Show Abstract ▼

Abstract: Fly ash represents a promising alternative source of rare earth elements (REE). However, information on REE containing mineral phases and their association with other fly ash components, vital for REE recovery from fly ash, is currently lacking. Herein, the mass fraction, distribution, crystallography and solid-state chemistry of REE, U and Th in Nigerian simulated fly ash samples were characterised using a range of laboratory and synchrotron x-ray based analytical techniques to underpin future extraction methodologies. Inductively coupled plasma mass spectrometry following full-acid digest of forty-five samples revealed recoverable average total REE content which ranged between 442 mgkg−1and 625 mgkg−1, comprising over 30 wt% of the critical REE Nd, Eu, Tb, Dy, Y and Er. These REE within the fly ash samples were found to be most frequently associated with discrete monazite, xenotime and Y-bearing zircon mineral particles, with the former the most detected, which could be beneficiated through gravity separation. Analysis of monazite particles isolated from the composite samples through a complimentary suite of analytical synchrotron radiation techniques revealed a core-shell pattern, with the shell rich in colocalised Ce, Nd and La, and the core enrich in both U and Th. Ce in monazite was found to exist in a mixed trivalent and tetravalent oxidation state, with the monazite structure amorphized due to the high temperature combustion process. Such results demonstrate the strong co-association and physical distribution of REE, U and Th within monazite in fly ash; knowledge of which can subsequently be used to optimise or develop a more selective, cost-effective and environmentally friendly solvent extraction methodology, by targeting the strongly colocalised and surface bound REE in fly ash monazite particles.

Open Access

Show Abstract ▼

Abstract: The neutral, distorted octahedral complex [TiCl4(SenBu2)2] (1), prepared from the reaction of TiCl4 with the neutral SenBu2 in a 1:2 ratio and characterized by IR and multinuclear (1H, 13C{1H}, 77Se{1H}) NMR spectroscopy and microanalysis, serves as an efficient single-source precursor for low-pressure chemical vapor deposition (LPCVD) of titanium diselenide, TiSe2, films onto SiO2 and TiN substrates. X-ray diffraction patterns on the deposited films are consistent with single-phase, hexagonal 1T-TiSe2 (P3̅m1), with evidence of some preferred orientation of the crystallites in thicker films. The composition and structural morphology was confirmed by scanning electron microscopy (SEM), energy dispersive X-ray, and Raman spectroscopy. SEM imaging shows hexagonal plate crystallites growing perpendicular to the substrate, but these tend to align parallel to the surface when the quantity of reagent is reduced. The resistivity of the crystalline TiSe2 films is 3.36 ± 0.05 × 10–3 Ω·cm with a carrier density of 1 × 1022 cm–3. Very highly selective film growth from the reagent was observed onto photolithographically patterned substrates, with film growth strongly preferred onto the conducting TiN surfaces of SiO2/TiN patterned substrates. TiSe2 is selectively deposited within the smallest 2 μm diameter TiN holes of the patterned TiN/SiO2 substrates. The variation in crystallite size with different diameter holes is determined by microfocus X-ray diffraction and SEM, revealing that the dimensions increase with the hole size, but that the thickness of the crystals stops increasing above ∼20 μm hole size, whereas their lengths/widths continue to increase.

Show Abstract ▼

Abstract: Two flow-through experiments were conducted to assess serpentinization of intact dunite cores. Permeability and fluid chemistry indicate significantly more reaction during the second experiment at 200°C than the first experiment at 150°C. Permeability decreased by a factor of 2.4 and 25 during the experiments at 150 and 200°C, respectively. Furthermore, hydrogen and methane concentrations exceeded 600 µmol/kg and 300 µmol/kg during the 200°C experiment, and were one and two orders of magnitude higher, respectively, than the 150°C experiment. Fe K-edge X-ray absorption near edge structure analyses of alteration minerals demonstrated Fe oxidation that occurred during the 200°C experiment. Vibrating sample magnetometer measurements on post-experimental cores indicated little to no magnetite production, suggesting that the hydrogen was largely generated by the oxidation of iron as olivine was converted to ferric iron (Fe(III)) serpentine and/or saponite. Scanning electron microscopy images suggested secondary mineralization on the post-experimental core from the 200°C experiment, portraying the formation of a secondary phase with a honeycomb-like texture as well as calcite and wollastonite. Scanning electron microscopy images also illustrated dissolution along linear bands through the interiors of olivine crystals, possibly along pathways with abundant fluid inclusions. Energy dispersive X-ray spectroscopy identified Cl uptake in serpentine, while Fourier transform-infrared spectroscopy suggested the formation of serpentine, saponite, and talc. However, no change was observed when comparing pre- and post-experimental X-ray computed tomography scans of the cores. Furthermore, (ultra) small angle neutron scattering datasets were collected to assess changes in porosity, surface area, and fractal characteristics of the samples over the ≈ 1 nm- to 10 µm-scale range. The results from the 200°C post-experimental core generally fell within the range of values for the two pristine samples and the 150°C post-experimental core that underwent negligible reaction, indicating that any change from reaction was smaller than the natural variability of the dunite. Even though there was little physical evidence of alteration, the initial stage of serpentinization at 200°C was sufficiently significant to have a dramatic effect on flow fields in the core. Furthermore, this experiment generated significant dissolved hydrogen concentrations, while simulating open system dynamics. Even though open systems prevent elevated hydrogen concentrations due to continual loss of hydrogen, we speculate that this process is responsible for stabilizing ferric Fe-rich serpentine in nature, while also oxidizing more ferrous Fe (Fe(II)) iron and cumulatively generating more hydrogen than would be possible in a closed system.

Open Access

Show Abstract ▼

Abstract: Bone remodelling is a crucial biological process needed to maintain elemental homeostasis. It is important to understand the trace elemental inventories that govern these processes as malfunctions in bone remodelling can have devastating effects on an organism. In this study, we use a combination of X-ray techniques to map, quantify, and characterise the coordination chemistry of trace elements within the highly remodelled bone tissues of extant and extinct Sirenia (manatees and dugongs). The dense bone structure and unique body chemistry of sirenians represent ideal tissues for studying both high remodelling rates as well as unique fossilisation pathways. Here, elemental maps revealed uncorrelated patterning of Ca and Zn within secondary osteons in both extant and fossil sirenians, as well as elevated Sr within the connecting canals of fossil sirenians. Concentrations of these elements are comparable between extant and fossil material indicating geochemical processing of the fossil bone has been minimal. Zn was found to be bound in the same coordination within the apatite structure in both extant and fossil bone. Accurate quantification of trace elements in extant material was only possible when the organic constituents of the bone were included. The comparable distributions, concentrations, and chemical coordination of these physiologically important trace elements indicate the chemistry of bone remodelling has been preserved for 19 million years. This study signifies the powerful potential of merging histological and chemical techniques in the understanding of physiological processes in both extant and extinct vertebrates.

Open Access

Show Abstract ▼

Abstract: Iceland is a highly active source of natural dust. Icelandic dust has the potential to directly affect the climate via dust–radiation interaction and indirectly via dust–cloud interaction, the snow/ice albedo effect and impacts on biogeochemical cycles. The impacts of Icelandic dust depend on its mineralogical and chemical composition. However, a lack of data has prevented an accurate assessment of the role of Icelandic dust in the Earth system. Here, we collected surface sediment samples from five major Icelandic dust hotspots. Dust aerosols were generated and suspended in atmospheric chambers, and PM10 and PM20 fractions were collected for further analysis. We found that the dust samples primarily consist of amorphous basaltic materials ranging from 8 wt % (from the Hagavatn hotspot) to 60 wt %–90 wt % (other hotspots). Samples had relatively high total Fe content (10 wt %–13 wt %). Sequential extraction of Fe to determine its chemical form shows that dithionite Fe (Fe oxides such as hematite and goethite) and ascorbate Fe (amorphous Fe) contribute respectively 1 %–6 % and 0.3 %–1.4 % to the total Fe in Icelandic dust. The magnetite fraction is 7 %–15 % of total Fe and 1 %–2 wt % of PM10, which is orders of magnitude higher than in mineral dust from northern Africa. Nevertheless, about 80 %–90% of the Fe is contained in pyroxene and amorphous glass. The initial Fe solubility (ammonium acetate extraction at pH 4.7) is from 0.08 % to 0.6 %, which is comparable to low-latitude dust such as that from northern Africa. The Fe solubility at low pH (i.e. pH 2) is significantly higher than typical low-latitude dust (up to 30 % at pH 2 after 72 h). Our results revealed the fundamental differences in composition and mineralogy of Icelandic dust from low-latitude dust. We attribute these differences to the low degree of chemical weathering, the basaltic composition of the parent sediments and glacial processes. Icelandic dust contributes to the atmospheric deposition of soluble Fe and can impact primary productivity in the North Atlantic Ocean. The distinct chemical and mineralogical composition, particularly the high magnetite content (1 wt %–2 wt %), indicates a potentially significant impact of Icelandic dust on the radiation balance in the subpolar and polar regions.