I20-Scanning-X-ray spectroscopy (XAS/XES)
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Diamond Proposal Number(s):
[16735, 17313]
Open Access
Abstract: Cobalt is essential for the modern technology that underpins the decarbonisation of our economies, but its supply is limited leading to its designation as a critical metal. Cobalt biogeochemistry is poorly understood, yet knowledge of how biogeochemical cycling impacts cobalt behaviour could assist the development of new techniques to recover cobalt from ores, and so improve the security of supply. Laterites are an important source of cobalt, they are primarily processed for nickel using energy or chemical intensive processes, with cobalt recovered as a by-product. Metal-reducing conditions were stimulated in laterite sediment microcosms by the addition of simple and cheaply available organic substrates (acetate or glucose). At the end of the experiment the amount of easily recoverable cobalt (aqueous or extractable with acetic acid) increased from < 1 % to up to 64 %, which closely mirrored the behaviour of manganese, while only a small proportion of iron was transformed into an easily recoverable phase. Sequencing of the microbial community showed that the addition of organic substrates stimulated the growth of indigenous prokaryotes closely related to known manganese(IV)/iron(III)-reducers, particularly from the Clostridiales, and that fungi assigned to Penicillium, known to produce organic acids beneficial for leaching cobalt and nickel from laterites, were identified. Overall, the results indicate that the environmental behaviour of cobalt in laterites is likely to be controlled by manganese biogeochemical cycling by microorganisms. These results are compelling given that similar behaviour was observed in four laterites (Acoje, Çaldağ, Piauí and Shevchenko) from different continents. A new bioprocessing strategy is proposed whereby laterites are treated with an organic substrate to generate metal-reducing conditions, then rinsed with acetic acid to remove the cobalt. Not only are organic substrates environmentally-friendly and potentially sourced from waste carbon substrates, a minimal amount of iron oxides was mobilised and consequently less waste generated.
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Oct 2019
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I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[13616]
Abstract: The whelk Buccinum undatum is commercially important in the North Atlantic. However, monitoring the ontogenetic age and growth of populations has been problematic for fisheries scientists owing to the lack of a robust age determination method. We confirmed the annual periodicity of growth rings present in calcified statoliths located in the foot of field-collected and laboratory reared whelks using microscale measurements of trace element geochemistry. Using Secondary Ion Mass Spectrometry (SIMS), annual trace element profiles were quantified at 2 μm resolution in statoliths removed from whelks collected alive from three locations spanning the length of the UK; the Shetland Isles (North), the Menai Strait, North Wales (Mid) and Jersey (South). Clear cycles in the Mg/Ca ratio were apparent with minimum values corresponding with the visible dark statolith rings and comparatively higher ratios displayed in the first year of growth. Statoliths from one and two-year-old laboratory reared whelks of known age and life history contained one and two Mg/Ca cycles respectively and demonstrated that the statolith growth ring is formed during winter (February and March). Cycles of Na/Ca were found to be anti-correlated to Mg/Ca cycles, whilst ratios of Sr/Ca were inconsistent and showed an apparent ontogenetic increase, suggesting strong physiological control. Variability in elemental data will likely limit the usefulness of these structures as environmental recorders. The results obtained using SIMS for trace element analysis of statoliths confirms the robustness of the statolith rings in estimating whelk age. μXRD at 2 μm spatial resolution demonstrated the statoliths were wholly aragonitic and thus trace element variation was not the result of possible differences in CaCO3 polymorph within the statolith. Changing XRD patterns along with SEM imaging also reveal an ‘hourglass’ microstructure within each statolith. The validation of the annual periodicity of statolith growth rings now provides a robust and novel age determination technique that will lead to improved management of B. undatum stocks.
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Sep 2017
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I18-Microfocus Spectroscopy
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Abstract: The colonization and weathering of young seafloor basaltic glass from the mid-Atlantic Ridge was examined. Microorganisms were localised to fractures in the surface of the basalt and grew on the surfaces of material in the fractures. XAS, Raman Spectroscopy and NanoSIMS analysis of the fracture-filling material shows that it contains non-crystallised iron-enriched altered glass and poorly ordered iron oxides. Organisms, which in places develop into contiguous biofilms, develop on the surface of the material. No putative biogenic alteration textures were observed in the basaltic glass at the fracture boundaries suggesting that the microbial community is restricted to the secondary alteration products. Microbial culturing shows the presence of heterotrophic bacteria including Sufitobacter and Halomonas consistent with observations of photic zone detritus associated with fracture-filling material. These data show that the interior of fresh basaltic glass is an endolithic habitat for microorganisms, but that the glass itself is not a primary source of cations or energy for the developing communities.
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Oct 2010
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I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[9166]
Abstract: Previous work has shown that Mo isotopes measurably fractionate between metal and silicate liquids, even at temperatures appropriate for core formation. However, the effect of variations in the structural environment of Mo in the silicate liquid, especially as a function of valence state, on Mo isotope fractionation remained poorly explored. We have investigated the role of valence state in metal-silicate experiments in a gas-controlled furnace at 1400 °C and at oxygen fugacities between 10−12.7 and 10–9.9, i.e. between three and 0.2 log units below the iron-wüstite buffer. Two sets of experiments were performed, both with a silicate liquid in the CaO-Al2O3-SiO2 system. One set used molybdenum metal wire loops as the metal source, the other liquid gold alloyed with 2.5 wt% Mo contained in silica glass tubes. X-ray absorption near-edge spectroscopy analysis indicates that Mo6+/ΣMo in the silicate glasses varies between 0.24 and 0.77 at oxygen fugacities of 10–12.0 and 10–9.9 in the wire loop experiments and between 0.15 and 0.48 at 10–11.4 and 10–9.9 in the experiments with Au-Mo alloys. Double-spiked analysis of Mo isotope compositions furthermore shows that Mo isotope fractionation between metal and silicate is a linear function of Mo6+/ΣMo in the silicate glasses, with a difference of 0.51‰ in 98Mo/95Mo between purely Mo4+-bearing and purely Mo6+-bearing silicate liquid. The former is octahedrally and the latter tetrahedrally coordinated. Our study implies that previous experimental work contained a mixture of Mo4+ and Mo6+ species in the silicate liquid. Our refined parameterisation for Mo isotope fractionation between metal and silicate can be described as
Δ98/95Mometal–silicate=−1.43±0.14×106Mo6+/ΣMo+8±6×104T2
Molybdenum isotope ratios therefore have potential as a proxy to constrain the oxygen fugacity during core formation on planetary bodies if the parameterisation of Mo6+/ΣMo variation with oxygen fugacity is expanded, for instance to include iron-bearing systems. On Earth literature data indicate that the upper mantle is depleted in heavy Mo isotopes relative to the bulk Earth, as represented by chondrites. As previously highlighted, this difference is most likely not caused by core formation, which either enriches the mantle in heavy Mo isotopes or causes no significant fractionation, depending on temperature and, as we determined here, Mo6+ content. We reaffirm that core formation does not account for the Mo isotope composition of the modern upper mantle, which may instead reflect the effect of fractionation during subduction as part of global plate recycling.
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Nov 2018
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B18-Core EXAFS
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Diamond Proposal Number(s):
[9621]
Open Access
Abstract: Np(V) behaviour in alkaline, calcite containing systems was studied over a range of neptunium concentrations (1.62 × 10−3 μM–1.62 μM) in two synthetic, high pH, cement leachates under a CO2 controlled atmosphere. The cement leachates were representative of conditions expected in an older (pH 10.5, Ca2+) and younger (pH 13.3, Na+, K+, Ca2+) cementitious geological disposal facility. These systems were studied using a combination of batch sorption and solubility experiments, X-ray absorption spectroscopy, and geochemical modelling to describe Np behaviour. Np(V) solubility in calcite equilibrated old and young cement leachates (OCL and YCL) was 9.7 and 0.084 μM, respectively. In the OCL system, this was consistent with a Np(V)O2OH(am) phase controlling solubility. However, this phase did not explain the very low Np(V) solubility observed in the YCL system. This inconsistency was explored further with a range of pH 13.3 solubility experiments with and variable Ca2+(aq) concentrations. These experiments showed that at pH 13.3, Np(V) solubility decreased with increasing Ca2+ concentration confirming that Ca2+ was a critical control on Np solubility in the YCL systems. X-ray absorption near-edge structure spectroscopy on the precipitate from the 42.2 μM Np(V) experiment confirmed that a Np(V) dioxygenyl species was dominant. This was supported by both geochemical and extended X-ray absorption fine structure data, which suggested a calcium containing Np(V) hydroxide phase was controlling solubility. In YCL systems, sorption of Np(V) to calcite was observed across a range of Np concentrations and solid to solution ratios. A combination of both surface complexation and/or precipitation was likely responsible for the observed Np(V) reaction with calcite in these systems. In the OCL sorption experiments, Np(V) sorption to calcite across a range of Np concentrations was dependent on the solid to solution ratio which is consistent with the formation of a mono-nuclear surface complex. All systems demonstrated slow sorption kinetics, with reaction times of weeks needed to reach apparent equilibrium. This could be explained by slow recrystallisation of the calcite surface and/or the presence of Np(V) colloidal species. Overall, these data provide valuable new insights into Np(V) and actinide(V) behaviour in alkaline conditions of relevance to the disposal of intermediate level radioactive wastes.
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Jun 2018
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I13-2-Diamond Manchester Imaging
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Diamond Proposal Number(s):
[9377]
Open Access
Abstract: We investigate the impact of initial pore structure and velocity field heterogeneity on the dynamics of fluid/solid reaction at high Péclet numbers (fast flow) and low Damköhler number (relatively slow reaction rates). The Diamond Lightsource Pink Beam was used to image dissolution of Estaillades and Portland limestones in the presence of CO2-saturated brine at reservoir conditions (10 MPa and 50 °C representing ~ 1 km aquifer depth) at two flow rates for a period of 2 h. Each sample was scanned between 51 and 94 times at 4.76-μm resolution and the dynamic changes in porosity, permeability, and reaction rate were examined using image analysis and flow modelling.
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Jun 2016
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I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[8462]
Open Access
Abstract: The effects of Sb on the precipitation of synthetic scorodite, and the resultant phases formed, were investigated. Nine synthetic precipitates with varying concentrations of Sb, together with As-only and Sb-only end members, were prepared using a scorodite synthesis method, and these were characterized using XRD, SEM, chemical digestion and μXRF mapping. XRD analysis shows that the end members are scorodite (FeAsO4.2H2O) and tripuhyite (FeSbO4), and that the intermediate members are not Sb-substituted scorodite, but instead are physical mixtures of scorodite and tripuhyite, with tripuhyite becoming more prominent with increasing amounts of Sb in the synthesis. Electron microprobe analysis on natural scorodites confirms that they contain negligible concentrations of Sb. With increasing Sb in the synthesis, the morphology of the scorodite changes from rosettes of intergrown crystals to anhedral masses of smaller crystallites. Chemical digestion of the series also became increasingly difficult with increasing Sb content. We conclude that Sb is not taken up in scorodite (perhaps due to its larger ionic radius and different co-ordination with O compared to As), that increasing amounts of Sb in the system affect scorodite morphology, and that tripuhyite is a highly stable and perhaps underestimated Sb-sink.
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Jun 2015
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B18-Core EXAFS
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Diamond Proposal Number(s):
[1986, 7527]
Open Access
Abstract: Phosphorus (P) is one of the most important limiting nutrients for the growth of oceanic phytoplankton and terrestrial ecosystems, which in turn contributes to CO2 sequestration. The solid-phase speciation of P will influence its solubility and hence its availability to such ecosystems. This study reports on the results of X-ray diffraction, electron microprobe chemical analysis and X-ray mapping, chemical extractions and X-ray absorption near-edge spectroscopy analysis carried out to determine the solid-phase speciation of P in dusts and their source sediments from the Saharan Bodélé Depression, the worlds largest single source of dust. Chemical extraction data suggest that the Bodélé dusts contain 28 to 60% (mean 49%) P sorbed to, or co-precipitated with Fe (hydr)oxides, < 10% organic P, 21-50% (mean 32%) detrital apatite P, and 10-22% (mean 15%) authigenic-biogenic apatite P. This is confirmed by the other analyses, which also suggest that the authigenic-biogenic apatite P is likely fish bone and scale, and that this might form a larger proportion of the apatite pool (33+/-22%) than given by the extraction data. This is the first-ever report of fish material in aeolian dust, and it is significant because P derived from fish bone and scale is relatively soluble and is often used as a soil fertilizer. Therefore, the fish-P will likely be the most readily form of Bodélé P consumed during soil weathering and atmospheric processing, but given time and acid dissolution, the detrital apatite, Fe-P and organic-P will also be made available. The Bodélé dust input of P to global ecosystems will only have a limited life, however, because its major source materials, diatomite in the Bodélé Depression, undergo persistent deflation and have a finite thickness.
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Sep 2014
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I08-Scanning X-ray Microscopy beamline (SXM)
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Diamond Proposal Number(s):
[12738]
Abstract: Iron (Fe) limits or co-limits primary productivity and nitrogen fixation in large regions of the world's oceans, and the supply of Fe from hydrothermal vents to the deep ocean is now known to be extensive. However, the mechanisms that control the amount of hydrothermal Fe that is stabilized in the deep ocean, and thus dictate the impact of hydrothermal Fe sources on surface ocean biogeochemistry, are unclear. To learn more, we have examined the dispersion of total dissolvable Fe (TDFe), dissolved Fe (dFe) and soluble Fe (sFe) in the buoyant and non-buoyant hydrothermal plume above the Beebe vent field, Caribbean Sea. We have also characterized plume particles using electron microscopy and synchrotron based spectromicroscopy.
We show that the majority of dFe in the Beebe hydrothermal plume was present as colloidal Fe (dFe − sFe = cFe). During ascent of the buoyant plume, a significant fraction of particulate Fe (pFe = TDFe − dFe) was lost to settling and exchange with colloids. Conversely, the opposite was observed in the non-buoyant plume, where pFe concentrations increased during non-buoyant plume dilution, cFe concentrations decreased apparently due to colloid aggregation. Elemental mapping of carbon, oxygen and iron in plume particles reveals their close association and indicates that exchanges of Fe between colloids and particles must include transformations of organic carbon and Fe oxyhydroxide minerals. Notably, sFe is largely conserved during plume dilution, and this is likely to be due to stabilization by organic ligands, in contrast to the more dynamic exchanges between pFe and cFe.
This study highlights that the size of the sFe stabilizing ligand pool, and the rate of iron-rich colloid aggregation will control the amount and physico-chemical composition of dFe supplied to the ocean interior from hydrothermal systems. Both the ligand pool, and the rate of cFe aggregation in hydrothermal plumes remain uncertain and determining these are important intermediate goals to more accurately assess the impact of hydrothermalism on the ocean's carbon cycle.
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Jan 2019
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I18-Microfocus Spectroscopy
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Abstract: The Moa Bay NiCo laterite deposits, placed in the so-called MayariBaracoa ophiolitic belt (eastern Cuba), are oxide type. Despite its geological relevance and economical impact no detailed studies exist with regards to cristallochemical characterization of Ni incorporated in (or attached to) the main Ni-containing minerals forming the lateritic profile. A sample corresponding to the ore limonite horizon has been studied by microfocus Raman, micro X-ray diffraction (μXRD), electron probe micro analysis (EPMA) and synchrotron radiation microfocus X-ray absorption spectroscopy (XAS) to gain structural and chemical information on Ni. The data obtained has revealed that Ni is preferably accumulated in quantities up to 21 wt.% in lithiophoriteasbolane intermediates. The local environment of Ni shows NiMn distances ∼3.5 Å suggesting that Ni is sorbed mostly in inner-sphere complexes sitting on Mn vacancies and at the edge of the Mn layers. However it is shown that in the presence of Al the Ni is incorporated within the lithiophoriteasbolane intermediate by developing brucite-like interlayers. The understanding of Ni sorption mechanisms within the limonite horizon suggests that combined physicochemical factors such as soil porosity and pH regime have important implications for Ni mobility across the profile.
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Jun 2010
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