The variation in the total sulfur partition coefficient positively correlates with cation-oxygen bond lengths in the crystals; the measured partition coefficients increase in the order: olivine < orthopyroxene < clinopyroxene ≤ amphibole and plagioclase. At high oxygen fugacities in hydrous experiments, the clinopyroxene/melt partition coefficients for total sulfur are only approximately one-third of those measured in low oxygen fugacity, anhydrous experiments. However when the partition coefficient is calculated as total sulfur in the crystal divided by S2– in the melt, the clinopyroxene/melt partition coefficients for experiments with melts between ~51 and 66 wt% SiO2 can be described by a single mean value of 0.063 ± 0.010 (1σ standard deviation about the mean). These two observations support the hypothesis that sulfur, as S2–, replaces oxygen in the crystal structure. The results of hydrous experiments at low oxygen fugacity and anhydrous experiments at high oxygen fugacity suggest that oxygen fugacity has a greater effect on sulfur partitioning than water. Although the total sulfur clinopyroxene-melt partition coefficients are affected by the Mg/(Mg+Fe) ratio of the crystal, partition coefficients calculated using S2– in the melt display no clear dependence upon the Mg# of the clinopyroxene. Both the bulk and the S 2– partition coefficients appear unaffected by IVAl in the clinopyroxene structure. No effect of anorthite content nor of iron concentration in the crystal was seen in the data for plagioclase-melt partitioning. The data obtained for orthopyroxene and olivine were too few to establish any trends. The partition coefficients of total sulfur and S 2– between the crystals studied and silicate melts are typically lower than those of fluorine, higher than those of carbon, and similar to those of chlorine and hydrogen. These sulfur partition coefficients can be combined with analyses of volatiles in nominally volatile-free minerals and previously published partition coefficients of H2O, C, F, and Cl to constrain the concentration of the igneous quintet, the five major volatiles in magmatic systems.
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May 2020
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I15-Extreme Conditions
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Diamond Proposal Number(s):
[17683]
Abstract: Compression and decompression experiments on face-centered cubic (fcc) γ′-Fe4N to 77 GPa at room temperature were conducted in a diamond-anvil cell with in situ X-ray diffraction (XRD) to examine its stability under high pressure. In the investigated pressure range, γ′-Fe4N did not show any structural transitions. However, a peak broadening was observed in the XRD patterns above 60 GPa. The obtained pressure-volume data to 60 GPa were fitted to the third-order Birch-Murnaghan equation of state (EoS), which yielded the following elastic parameters: K0 = 169 (6) GPa, K′ = 4.1 (4), with a fixed V0 = 54.95 Å at 1 bar. A quantitative Schreinemakers' web was obtained at 15–60 GPa and 300–1600 K by combining the EoS for γ′-Fe4N with reported phase stability data at low pressures. The web indicates the existence of an invariant point at 41 GPa and 1000 K where γ′-Fe4N, hexagonal closed-packed (hcp) ε-Fe7N3, double hexagonal closed-packed β-Fe7N3, and hcp Fe phases are stable. From the invariant point, a reaction γ′-Fe4N = β-Fe7N3 + hcp Fe originates toward the high-pressure side, which determines the high-pressure stability of γ′-Fe4N at 56 GPa and 300 K. Therefore, the γ′-Fe4N phase observed in the experiments beyond this pressure must be metastable. The obtained results support the existing idea that β-Fe7N3 would be the most nitrogen-rich iron compound under core conditions. An iron carbonitride Fe7(C,N)3 found as a mantle-derived diamond inclusion implies that β-Fe7N3 and Fe7C3 may form a continuous solid solution in the mantle deeper than 1000 km depth. Diamond formation may be related to the presence of fluids in the mantle, and dehydration reactions of high-pressure hydrous phase D might have supplied free fluids in the mantle at depths greater than 1000 km. As such, the existence of Fe7(C,N)3 in diamond can be an indicator of water transportation to the deep mantle.
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Dec 2019
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I12-JEEP: Joint Engineering, Environmental and Processing
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Matthew J.
Pankhurst
,
Nghia T.
Vo
,
Alan R.
Butcher
,
Haili
Long
,
Hongchang
Wang
,
Sara
Nonni
,
Jason
Harvey
,
Guđmundur
Guđfinnsson
,
Ronald
Fowler
,
Robert
Atwood
,
Richard
Walshaw
,
Peter D.
Lee
Diamond Proposal Number(s):
[14033]
Abstract: Olivine is a key constituent in the silicate Earth; its composition and texture informs petrogenetic understanding of numerous rock types. Here we develop a quantitative and reproducible method to measure olivine composition in three dimensions without destructive analysis, meaning full textural context is maintained. The olivine solid solution between forsterite and fayalite was measured using a combination of three-dimensional (3D) X-ray imaging techniques, 2D backscattered electron imaging, and spot-analyses using wavelength-dispersive electron probe microanalysis. The linear attenuation coefficient of natural crystals across a range of forsterite content from ∼73–91 mol% were confirmed to scale linearly with composition using 53, 60, and 70 kV monochromatic beams at I12-JEEP beamline, Diamond Light Source utilizing the helical fly-scan acquisition. A polychromatic X-ray source was used to scan the same crystals, which yielded image contrast equivalent to measuring the mol% of forsterite with an accuracy of <1.0%. X-ray tomography can now provide fully integrated textural and chemical analysis of natural samples containing olivine, which will support 3D and 3D+time petrologic modeling. The study has revealed >3 mm domains within a large crystal of San Carlos forsterite that varies by ∼2 Fo mol%. This offers a solution to an outstanding question of inter-laboratory standardization, and also demonstrates the utility of 3D, non-destructive, chemical measurement. To our knowledge, this study is the first to describe the application of XMT to quantitative chemical measurement across a mineral solid solution. Our approach may be expanded to calculate the chemistry of other mineral systems in 3D, depending upon the number, chemistry, and density of end-members.
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Nov 2018
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B18-Core EXAFS
I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[9044, 9598, 9647]
Open Access
Abstract: A critical radiation damage assessment of the materials that will be present in a Geological
Disposal Facility (GDF) for radioactive waste is a priority for building a safety case. Detailed analysis
of the effects of high-energy
a
-particle damage in phyllosilicates such as mica is a necessity, as these
are model structures for both the clay-based backfill material and the highly sorbent components of a
crystalline host rock. The
a
-radiation stability of biotite mica [general formula:
K(Mg,Fe)3(Al,Si3O10)(F,OH)2
] has been investigated using the 5 MV tandem pelletron at the University of Manchester’s
Dalton Cumbrian Facility (DCF) and both the microfocus spectroscopy (I18) and core X
-ray absorption
spectroscopy (B18) beamlines at Diamond Light Source (U.K.). Microfocus X-ray diffraction
mapping has demonstrated extensive structural aberrations in the mica resulting from controlled exposure
to the focused
4He2+ ion (a-particle) beam. Delivered doses were comparable to
a-particle fluences
expected in the highly active, near-field of a GDF. At doses up to 6.77 displacements per atom (dpa)
in the region of highest particle fluence, biotite mica displays a heterogeneous structural response to
irradiation on a micrometer scale, with sequential dilation and contraction of regions of the structure
perpendicular to the sheets, as well as a general overall contraction of the phyllosilicate layer spacing.
At the peak of ion fluence, the structure collapses under a high point defect density and amorphous
areas are pervasive among altered domains of the original lattice. Such structural alterations are likely
to affect the material’s capacity to sorb and retain escaped radionuclides over long timescales; increased
edge site availability may favor increased sorption while interlayer uptake will likely be reduced due
to collapse. Radiation-induced reduction of structural iron at the region of highest structural damage
across an
a-particle’s track has been demonstrated by Fe
K-edge X-ray absorption near edge spectroscopy (XANES) and local structural disorder has been confirmed by analysis of both potassium
K-edge
XANES and Fe
K-edge extended X-ray absorption fine structure analysis. An infrared absorption study
of deformations in the OH–
stretching region, along with electron probe microanalysis complements
the synchrotron data presented here
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Apr 2016
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I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[8522]
Abstract: Interface coupled dissolution-reprecipitation reactions (ICDR) are a common feature of fluid-rock interaction during crustal fluid flow. We tested the hypothesis that ICDR reactions can play a key role in scavenging minor elements by exploring the fate of U during the experimental sulfidation of hematite to chalcopyrite under hydrothermal conditions (220–300 °C). The experiments where U was added, either as solid UO2+x(s) or as a soluble uranyl complex, differed from the U-free experiments in that pyrite precipitated initially, before the onset of chalcopyrite precipitation. In addition, in UO2+x(s)-bearing experiments, enhanced hematite dissolution led to increased porosity and precipitation of pyrite+magnetite within the hematite core, whereas in uranyl nitrate-bearing experiments, abundant pyrite formed initially, before being replaced by chalcopyrite. Uranium scavenging was mainly associated with the early reaction stage (pyrite precipitation), resulting in a thin U-rich line marking the original hematite grain surface. This “line” consists of nanocrystals of UO2+x(s), based on chemical mapping and XANES spectroscopy. This study shows that the presence of minor components can affect the pathway of ICDR reactions. Reactions between U- and Cu-bearing fluids and hematite can explain the Cu-U association prominent in some iron oxide-copper-gold (IOCG) deposits.
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Aug 2015
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Abstract: The 10 Å phase is a high-pressure hydrous magnesium silicate whose composition appears to depend on synthesis conditions. We have measured the compressibility to 10.5 GPa and thermal expansivity to 400 °C of samples of 10 Å phase synthesized in long experiments (400 and 169 h, respectively) designed to maximize compositional equilibrium. The structure was refined using a metrically trigonal unit cell. Compression is highly anisotropic, especially over the first 2 GPa of compression, indicating weak bonding across the interlayer. There is an inflection in the compression curve of c at 8 GPa, suggesting a change in compression mechanism or the onset of non-hydrostaticity in the pressure medium. Fitting the compression data collected below 8 GPa to a Murnaghan equation-of-state gives V0 = 734.8(7) Å3, K0 = 25(1) GPa, K' = 18(1). Thermal expansion is also strongly anisotropic: coefficients for data up to 200 °C are {alpha}a = 0.15(5) x 10^-5 K^-1, {alpha}c = 3.1(2) x 10^-5 K^-1, {alpha}V = 3.4(2) x 10^-5 K^-1. Above 200 °C, the expansivity of c decreased, and all parameters showed a contraction after the experiment, suggesting partial dehydration at high temperatures. Comparison of our compressibility data with those of previous studies suggests that 10 Å phase synthesized in short experiments does not retain all of its interlayer H2O during quenching and decompression. In contrast, samples annealed for many hours at high pressure and temperature are stabilized by small amounts of hydrogarnet-type substitution and consequent hydrogen bond strengthening.
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Nov 2010
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Abstract: Ordering of Fe3+ and Fe2+ cations between octahedral and tetrahedral sites in synthetic members of the magnetite-ulvospinel (Fe3O4-Fe2TiO4) solid-solution series was determined using Fe L-2,L-3-edge X-ray magnetic circular dichroism (XMCD) coupled with electron microprobe and chemical analysis, Ti L-2,L-3-edge and Fe K-edge X-ray absorption spectroscopy (XAS), and unit-cell parameters. Microprobe analyses, cell edges, and chemical FeO determinations showed that bulk compositions were stoichiometric magnetite-ulvospinel solid solutions. XMCD showed that the surface was sensitive to redox conditions, and samples required re-equilibration with solid-solid buffers. Detailed site-occupancy analysis gave Fe2+/Fe3+ XMCD-intensity ratios close to stoichiometric values. L-2,L-3-edge XAS confirmed that Ti4+ was restricted to octahedral sites. XMCD showed that significant Fe2+ only entered the tetrahedral sites when Ti content was >0.40 atoms per formula unit (apfu), whereas Fe2+ in octahedral sites increased from 1 apfu in magnetite to a maximum of similar to 1.4 apfu when Ti content was 0.45 apfu. As Ti content increased, a steady increase in Fe2+ in tetrahedral sites was observable in the XMCD spectra, concurrent with a slow decrease in Fe2+ in octahedral sites. Calculated magnetic moments decreased rapidly from magnetite (4.06 mu(B)) to USP45 (1.5 mu(B)), then more slowly toward ulvospinel (0 mu(B)). Two synthesized samples were maghemitized by re-equilibrating with an oxidizing buffer. XMCD showed that Fe2+ oxidation, with concomitant vacancy formation, was restricted to octahedral sites. Through the direct measurement of Fe oxidation states, XMCD results can be used to rationalize the magnetic properties of titanomagnetites, along with oxidized titanomaghemitized analogs, in Earth's crustal rocks.
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Jan 2010
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Abstract: We recorded angle-dependent XANES (AXANES) spectra at the potassium K-edge for three compositionally intermediate polylithionite-siderophyllite trioctahedral 1M-micas using polarized synchrotron radiation. We evaluated the experimental spectra for both their in-plane and out-of-plane component fractions of the electric dipole contribution using the analytical formulae of Brouder (1990), referring to theory to extract the origin of their multiple-scattering pathways of Natoli et al. (2003). This analysis was extended to a fourth lithian mica studied previously and allowed characterization of the local environment and ordering around the potassium atoms in the interlayer of the entire set of micas. The AXANES in-plane components are notably similar to the XANES spectra recorded on randomly oriented powders, provided these are oriented at the "magic angle" (Pettifer et al. 1992). Most observed contributions arise from multiple-scattering interactions of the photoelectron ejected from the potassium absorber colliding with atoms located in the interlayer itself. Note that this includes not only interactions with other coplanar potassium and/or alkali atoms distributed along the interlayer plane, but also with their near- and next-nearest neighboring oxygen atoms which lie on the basal planes of the tetrahedral sheets facing the interlayer. By contrast, the AXANES out-of-plane component suggests that several multiple-scattering pathways cross the energetic and structural-barrier represented by the tetrahedral sheets. They reach not only the X anions that are located on the upper level of the octahedral sheets, at the center of the open cavity in the tetrahedral sheet, but also the metal cations centering the octahedral sheet itself. Therefore, the out-of-plane components provide indirect information on the number of independent octahedral sites, the cation oxidation state, and the trans- vs. cis-orientation of the anionic sites.
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Jan 2010
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NONE-No attached Diamond beamline
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Abstract: Ferrimagnetic nanoparticles have many uses in industry including in magnetic recording media and transformers, however these particles are often expensive to synthesize. In this study, the Fe3+-reducing bacteria Geobacter sulfurreducens and Shewanella oneidensis were used to synthesize spinel ferrite nanoparticles of the general chemical formula MxFe3–xO4, where M is either Co, Ni, Mn, Zn, or a combination of Mn and Zn. This was done at ambient temperatures through the dissimilatory reduction of Fe3+-oxyhydroxides containing the appropriate substitutional cations. A combination of L-edge and K-edge X-ray absorption spectroscopy (XAS) and L-edge X-ray magnetic circular dichroism (XMCD) was used to determine the site occupancies, valence, and local structure of the Fe and substitutional cations within the spinels. The Ni and Co ferrites produced using each bacterium were very similar and therefore this study concludes that, despite the difference in reduction mechanism of the bacteria used, the end-product is remarkably unaltered. Nickel ferrites contained only Ni2+, with at least 80% in Oh coordination. Cobalt ferrites contained only Co2+ but with a significant proportion (up to 45%) in Td coordination, showing a slight preference for Td sites. The Mn-ferrites contained Mn2+ only on the Oh sites but a mixture of Mn2+ and Mn3+ on Td sites when the amount of Mn exceeded 3% (compared to the amount of Fe) or some Zn was also present. This study successfully produced a range of nanoparticulate ferrites that could be produced industrially using relatively environmentally benign methodologies.
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Jul 2008
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