I12-JEEP: Joint Engineering, Environmental and Processing
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Fabio
Arzilli
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Margherita
Polacci
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Giuseppe
La Spina
,
Nolwenn
Le Gall
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Edward W.
Llewellin
,
Richard A.
Brooker
,
Rafael
Torres-Orozco
,
Danilo
Di Genova
,
David A.
Neave
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Margaret E.
Hartley
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Heidy M.
Mader
,
Daniele
Giordano
,
Robert
Atwood
,
Peter D.
Lee
,
Florian
Heidelbach
,
Mike R.
Burton
Diamond Proposal Number(s):
[16188]
Open Access
Abstract: The majority of basaltic magmas stall in the Earth’s crust as a result of the rheological evolution caused by crystallization during transport. However, the relationships between crystallinity, rheology and eruptibility remain uncertain because it is difficult to observe dynamic magma crystallization in real time. Here, we present in-situ 4D data for crystal growth kinetics and the textural evolution of pyroxene during crystallization of trachybasaltic magmas in high-temperature experiments under water-saturated conditions at crustal pressures. We observe dendritic growth of pyroxene on initially euhedral cores, and a surprisingly rapid increase in crystal fraction and aspect ratio at undercooling ≥30 °C. Rapid dendritic crystallization favours a rheological transition from Newtonian to non-Newtonian behaviour within minutes. We use a numerical model to quantify the impact of rapid dendritic crystallization on basaltic dike propagation, and demonstrate its dramatic effect on magma mobility and eruptibility. Our results provide insights into the processes that control whether intrusions lead to eruption or not.
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Jun 2022
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B22-Multimode InfraRed imaging And Microspectroscopy
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Abstract: Breadcrust bombs are pyroclasts displaying fractured, dense surfaces enveloping expanded interiors, and are associated with Vulcanian explosions. We document pyroclasts from the 2008–2009 CE eruption of Chaitén (Chile) that are internally as well as externally breadcrusted. The pyroclasts are cut by intersecting micrometer- to millimeter-thick tuffisites with dense glassy walls, which grade into strongly inflated pumiceous material. We find H2O diffusion gradients proximal to the breadcrusted surfaces, such that H2O is depleted from far-field magma (0.68 ± 0.04 wt%) into dense, fractured vein walls (0.2–0.3 wt%), indicating a spatial association between H2O mass transfer within the pyroclast interior and both suppressed vesiculation and breadcrusting. We experimentally confirm that diffusive H2O depletion suppresses bubble growth at shallow conduit conditions. Therefore, we interpret the breadcrust formation to be induced by H2O diffusion and the associated rise in viscosity rather than by cooling in the classical breadcrust-formation models. We posit that a “dehydration quench” is important as degassing continues to very low H2O contents in shallow-conduit magma that continues to vesiculate.
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Jun 2022
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I08-Scanning X-ray Microscopy beamline (SXM)
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Dawn M.
Buchanan
,
Laura
Newsome
,
Jonathan R.
Lloyd
,
Majid
Kazemian
,
Burkhard
Kaulich
,
Tohru
Araki
,
Heath
Bagshaw
,
John
Waters
,
Gerrit
Van Der Laan
,
Alpha
N’diaye
,
Victoria S.
Coker
Diamond Proposal Number(s):
[17626]
Open Access
Abstract: Cobalt is an essential element for life and plays a crucial role in supporting the drive to clean energy, due to its importance in rechargeable batteries. Co is often associated with Fe in the environment, but the fate of Co in Fe-rich biogeochemically-active environments is poorly understood. To address this, synchrotron-based scanning X-ray microscopy (SXM) was used investigate the behaviour of cobalt at the nanoscale in Co-Fe(III)-oxyhydroxides undergoing microbial reduction. SXM can assess spatial changes in metal speciation and organic compounds helping to elucidate the electron transfer processes occurring at the cell-mineral interface and inform on the fate of cobalt in redox horizons. G. sulfurreducens was used to reduce synthetic Co-ferrihydrite as an analogue of natural cobalt-iron-oxides. Magnetite [Fe(II)/Fe(III)3O4] production was confirmed by powder X-ray diffraction (XRD), SXM and X-ray magnetic circular dichroism (XMCD) data, where best fits of the latter suggested Co-bearing magnetite. Macro-scale XAS techniques suggested Co(III) reduction occurred and complementary SXM at the nanoscale, coupled with imaging, found localised biogenic Co(III) reduction at the cell-mineral interface via direct contact with outer membrane cytochromes. No discernible localised changes in Fe speciation were detected in the reordered cobalt-iron-oxides that were formed and at the end point of the experiment only 11% Co and 1.5% Fe had been solubilised. The solid phase retention, alongside the highly localised and preferential cobalt bioreduction observed at the nanoscale is consistent with retention of Co in redox zones. This work improves our fundamental molecular-scale understanding of the fate of Co in complex environmental systems and supports the development of biogenic Co-doped magnetite for industrial applications from drug delivery systems to magnetic recording media.
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May 2022
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I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[16025]
Open Access
Abstract: Assessing element speciation and solubility control mechanisms in multi-contaminated soils poses great challenges. In this study, we examined the speciation and mechanisms controlling the solubility of As and Zn in a soil historically contaminated with As, Cu, Cr, and Zn salts used for wood preservation. The leaching behavior of dissolved species, particles, and colloids was studied in an irrigation experiment with intact soil columns. Batch experiments were used to study the solubility of dissolved species as a function of pH (2–8). The speciation of As and Zn in bulk soil and leached particles was studied with microscale X-ray fluorescence (μ-XRF) and extended X-ray absorption fine structure (EXAFS) spectroscopy. Chemical speciation and solubility were evaluated by geochemical modelling. μ-XRF of bulk soil and particles showed that As and Zn were correlated in space. Bulk- and μ-EXAFS of As and Zn, in combination with calculated ion activity products of possible As-Zn minerals, suggested a koritnigite (ZnHAsO4·H2O) phase controlling the dissolved fraction of As(V) and Zn with an apparent log Ksp of −21.9 ± 0.46. This phase lowered the solubility of As by almost two orders of magnitude in soil at pH > 5, and could therefore be of great importance at other multi-contaminated sites.
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Apr 2022
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Open Access
Abstract: The structure of a new polymorph of MgSO4·6H2O, a potentially important mineral on the surface of Europa, one of Jupiter’s icy moons, was reported by Maynard-Casely et al. [Maynard-Casely, H. E.; Brand, H. E.; Wilson, S. A.; Wallwork, K. S. Mineral Diversity on Europa: Exploration of Phases Formed in the MgSO4–H2SO4–H2O Ternary. ACS Earth Space Chem. 2021, 5 (7), 1716−1725. DOI: 10.1021/acsearthspacechem.1c00073]. The reported structure is unambiguously incorrect because the stoichiometry is wrong; the formula unit contains only half of the SO42– oxyanions required. We highlight where this error could have been detected at various stages of the analysis, writeup, and submission process and make recommendations to avoid repetition of the mistake.
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Apr 2022
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I20-Scanning-X-ray spectroscopy (XAS/XES)
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Diamond Proposal Number(s):
[21441]
Open Access
Abstract: Selenium (Se) is a toxic contaminant with multiple anthropogenic sources, including 79Se from nuclear fission. Se mobility in the geosphere is generally governed by its oxidation state, therefore understanding Se speciation under variable redox conditions is important for the safe management of Se contaminated sites. Here, we investigate Se behavior in sediment groundwater column systems. Experiments were conducted with environmentally relevant Se concentrations, using a range of groundwater compositions, and the impact of electron-donor (i.e., biostimulation) and groundwater sulfate addition was examined over a period of 170 days. X-Ray Absorption Spectroscopy and standard geochemical techniques were used to track changes in sediment associated Se concentration and speciation. Electron-donor amended systems with and without added sulfate retained up to 90% of added Se(VI)(aq), with sediment associated Se speciation dominated by trigonal Se(0) and possibly trace Se(-II); no Se colloid formation was observed. The remobilization potential of the sediment associated Se species was then tested in reoxidation and seawater intrusion perturbation experiments. In all treatments, sediment associated Se (i.e., trigonal Se(0)) was largely resistant to remobilization over the timescales of the experiments (170 days). However, in the perturbation experiments, less Se was remobilized from sulfidic sediments, suggesting that previous sulfate-reducing conditions may buffer Se against remobilization and migration.
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Apr 2022
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I14-Hard X-ray Nanoprobe
I18-Microfocus Spectroscopy
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Abstract: New mineralogical studies of Lafayette reveal that it contains a notably variable abundance of martian carbonate. Four percent was identified in mesostasis (3.2%) and olivine-hosted (0.8%) fractures in one polished section, but only 0.2% of both textural types in another. The Lafayette carbonates are Mg0.0-2.0Cc13.2-38.6Sd17.7-81.9Rh3.1-42.9. They have undergone variable but extensive amounts of dissolution and replacement as the nakhlite secondary fluid evolved, associated with the precipitation of ferric saponite in olivine fractures and a serpentine-like phyllosilicate in the mesostasis. The mesostasis carbonate has undergone the highest degree of corrosion and replacement. TEM analysis has shown the presence of Fe-(hydr)oxide (likely ferrihydrite) nanoparticles on olivine-hosted carbonates which can be linked to the cessation of more extensive carbonate dissolution at those sites. The mesostasis serpentine-like mineral has been described here on the basis of WDS and EDX analyses, HRTEM and Fe-K XANES, as odinite, a ferric, 0.7 nm d001-spacings phyllosilicate mineral with a characteristic 1:1 serpentine-like structure. The carbonate dissolution stage and then formation of Fe-(hydr)oxide nanoparticles occurred under circumneutral-alkaline conditions 7 < pH < 10. This range of pH is also where the general dissolution mechanism switched from a proton-promoted, to a water hydrolysis reaction associated with a reduction in the dissolution rates. As dissolution rates were reduced and the fluid had cooled to ≤50°C, the precipitation of the ferric saponite and odinite, a phyllosilicate associated with temperatures of ∼25°C, dominated over the carbonate dissolution. The extensive dissolution of such crustal carbonate across the upper martian crust, producing bicarbonate and carbon dioxide, and the coupled formation of ferric phyllosilicates, would lead to the formation of CH4 in substantial amounts via a Fischer-Tropsch type reaction. The results of our study illustrate a process to explain the relatively low abundance of detected carbonate on Mars and a likely source for some of the methane on Mars.
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Feb 2022
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B18-Core EXAFS
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Diamond Proposal Number(s):
[21441, 18594]
Abstract: Molybdenum (Mo) is a key trace element and a contaminant in many environments including mine tailings and acid mine drainage systems. Under oxic conditions Mo exists in a number of forms, including mono-molybdate (Mo(VI)O42-) and various poly-molybdate species (e.g. Mo(VI)7O246-) depending on the geochemical conditions (e.g. pH). The mobility and bioavailability of Mo is often controlled by sorption to mineral surfaces, including iron (oxyhydr)oxides e.g. hematite (Fe2O3). This study uses adsorption isotherms, PHREEQC geochemical modelling, Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy (ATR-FTIR), and X-ray Absorption Spectroscopy (XAS) to holistically characterise the molecular scale adsorption of molybdate to hematite as a function of pH (3-12) and Mo(VI) concentration (0.01 ×10-4 - 2 ×10-3 M). PHREEQC and ATR-FTIR indicated both pH and Mo concentration are important variables when forming mono- vs. poly- molybdate and suggest low pH (≤ 4) and high Mo(VI) concentration (≥ 5 ×10-4 M) contribute to the formation of poly-molybdate (heptamolybdate Mo7O246-). XAS found Mo adsorbed to hematite via an inner-sphere corner-sharing bidentate binuclear complex with an octahedral mono-molybdate structure at a Mo concentration of 0.6 ×10-4 M across the pH range, and at a Mo(VI) concentration of 5 ×10-4 M and pH over 5. This is the first direct observation of octahedrally coordinated Mo(VI) adsorption species on hematite, and this information has broad implications for the mobility and transport of Mo as a contaminant in the environment.
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Feb 2022
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I08-Scanning X-ray Microscopy beamline (SXM)
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A.
Steele
,
L. G
Benning
,
R.
Writh
,
A.
Schreiber
,
T.
Araki
,
F. M.
Mccubbin
,
M. R.
Fries
,
L. R.
Nittler
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J.
Wang
,
L. J.
Hallis
,
P. G.
Conrad
,
C.
Conley
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S.
Vitale
,
A. C.
O'Brien
,
V.
Riggi
,
K.
Rogers
Diamond Proposal Number(s):
[2444]
Abstract: Water-rock interactions are relevant to planetary habitability, influencing mineralogical diversity and the production of organic molecules. We examine carbonates and silicates in the martian meteorite Allan Hills 84001 (ALH 84001), using colocated nanoscale analyses, to characterize the nature of water-rock reactions on early Mars. We find complex refractory organic material associated with mineral assemblages that formed by mineral carbonation and serpentinization reactions. The organic molecules are colocated with nanophase magnetite; both formed in situ during water-rock interactions on Mars. Two potentially distinct mechanisms of abiotic organic synthesis operated on early Mars during the late Noachian period (3.9 to 4.1 billion years ago).
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Jan 2022
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B18-Core EXAFS
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Diamond Proposal Number(s):
[28383]
Open Access
Abstract: Limonitic layers of the regolith, which are often stockpiled as waste materials at laterite mines, commonly contain significant concentrations of valuable base metals, such as nickel, cobalt, and manganese. There is currently considerable demand for these transition metals, and this is projected to continue to increase (alongside their commodity values) during the next few decades, due in the most part to their use in battery and renewable technologies. Limonite bioprocessing is an emerging technology that often uses acidophilic prokaryotes to catalyse the oxidation of zero-valent sulphur coupled to the reduction of Fe (III) and Mn (IV) minerals, resulting in the release of target metals. Chromium-bearing minerals, such as chromite, where the metal is present as Cr (III), are widespread in laterite deposits. However, there are also reports that the more oxidised and more biotoxic form of this metal [Cr (VI)] may be present in some limonites, formed by the oxidation of Cr (III) by manganese (IV) oxides. Bioleaching experiments carried out in laboratory-scale reactors using limonites from a laterite mine in New Caledonia found that solid densities of ∼10% w/v resulted in complete inhibition of iron reduction by acidophiles, which is a critical reaction in the reductive dissolution process. Further investigations found this to be due to the release of Cr (VI) in the acidic liquors. X-ray absorption near edge structure (XANES) spectroscopy analysis of the limonites used found that between 3.1 and 8.0% of the total chromium in the three limonite samples used in experiments was present in the raw materials as Cr (VI). Microbial inhibition due to Cr (VI) could be eliminated either by adding limonite incrementally or by the addition of ferrous iron, which reduces Cr (VI) to less toxic Cr (III), resulting in rates of extraction of cobalt (the main target metal in the experiments) of >90%.
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Jan 2022
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