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Abstract: Biogas-energy is marginally profitable against the “parasitic” energy demands of processing biomass. Biogas involves microbial fermentation of feedstock hydrolyzate generated enzymatically or thermochemically. The latter also produces 5-hydroxymethyl furfural (5-HMF) which can be catalytically upgraded to 2, 5-dimethyl furan (DMF), a “drop in fuel.” An integrated process is proposed with side-stream upgrading into DMF to mitigate the “parasitic” energy demand. 5-HMF was upgraded using bacterially-supported Pd/Ru catalysts. Purpose-growth of bacteria adds additional process costs; Pd/Ru catalysts biofabricated using the sulfate-reducing bacterium (SRB) Desulfovibrio desulfuricans were compared to those generated from a waste consortium of acidophilic sulfidogens (CAS). Methyl tetrahydrofuran (MTHF) was used as the extraction-reaction solvent to compare the use of bio-metallic Pd/Ru catalysts to upgrade 5-HMF to DMF from starch and cellulose hydrolyzates. MTHF extracted up to 65% of the 5-HMF, delivering solutions, respectively, containing 8.8 and 2.2 g 5-HMF/L MTHF. Commercial 5% (wt/wt) Ru-carbon catalyst upgraded 5-HMF from pure solution but it was ineffective against the hydrolyzates. Both types of bacterial catalyst (5wt%Pd/3-5wt% Ru) achieved this, bio-Pd/Ru on the CAS delivering the highest conversion yields. The yield of 5-HMF from starch-cellulose thermal treatment to 2,5 DMF was 224 and 127 g DMF/kg extracted 5-HMF, respectively, for CAS and D. desulfuricans catalysts, which would provide additional energy of 2.1 and 1.2 kWh/kg extracted 5-HMF. The CAS comprised a mixed population with three patterns of metallic nanoparticle (NP) deposition. Types I and II showed cell surface-localization of the Pd/Ru while type III localized NPs throughout the cell surface and cytoplasm. No metallic patterning in the NPs was shown via elemental mapping using energy dispersive X-ray microanalysis but co-localization with sulfur was observed. Analysis of the cell surfaces of the bulk populations by X-ray photoelectron spectroscopy confirmed the higher S content of the CAS bacteria as compared to D. desulfuricans and also the presence of Pd-S as well as Ru-S compounds and hence a mixed deposit of PdS, Pd(0), and Ru in the form of various +3, +4, and +6 oxidation states. The results are discussed in the context of recently-reported controlled palladium sulfide ensembles for an improved hydrogenation catalyst.

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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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Abstract: Zinc incorporation into marine bivalve shells belonging to different genera (Donax, Glycymeris, Lentidium, and Chamelea) grown in mine-polluted seabed sediments (Zn up to 1% w/w) was investigated using x-ray diffraction (XRD), chemical analysis, soft x-ray microscopy combined with low-energy x-ray fluorescence (XRF) mapping, x-ray absorption spectroscopy (XAS), and transmission electron microscopy (TEM). These bivalves grew their shells, producing aragonite as the main biomineral and they were able to incorporate up to 2.0–80 mg/kg of Zn, 5.4–60 mg/kg of Fe and 0.5–4.5 mg/kg of Mn. X-ray absorption near edge structure (XANES) analysis revealed that for all the investigated genera, Zn occurred as independent Zn mineral phases, i.e., it was not incorporated or adsorbed into the aragonitic lattice. Overall, our results indicated that Zn coordination environment depends on the amount of incorporated Zn. Zn phosphate was the most abundant species in Donax and Lentidium genera, whereas, Chamelea shells, characterized by the highest Zn concentrations, showed the prevalence of Zn-cysteine species (up to 56% of total speciation). Other Zn coordination species found in the investigated samples were Zn hydrate carbonate (hydrozincite) and Zn phosphate. On the basis of the coordination environments, it was deduced that bivalves have developed different biogeochemical mechanisms to regulate Zn content and its chemical speciation and that cysteine plays an important role as an active part of detoxification mechanism. This work represents a step forward for understanding bivalve biomineralization and its significance for environmental monitoring and paleoreconstruction.

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Abstract: During 4H silicon carbide (4H-SiC) homoepitaxy and post-growth processes, the development of stress relaxation has been observed, in which interfacial dislocations (IDs) are formed at the epilayer/substrate interface, relaxing the misfit strain induced by the nitrogen doping concentration difference between the epilayer and substrate. It is widely believed that an interfacial dislocation is created by the glide of a mobile segment of a basal plane dislocation (BPD) in the substrate or epilayer towards the interface, leaving a trailing edge component right at the interface. However, direct observation of such mechanisms has not been made in SiC before. In this work, we present an in situ study of the stress relaxation process, in which a specimen cut from a commercial 4H-SiC homoepitaxial wafer undergoes the stress relaxation process during a high-temperature heat treatment while sequential synchrotron white beam X-ray topographs were recorded simultaneously. Based on the dynamic observation of this process, it can be concluded that thermal stress plays a role in the relaxation process while the increased misfit strain at elevated temperature most likely drives the formation of an interfacial dislocation.

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Abstract: Altered metabolism of biometals in the brain is a key feature of Alzheimer’s disease, and biometal interactions with amyloid-β are linked to amyloid plaque formation. Iron-rich aggregates, including evidence for the mixed-valence iron oxide magnetite, are associated with amyloid plaques. To test the hypothesis that increased chemical reduction of iron, as observed in vitro in the presence of aggregating amyloid-β, may occur at sites of amyloid plaque formation in the human brain, the nanoscale distribution and physicochemical states of biometals, particularly iron, were characterised in isolated amyloid plaque cores from human Alzheimer’s disease cases using synchrotron X-ray spectromicroscopy. In situ X-ray magnetic circular dichroism revealed the presence of magnetite: a finding supported by ptychographic observation of an iron oxide crystal with the morphology of biogenic magnetite. The exceptional sensitivity and specificity of X-ray spectromicroscopy, combining chemical and magnetic probes, allowed enhanced differentiation of the iron oxides phases present. This facilitated the discovery and speciation of ferrousrich phases and lower oxidation state phases resembling zero-valent iron as well as magnetite. Sequestered calcium was discovered in two distinct mineral forms suggesting a dynamic process of amyloid plaque calcification in vivo. The range of iron oxidation states present and the direct observation of biogenic magnetite provide unparalleled support for the hypothesis that chemical reduction of iron arises in conjunction with the formation of amyloid plaques. These new findings raise challenging questions about the relative impacts of amyloid-β aggregation, plaque formation, and disrupted metal homeostasis on the oxidative burden observed in Alzheimer’s disease.