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Abstract: The use of solar energy to activate chemical pathways in a sustainable manner drives the development in photocatalysis. While catalyst optimisation is a major theme in this pursuit, the development of novel photocatalytic reactors to enhance productivity is also imperative. In this work we combine, for the first time, microstructured optical fibre technology with photocatalysis, creating a photocatalytic microreactor coated with titania decorated with palladium nanoparticles. By doing so, we can create a system capable of effectively combining photons, liquids and gases within a monolithic, highly confined, transparent silica geometry. We utilise a range of characterisation techniques to selectively focus on the photocatalyst that resides exclusively within the internal capillaries of this system. In doing so we validate our design approach, and demonstrate the ability to simultaneously control both nanoparticle size and metal content. Further, we justify our unique design, showing its activity in photocatalytic hydrogen generation from water. In doing so highlighting the importance in developing light propagation properties from optical fibres, and the significant potential of this technology in the expansive photocatalysis landscape.

Open Access

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Abstract: The use of fluorescence full spectral micro-X-ray absorption near-edge structure (µXANES) mapping is becoming more widespread in the hard energy regime. This experimental method using the Ca K-edge combined with micro-X-ray diffraction (µXRD) mapping of the same sample has been enabled on beamline I18 at Diamond Light Source. This combined approach has been used to probe both long- and short-range order in calcium carbonate granules produced by the earthworm Lumbricus terrestris. In granules produced by earthworms cultured in a control artificial soil, calcite and vaterite are observed in the granules. However, granules produced by earthworms cultivated in the same artificial soil amended with 500 p.p.m. Mg also contain an aragonite. The two techniques, µXRD and µXANES, probe different sample volumes but there is good agreement in the phase maps produced.

Open Access

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Abstract: We have determined the chemical speciation of dissolved sulfur and the sulfur concentration at fixed oxygen and sulfur fugacities for a wide range of silicate melt compositions (from Fe-rich basalt to dacite). Each melt was equilibrated at 1300 °C and 1-atmosphere pressure at oxygen fugacities (fO2) between −1.67 and +1.6 log units relative to the Fayalite–Magnetite–Quartz (FMQ) buffer and absolute sulfur fugacities between −5.1 and −1.2 log units. The fO2 and fS2 of the experiments were controlled by using gas mixtures of CO–CO2–SO2. The speciation of sulfur in the quenched glasses was determined using both X-ray Absorption Near-Edge Spectroscopy (XANES), and from the dependence of equilibrium sulfur concentration on the fS2/fO2 ratio measured by secondary-ion mass spectrometry (SIMS) and electron microprobe. The speciation of dissolved sulfur in each melt undergoes an abrupt transformation from S2− to S6+ with increasing fO2, and this transition is shifted ∼0.5 log units higher in fO2 as melt FeO concentration increases from ∼5 wt% to ∼18 wt%. Since sulfide concentrations at constant fO2 and fS2 are consistently greater for more FeO-rich melts, the compositional effect on speciation may be explained by the well-known sensitivity of the sulfide capacity ( CS2− ) of the melt to FeO concentration. S6+/S2− ratios for the glasses exhibit a linear relationship with Fe3+/Fe2+, indicating that the redox couples for iron and sulfur can be directly related to one another. We used thermodynamic data to model the interrelationship between Fe and S oxidation states in terms of the equilibrium FeS+8FeO1.5=8FeO+FeSO4 Fitting the data to our experiments at 1300 °C we obtained the following expression for the temperature-dependence of speciation: log⁡(S6+S2−)=8log⁡(Fe3+Fe2+)+8.7436×106T2−27703T+20.273 This equation fits the data for all our compositions and is also consistent with earlier results at 1050 °C and 950 °C. We used the interdependence of S and Fe oxidation states to infer electron transfer between Fe2+ and S6+ during quenching of glasses from Mauna Kea, Hawaii. The effect is sufficient to cause significant overestimation of equilibrium Fe3+/ΣFe in natural glasses and corresponding overestimate of fO2 by about 0.8 log units. Glasses equilibrated under the most oxidizing conditions (containing S6+ only) have equilibrium S concentrations that are negatively correlated with their mole fractions of tetrahedral (Si + Ti) cations.

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Abstract: We present a newly developed capsule design that resolves some common problems associated with the moni- toring and control of oxygen fugacity (fO2) in high-pressure piston cylinder experiments. The new fO2 control assem- bly consists of an AuPd outer capsule enclosing two inner capsules: one of AuPd capsule containing the experimental charge (including some water), and the other of Pt containing a solid oxygen buffer plus water. The inner capsules are sepa- rated by crushable alumina. The outer capsule is surrounded by a Pyrex sleeve to simultaneously minimise hydrogen loss from the cell and carbon infiltration from the graphite fur- nace. Controlled fO2 experiments using this cell design were carried out at 1.0 GPa and 1,000 °C. We used NiPd, CoPd and (Ni, Mg)O fO2 sensors, whose pressure sensitivity is well cal- ibrated, to monitor the redox states achieved in experiments buffered by Re–ReO2, Ni–NiO and Co–CoO, respectively. Results for the fO2 sensors are in good agreement with the intended fO2 established by the buffer, demonstrating excel- lent control for durations of 24–48 h, with uncertainties less than ± 0.3 log bar units of fO2.

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Abstract: Arsenic (As) is one of four metals/metalloids in tobacco being considered for regulation. In vitro toxicological response to As varies substantially, determined primarily by valence and compound speciation, and inorganic arsenite (As(III)) compounds are the most toxic to humans. This study uses X-ray absorption near edge structure (XANES) to determine valence states of As from the tobacco plant to the crucial combustion stage that creates respirable smoke. Samples studied include cultivated plants (some burdened with additional As), reference standards, and commercial products, along with smoke condensate and ash from these samples. The relative contributions of As(III) and As(V) to the XANES spectra are analyzed, and a consistent pattern of redox changes emerges. Tobacco leaf and manufactured products tend to be dominated by As(V) whereas combustion produces respirable smoke invariably in As(III) form and ash invariably as As(V). The valence state of precursor tobacco is not a controlling factor because all the As mobilized in smoke is reduced during combustion. This study concludes that tobacco combustion exposes smokers to potentially the most toxic forms of arsenic, and this exposure is magnified in regions where arsenic is present in tobacco crops at relatively high concentrations.