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Arsenic (As) is a toxic element, and elevated levels of geogenic As in drinking water pose a threat to the health of several hundred million people worldwide. In this study, we used microfluidics in combination with optical microscopy and X-ray spectroscopy to investigate zerovalent iron (ZVI) corrosion, secondary iron (Fe) phase formation, and As retention processes at the pore scale in ZVI-based water treatment filters. Two 250 μm thick microchannels filled with single ZVI and quartz grain layers were operated intermittently (12 h flow/12 h no-flow) with synthetic groundwater (pH 7.5; 570 μg/L As(III)) over 13 and 49 days. Initially, lepidocrocite (Lp) and carbonate green rust (GRC) were the dominant secondary Fe-phases and underwent cyclic transformation. During no-flow, lepidocrocite partially transformed into GRC and small fractions of magnetite, kinetically limited by Fe(II) diffusion or by decreasing corrosion rates. When flow resumed, GRC rapidly and nearly completely transformed back into lepidocrocite. Longer filter operation combined with a prolonged no-flow period accelerated magnetite formation. Phosphate adsorption onto Fe-phases allowed for downstream calcium carbonate precipitation and, consequently, accelerated anoxic ZVI corrosion. Arsenic was retained on Fe-coated quartz grains and in zones of cyclic Lp-GRC transformation. Our results suggest that intermittent filter operation leads to denser secondary Fe-solids and thereby ensures prolonged filter performance., Environmental Science & Technology, 56 (19), ISSN:0013-936X, ISSN:1520-5851

The chemical and electronic structures of 15 different sulfates are studied using S L2,3 soft X-ray emission spectroscopy (XES). Sulfur L2,3 XES spectra of sulfates are distinctively different from those of other sulfur compounds, which makes XES a powerful technique for sulfate detection. Furthermore, subtle but distinct differences between the spectra of sulfates with different cations are observed, which allow a further differentiation of the specific compound. Most prominently, the position and width of the emission from "S 3s" derived bands systematically vary for different compounds, which can be understood with electronic structure and spectral calculations based on density functional theory.

X-SPEC is a high-flux undulator beamline for electron and X-ray spectroscopy with an energy range from 70 eV to 15 keV. It offers X-ray absorption spectroscopy (XAS), extended X-ray absorption fine structure (EXAFS), photoelectron spectroscopy (PES) and hard X-ray PES (HAXPES), as well as X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS) for in vacuo, in situ and operando sample environments., X-SPEC is a high-flux spectroscopy beamline at the KIT (Karlsruhe Institute of Technology) Synchrotron for electron and X-ray spectroscopy featuring a wide photon energy range. The beamline is equipped with a permanent magnet undulator with two magnetic structures of different period lengths, a focusing variable-line-space plane-grating monochromator, a double-crystal monochromator and three Kirkpatrick–Baez mirror pairs. By selectively moving these elements in or out of the beam, X-SPEC is capable of covering an energy range from 70 eV up to 15 keV. The flux of the beamline is maximized by optimizing the magnetic design of the undulator, minimizing the number of optical elements and optimizing their parameters. The beam can be focused into two experimental stations while maintaining the same spot position throughout the entire energy range. The first experimental station is optimized for measuring solid samples under ultra-high-vacuum conditions, while the second experimental station allows in situ and operando studies under ambient conditions. Measurement techniques include X-ray absorption spectroscopy (XAS), extended X-ray absorption fine structure (EXAFS), photoelectron spectroscopy (PES) and hard X-ray PES (HAXPES), as well as X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS).

Lead(II) is a toxic pollutant often found in metal-contaminated soils and wastewaters. In acidic aqueous environments, Pb(II) is highly mobile. Chemical treatment strategies of such systems therefore often include neutralization agents and metal sorbents. Since metal solubility and the retention potential of sorbents depend on the redox state of the aqueous system, we tested the efficiency of the naturally occurring redox-sensitive ferrous iron carbonate mineral siderite to remove Pb(II) from acidic aqueous solutions in batch experiments under oxic and anoxic conditions over a total of 1008 h. Siderite dissolution led to an increase in reactive solution pH from 3 to 5.3 and 6.9, while 90 and 100% of the initial aqueous Pb(II) (0.48 × 10–3 mol kg–1) were removed from the oxic and anoxic systems, respectively. Scanning and transmission electron microscopy, combined with X-ray absorption and photoelectron spectroscopy, indicated that under oxic conditions, Pb(II) was consumed by cerussite precipitation and inner-sphere surface complexation to secondary goethite. Under anoxic conditions, Pb(II) was removed by the rapid precipitation of cerussite. This efficient siderite dissolution-coupled sequestration of Pb(II) into more stable solid phases demonstrates this potential method for contaminated water treatment regardless of the redox environment.

Thermoresistive catalytic combustion sensors based on noble metals are very stable stable and highly sensitive devices to monitor potentially explosive atmospheres. We studied and proved the high stability of rhodium oxide-based sensors under working conditions in different CH4/air mixtures (up to 3.5 vol % methane) with the help of operando X-ray-based characterization techniques, DC resistance measurements, and IR thermography using a specially designed in situ cell. Operando X-ray diffraction and X-ray absorption spectroscopy showed that the active Rh species are in the oxidized state and their chemical state is preserved during operation under realistic conditions. The resistance correlated with the surface temperature of the pellistor and is related to the combustion of CH4, confirming the catalytic nature of the observed sensing process. Only under harsh operation conditions such as an oxygen-free atmosphere or enhanced working current, a reduction in the active Rh2O3 phase was observed. Finally, the effect of poisoning causing the lowered activity on the catalytic combustion of methane was investigated. While stable rhodium sulfate might form in a sulfur-poisoned pellistor, silicon dioxide seems to additionally physically block the pores in the alumina ceramics of the pellistor poisoned by hexamethyldisiloxane.

Chromium contamination is a serious environmental issue in areas affected by leather tanning and metal plating, and green rust sulfate has been tested extensively as a potential material for in situ chemical reduction of hexavalent chromium in groundwater. Reported products and mechanisms for the reaction have varied, most likely because of green rust’s layered structure, as reduction at outer and interlayer surfaces might produce different reaction products with variable stabilities. Based on studies of Cr(III) oxidation by biogenic Mn (IV) oxides, Cr mobility in oxic soils is controlled by the solubility of the Cr(III)-bearing phase. Therefore, careful engineering of green rust properties, i.e., crystal/particle size, morphology, structure, and electron availability, is essential for its optimization as a remediation reagent. In the present study, pure green rust sulfate and green rust sulfate with Al, Mg and Zn substitutions were synthesized and reacted with identical chromate (CrO42−) solutions. The reaction products were characterized by X-ray diffraction, pair distribution function analysis, X-ray absorption spectroscopy and transmission electron microscopy and treated with synthetic δ-MnO2 to assess how easily Cr(III) in the products could be oxidized. It was found that Mg substitution had the most beneficial effect on Cr lability in the product. Less than 2.5% of the Cr(III) present in the reacted Mg-GR was reoxidized by δ-MnO2 within 14 days, and the particle structure and Cr speciation observed during X-ray scattering and absorption analyses of this product suggested that Cr(VI) was reduced in its interlayer. Reduction in the interlayer lead to the linkage of newly-formed Cr(III) to hydroxyl groups in the adjacent octahedral layers, which resulted in increased structural coherency between these layers, distinctive rim domains, sequestration of Cr(III) in insoluble Fe oxide bonding environments resistant to reoxidation and partial transformation to Cr(III)-substituted feroxyhyte. Based on the results of this study of hexavalent chromium reduction by green rust sulfate and other studies, further improvements can also be made to this remediation technique by reacting chromate with a large excess of green rust sulfate, which provides excess Fe(II) that can catalyze transformation to more crystalline iron oxides, and synthesis of the reactant under alkaline conditions, which has been shown to favor chromium reduction in the interlayer of Fe(II)-bearing phyllosilicates.

The inelastic background of hard x-ray photoelectron spectroscopy data is analyzed to paint a depth-resolved picture of the CdS/Cu(In,Ga)Se2 (CdS/CIGSe) layer structure. The CdS/CIGSe interface is the central component in next-generation chalcopyrite thin-film photovoltaic devices. By analyzing both, the (unscattered) core-level peaks and the inelastic background, and by varying the excitation photon energy from 2.1 up to 14 keV, we can derive photoemission information over a broad range of electron kinetic energies and, hence, sampling depths. With this complementary information, the CdS film thickness of a CdS/CIGSe interface can be accurately determined as a function of the CdS deposition time. For the thinner CdS films, the film thickness can be shown to vary laterally. Furthermore, small amounts of Se and process-related Rb can be detected in a thin (∼2 nm) surface layer of all investigated CdS films.

2D/3D perovskite heterostructures have emerged as a promising material composition to reduce nonradiative recombination in perovskite-based LEDs and solar cells. Such heterostructures can be created by a surface treatment with large organic cations, for example

Eudialyte-group minerals (EGM) attract global interest as potential resources for high-field-strength elements (e.g. Zr, Nb, Ta, and rare-earth elements), i.e. critical materials for modern technologies. They are particularly valued for their relative enrichment in the most critical lanthanides, i.e. Nd and heavy rare earth elements (Gd–Lu). However, rare earth element (REE) substitution mechanisms into the EGM structure are still poorly understood. Light and heavyREEmay occupy different sites and there may be ordering and/or defect clustering in the structure. This study uses X-ray absorption spectroscopy to determine the structural state ofREEin EGM from prospective eudialyte-bearing complexes. YttriumK-edge and NdL3-edge spectra were collected as proxies for heavy and lightREE, respectively, and compared to natural and syntheticREE-bearing standards. Extended X-ray absorption fine structure data yield best fits for Y in six-fold coordination with Y–O distances of 2.24–2.32 Å, and a second coordination sphere comprising Fe, Na, Ca, Si and O at radial distances of 3.6–3.8 Å. These findings are consistent with dominant Y3+substitution for Ca2+on the octahedralM1 site in all the samples studied, and exclude preferential substitution of Y3+onto the smaller octahedralZsite or the large low-symmetryN4 site.Using lattice strain theory, we constructed relative partitioning models to predict site preferences of lanthanides we have not measured directly. The models predict that allREEare favoured on the Ca-dominantM1 site and that preferential partitioning of heavy over lightREEincreases in EGM containing significant Mn in theM1-octahedral rings (oneillite subgroup). Thus, the flatREEprofiles that make EGM such attractive exploration targets are not due to preferential partitioning of light and heavyREEonto different sites. Instead, local ordering of Mn- and Ca-occupiedM1 sites may influence the capacity of EGM to accommodate heavyREE.

The potential to control the structure of amorphous materials and establish correlations with their properties would constitute an extraordinary step in formulating new pathways to design and tailor amorphous structures, which correspondingly would exhibit novel properties. Towards achieving this goal, a bottom-up approach is proposed here. In the present study, cluster-assembled Fe80Sc20 metallic glasses are used as the model systems to illustrate this potentially groundbreaking approach. Accordingly, Fe80Sc20 amorphous films are nanofabricated under well-defined conditions with precise control over cluster size and impact energy. Their local atomic structures are characterized by X-ray absorption spectroscopy around both constituent metals, i.e., Fe and Sc. The capability of controlling the local structure by controlling the deposition energy (i.e., the clusters’ impact energy) has resulted in substantial changes in the magnetic Curie temperature. In fact, the Curie temperature changes by as much as 60 K when the deposition energy is increased from 50 eV per cluster (the lowest deposition energy) to 500 eV per cluster (the highest deposition energy). This remarkable result, clearly establishing a structure–property relationship, observed for the first time in cluster-assembled metallic glasses, opens up new pathways for synthesizing novel amorphous materials with engineered structures and accompanying new properties.

Bauxitic Fe-Ni-laterite ore from the Patitira mine in Lokris area (Greece) contains assemblages of unusual As-bearing goethite-type phases in samples with significant organic matter. The material was initially characterized by bulk ICP-MS and SEM-EDS. Furthermore, the distribution and speciation of As were studied by Synchrotron Radiation (SR) spectroscopic techniques, for first time in the literature. The SR μ-XRF elemental maps and the As K-edge μ-XAFS spectra revealed that As is exclusively correlated to Fe, occurring as As5+ in the form of arsenate anions (AsO43−). However, the arsenate anions, being considered as sorbed species on goethite-type phases, exhibit -at molecular scale- a disordered structural environment, resembling locally to the configuration of such anions in natural hydrated Ni arsenates (annabergite) rather than to natural hydrated ferric arsenates (scorodite). The metalloid element in study, possibly derived from As-mineralizations or volcanic rocks, has been transferred in the environment of the laterite re-deposition, where arsenates could interact with the aforementioned Fe-phases.

Hackmanites, a variety of sodalite with the general formula Na$_{8}$Al$_{6}$Si$_{6}$O$_{24}$(Cl,S)$_{2}$, are a family of nature-based smart materials having the ability for reversible photochromism upon UV or X-ray exposure. Being nontoxic, cheap, and durable, hackmanite would be an optimal material for the visual detection of the presence of X-rays in simple portable systems. However, its X-ray-induced coloring abilities are so far known only qualitatively. In this work, a combination of experimental and computational methods is used to reveal the mechanism of X-ray-induced color changing in these materials. Finally, their use is demonstrated both in color intensity-based X-ray dosimetry and photochromic X-ray imaging.

The electronic structures of four precursors for organic���inorganic hybrid perovskites, namely, methylammonium chloride and iodide, as well as formamidinium bromide and iodide, are investigated by X-ray emission (XE) spectroscopy at the carbon and nitrogen K-edges. The XE spectra are analyzed based on density functional theory calculations. We simulate the XE spectra at the Kohn���Sham level for ground-state geometries and carry out detailed analyses of the molecular orbitals and the electronic density of states to give a thorough understanding of the spectra. Major parts of the spectra can be described by the model of the corresponding isolated organic cation, whereas high-emission energy peaks in the nitrogen K-edge XE spectra arise from electronic transitions involving hybrids of the molecular and atomic orbitals of the cations and halides, respectively. We find that the interaction of the methylammonium cation is stronger with the chlorine than with the iodine anion. Furthermore, our detailed theoretical analysis highlights the strong influence of ultrafast proton dynamics in the core-excited states, which is an intrinsic effect of the XE process. The inclusion of this effect is necessary for an accurate description of the experimental nitrogen K-edge X-ray emission spectra and gives information on the hydrogen-bonding strengths in the different precursor materials.

Among all iron oxides, hematite (α-Fe2O3), goethite (α-FeOOH), and ferrihydrite (FeOOH⋅nH2O) are the most common mineral species. While immobilization of Mo6+ by surface adsorption on ferric oxides has been studied extensively, the mechanisms of incorporation in their structure have been researched little. The objective of this study was to investigate the relation between Mo content and its structural incorporation in hematite, goethite, and six-line ferrihydrite by a combination of X-ray absorption spectroscopy (XAS), powder X-ray diffraction (pXRD), and inductively-coupled plasma optical emission spectrometry (ICP-OES). Synthesized in the presence of Mo, the hematite, goethite, and six-line ferrihydrite phases incorporated up to 8.52, 0.03, and 17.49 wt. % Mo, respectively. For hematite and goethite, pXRD analyses did not indicate the presence of separate Mo phases. Refined unit-cell parameters correlated with increasing Mo concentration in hematite and goethite. The unit-cell parameters indicated an increase in structural disorder within both phases and, therefore, supported the structural incorporation of Mo in hematite and goethite. Analysis of pXRD measurements of Mo-bearing six-line ferrihydrites revealed small amounts of coprecipitated akaganéite. X-ray absorption near edge structure (XANES) measurements at the Mo L3-edge indicated a strong distortion of the MoO6 octahedra in all three phases. Fitting of extended X-ray absorption fine structure (EXAFS) spectra of the Mo K-edge supported the presence of such distorted octahedra in a coordination environment similar to the Fe position in the investigated specimen. Incorporation of Mo6+ at the Fe3+-position for both hematite and goethite resulted in the formation of one Fe vacancy in close proximity to the newly incorporated Mo6+ and, therefore, charge balance within the hematite and goethite structures.

Physical review / B 102(19), 195414 (1-9) (2020). doi:10.1103/PhysRevB.102.195414, Self-organized silicide nanowires are considered as building blocks of future nanoelectronics and have been intensively investigated. In nanostructures, the lattice vibrational waves (phonons) deviate drastically from those in bulk crystals, which gives rise to anomalies in thermodynamic, elastic, electronic, and magnetic properties. Hence a thorough understanding of the physical properties of these materials requires a comprehensive investigation of the lattice dynamics as a function of the nanowire size. We performed a systematic lattice dynamics study of endotaxial FeSi$_2$ nanowires, forming the metastable, surface-stabilized $\alpha$ phase, which are in-plane embedded into the Si(110) surface. The average widths of the nanowires ranged from 24 to 3 nm, and their lengths ranged from several micrometers to about 100 nm. The Fe-partial phonon density of states, obtained by nuclear inelastic scattering, exhibits a broadening of the spectral features with decreasing nanowire width. The experimental data obtained along and across the nanowires unveiled a pronounced vibrational anisotropy that originates from the specific orientation of the tetragonal $\alpha$−FeSi$_2$ unit cell on the Si(110) surface. The results from first-principles calculations are fully consistent with the experimental observations and allow for a comprehensive understanding of the lattice dynamics of endotaxial silicide nanowires., Published by Inst., Woodbury, NY

Thermoresistive catalytic combustion sensors based on noble metals are very stable stable and highly sensitive devices to monitor potentially explosive atmospheres. We studied and proved the high stability of rhodium oxide-based sensors under working conditions in different CH

Chromium-bearing clays occurring at Crommyonia (Soussaki), Greece, are studied in detail. In this area Mesozoic ultramafic ophiolitic rocks were affected by a Pliocene volcanic activity continuing, nowadays, with intense post-volcanic phenomena. Particularly, the Cr-bearing clays were formed at the margins of the ophiolite into highly altered serpentinized peridotite. These clays were studied by means of x-ray diffraction (powder-XRD), microscopic (SEM-EDS), nanoscopic (TEM-EDS/STEM-HAADF), and spectroscopic (FTIR, XANES) techniques. The XRD and SEM-EDS studies confirmed smectites and halloysites, with average Cr2O3 content ca 6.2 wt% and 4.3 wt%, respectively. The mineralogy and mineral-chemistry of the above unique Cr-clays was also confirmed by TEM-EDS/STEM-HAADF measurements. Subsequent FT-IR investigation indicated the relation of chromium ions with structural hydroxyls whereas a XANES study showed the presence of only Cr(III) in both phases and the absence of Cr(VI). According to the above data, Cr(III) ions should occupy octahedral sites in the structure of the studied clays. Geochemical data indicated high enrichment in Cr, and also in As, Se, Ni, V, Sc, Tl, when compared to Upper Continental Crust (UCC), and in Cr when compared to average global peridotite and primitive mantle. The formation of Cr-bearing clays is attributed to additional alteration of serpentinized peridotite minerals (such as Cr-spinels), due to hydrothermal fluids leaching different elements from the volcanic, sedimentary, and ophiolitic rocks of the area.

This contribution investigates the natural attenuation of arsenic (As) and antimony (Sb) in highly contaminated soils at the abandoned Sb-deposit Poproc in eastern Slovakia. The studied soils were identified as technosols with pH values of 3.5–7.0 and high metal and metalloid load: antimony, arsenic, lead, and zinc up to 5757, 2484, 683, and 407 mg/kg, respectively. These toxic elements occur in the soils mainly as constituents of secondary minerals, which are products of sulphide oxidation. Bulk correlation between Fe and As is weak (p > 0.05), but inspection of micro-X-ray fluorescence maps shows that the secondary iron oxides are always associated with elevated As. Electron microprobe (EMP) and micro-X-ray diffraction analyses showed significant chemical and mineralogical heterogeneity of the secondary minerals, with wide variations of their Fe/Sb ratio and occasionally elevated Ca and Pb (> 5 wt%). The most common secondary minerals are goethite (α-FeOOH) with concentrations of Sb up to 3.14 wt% and As (1.29 wt%) and tripuhyite (FeSbO4) with increased content of As (1.14 wt%). Sb-rich secondary phases were identified as valentinite/senarmontite (Sb2O3), cervantite (Sb2O4), and a pyrochlore-group mineral stibiconite. High Sb phases with increased concentrations of Ca (up to 6.48 wt%) or Pb (20.78 wt%) were identified as stibiconite (EMP). This study shows that the secondary mineralogy in naturally attenuated contaminated soils and in Sb-containing tailings is identical. Hence, such tailings achieve their final state with respect to the Sb minerals within decades and are unlikely to change further.

Cerium is the most abundant rare earth element (REE) within the waste product of alumina production (red mud), but its speciation in this complex material is still barely understood. Previous studies showed evidence for a correlation between Ce and the main constituent of red mud, iron oxides, which led us to investigate the most abundant iron oxide in red mud, hematite, as possible carrier phase for Ce. Synthetic hematite can incorporate up to 1.70±0.01wt% Ce, which leads to a systematical increase of all unit cell parameters. Investigations by extended X-ray absorption fine structure spectroscopy suggest an incorporation of Ce4+O6 into the hematite structure by a novel atomic arrangement, fundamentally different from the close-range order around Fe3+ in hematite. Samples of red mud were taken in Lauta (Saxony), Germany and analyzed by powder X-ray diffraction, inductively coupled plasma mass and optical emission spectrometry, electron microprobe analysis and X-ray absorption near-edge structure spectroscopy. Red mud samples consist of hematite (Fe2O3) (34-58wt%), sodalite (Na8Al6Si6O24Cl2) (4-30wt%), gibbsite (Al(OH)3) (0-25wt%), goethite (FeOOH) (10-23wt%), bohmite (AlOOH) (0-11wt%), rutile (TiO2) (4-8wt%), cancrinite (Na6Ca2Al6Si6O24(CO3)2) (0-5wt%), nordstrandite (Al(OH)3) (0-5wt%) and quartz (SiO2) (0-4wt%). While the main elemental composition is Fe>Al>Na>Ti>Ca (Si not included), the average concentration of REE is 1109±6mg/kg with an average Ce concentration of 464±3mg/kg. The main carrier of Ce was located in the Fe-rich fine-grained fraction of red mud (0.10wt% Ce2O3), while other potential Ce carriers like monazite, lead oxides, secondary Ce-minerals and particles of potentially anthropogenic origin are of subordinated relevance. Cerium in red mud occurs predominantly as Ce4+, which further excludes Ce3+ minerals as relevant sources.

We studied the effect of 973 K heating in argon atmosphere on the magnetic and structural properties of a magnetite‐bearing ore, which was previously exposed to laboratory shock waves between 5 and 30 GPa. For this purpose magnetic properties were studied using temperature‐dependent magnetic susceptibility, magnetic hysteresis and low‐temperature saturation isothermal remanent magnetization. Structural properties of magnetite were analyzed using X‐ray diffraction, high‐resolution scanning electron microscopy and synchrotron‐assisted X‐ray absorption spectroscopy. The shock‐induced changes include magnetic domain size reduction due to brittle and ductile deformation features and an increase in Verwey transition temperature due to lattice distortion. After heating, the crystal lattice is relaxed and apparent crystallite size is increased suggesting a recovery of lattice defects documented by a mosaic recrystallization texture. The structural changes correlate with modifications in magnetic domain state recorded by temperature‐dependent magnetic susceptibility, hysteresis properties and low‐temperature saturation isothermal remanent magnetization. These alterations in both, magnetic and structural properties of magnetite can be used to assess impact‐related magnetic anomalies in impact structures with a high temperature overprint.

The adsorption of copper on the 2:1 clay mineral illite (0.4 to 20 μm in size) was studied using a combination of extended X-ray adsorption fine structure (EXAFS) and hybrid-Density Functional Theory (DFT) modelling. The study evaluates the effect of varying pH and copper concentration on the mechanisms of copper adsorption in solutions at background electrolyte concentration typical of natural surface continental freshwaters in granitic environments. The EXAFS spectra revealed both the elongated square pyramidal and Jahn-Teller octahedral coordinated copper clusters as feasible with the former providing better fits using spertiniite (crystalline copper hydroxide) as model compound. Additionally, ab initio calculations also predicted the square pyramidal geometry to be more stable. Copper ions have four Oeq at an average distance of 1.95(1) A and two independent Oax at average distances of 2.32(16) A and 3.06(9) A, with the latter decreasing to 2.97(2) A as copper concentration and pH are increased. This may reveal different mechanism by which copper adsorbs on illite, as a weakly bound complex at low pH likely at exchange and edge sites and changing towards more strongly bound complexes at high affinity edge sites at higher pH and copper loads. Above 1% Cu model fits suggest formation of copper oligomers with average Cu-Cu distance of 3.10(2) A. These occur at pH > 6, where the correlation between Cu-Cu and Al-Al distances in the illite edge surfaces supports the formation of surface precipitates.

Cr–Al–N coatings with a lateral composition gradient were deposited from two segmented Cr/Al targets with different segment size, thus covering the Al content range 0.22 ≲ c ≲ 0.87 and a thickness range from several hundred nanometres to several micrometres. The two-dimensional thickness and composition profiles were determined nondestructively from X-ray fluorescence maps. The results were reproduced by simulations of the flux distribution on the sample surface, combiningTRIDYNsimulations of the reactive sputter process at the target surface andSIMTRAsimulations of the subsequent transport through the gas phase. The phase formation was studied by spatially resolved X-ray diffraction and X-ray absorption spectroscopy at the Cr Kedge. Forc ≲ 0.69, a single-phase solid solution face-centered cubic (f.c.c.) (Cr,Al)N phase was found, and for 0.69 ≲ c ≲ 0.87 coexisting f.c.c. (Cr,Al)N and hexagonal close packed (h.c.p.) (Cr,Al)N phases were observed. The biaxial texture formation in nearly the entire composition range indicates a zone T growth. Four, mainly composition-dependent, texture regions were identified. All observed textures are closely related to textures reported for the h.c.p. AlN and f.c.c. CrN parent phases. Forc ≳ 0.69, a strong thickness dependence of the textures was observed. The measurements reveal an orientation relation between different f.c.c. and h.c.p. textures, indicating that local epitaxy might play a role in the structure formation.

In the present work, a combination of various techniques is utilized for the study of nano-mineralogy and -geochemistry of high-grade karst-type bauxite (Al-rich and Fe-depleted samples; Al2O3 ca. 80 wt.%) from the Parnassos-Ghiona mines located in Greece. Initial characterization using PXRD and electron microscopy in microscale and mesoscale (SEM-EDS including STEM mode), proved the presence of “Fe-Cr-Ti-containing diaspore”, anatase and minor rutile. The study by means of 57Fe Mössbauer spectroscopy, in correlation with magnetic susceptibility measurements and, complemented, with Synchrotron-based spectroscopies at the microscale (SR micro-XRF and micro-XANES/-EXAFS), indicated that Fe3+, in contrast to [6]Cr3+, is not exclusively a component of the diaspore structure. While Cr3 + substitutes Al3 + in octahedral sites of diaspore ([6]Cr3+ ↔ [6]Al3+), the electron microscopy in nanoscale (TEM-EDS & EELS) revealed that Fe exists in the form of peculiar Fe3+-bearing nanominerals (most likely maghemite-type phases) between 25 and 45 nm in size, in addition to the Fe3+ ions substituting Al3+ in the diaspore structure. Moreover, it was proven that TiO2 polymorph mineral nanoparticles, particularly rounded anatase mesocrystals and nanocrystals and individual needle-shaped rutiles, are dispersed into the diaspore matrix. Thus, diaspore in the studied bauxite concerns -in fact- a distinct Fe3+-Cr3+-AlOOH low-T authigenic phase, demonstrated for the first time in literature. On the other hand, the observed TiO2 mineral nanoparticles (formed, together with diaspore, during diagenesis) and Fe nanominerals (formed during epigenesis) were hitherto unknown not only for the allochthonous karst-type bauxite deposits of Greece, but also for the overall bauxite deposits, worldwide.

Among all highly-crystalline iron oxides present in the environment, akaganeite (β-FeO(OH, Cl)) possesses one of the most unconventional structural setups and is a known scavenger for large quantitates of molybdenum (Mo6+). The factors controlling the exact mechanism for Mo6+ incorporation into the akaganeite crystal structure are poorly understood and the ability of dissimilatory Fe(III)-reducing microorganisms to reduce pure akaganeite or Mo-carrying iron oxides is not well characterized. In the current study, we investigated the short-range order around Mo6+ in akaganeite and the fate of Mo6+ under microbially-mediated Fe(III)-reducing conditions. We found that akaganeite can incorporate up to 14.11 ± 0.22 wt% Mo, while the Fe content decreases from 59.70 ± 0.31 to 40.40 ± 0.24 wt%, which indicates a loss of 2–3 Fe atoms for each Mo incorporated. Simultaneously, the crystal structure unit cell parameters a, b and c decrease, while β increases with increasing Mo content. Surprisingly, dissolution of akaganeite by Shewanella loihica PV-4 showed higher dissolution rates of Mo-bearing akaganeite compared to Mo-free akaganeite. Moreover, these results suggest the reduction of Mo6+ is most likely microbially-induced (Fe3+ → Fe2+, Mo6+ + 2Fe2+ → Mo4+ + 2Fe3+). Furthermore, X-ray absorption spectra collected at the Mo L3-edge show a peak-splitting of the white line with a splitting gap of 2.7 eV and an increased amplitude for the first peak. This observation indicates Mo6+ is octahedrally coordinated by oxygen, assuming a strongly distorted MoO6-octhaedron. Fitting of the short-range order around Mo6+ in akaganeite supports the presence of a strongly distorted MoO6-octahedron in a coordination environment similar to the Fe position in akaganeite and the formation of Fe-vacancies close to the newly incorporated Mo6+.

Hematite (α-Fe 2 O 3 ) and goethite (α-FeOOH) can incorporate considerable amounts of tungsten (W). Although W concentrations up to several wt% in hematite and goethite have been reported in the literature, none of the proposed models for a structural incorporation has been generally accepted yet. Here, the first combination of X-ray absorption fine structure (XAFS) measurements with X-ray diffraction (XRD), Raman spectroscopy (RS), electron microprobe (EMPA) and total reflection X-ray fluorescence (TXRF) provides a general relation between W content and its structural incorporation into hematite and goethite. Botryoidal specimens of goethite and hematite, obtained from the Schwarzwald ore district, Black Forest, SW Germany, and from the Grantcharitza W deposit, Bulgaria, display W concentrations of up to 5.5 and 2.15 mol% W for goethite and hematite, respectively. In addition to these natural specimens, goethite and hematite were synthesized in the presence of W and incorporate up to 7 and 1.3 mol% W, respectively. X-ray diffraction analysis does not indicate the presence of separate W-phases, supporting the structural incorporation of W into the hematite and goethite. Refined unit-cell parameters indicate no changes with increasing W concentration in hematites but a rising structural disorder within the structure of the synthetic goethites. Raman spectroscopy, however, shows an increasing structural disorder for both synthetics, indicating an increase of Fe vacancies in both hematite and goethite. A deprotonation mechanism for the goethite structure is unlikely according to the Raman results. XAS near-edge spectra indicate a strong distortion of the WO 6 octahedra in both hematite and goethite. Extended XAFS spectra of the natural and synthetic goethites and hematites show striking similarities and suggest that W 6+ resides in all samples on the Fe 3+ position, again without developing separate W phases. Calculations of the Fe-loss related to W incorporation reach mean values of ~2.9 and ~2.8 for goethite and hematite, respectively. The formation of two Fe 3+ vacancies in close proximity to the newly incorporated W 6+ in addition to a protonation of the structures achieves charge balance within the hematite and goethite structure. Hematite and goethite record the presence of W in fluids even in the absence of visible W minerals. After W adsorption to ferrihydrite (the hematite and goethite precursor phase) and after its transformation to either hematite or goethite, only hematite with up to 0.4 wt% W is clearly able to continuously monitor a changing W signature as a record of the fluid history within its oscillatory growth zones. In contrast, goethite is probably not a good monitor of a primary W fluid history. Their combination, however, could be particularly useful, as hematite records the W concentrations in a fluid during ferihydrite precipitation, while goethite records W concentrations during later ferrihydrite maturation. Botryoidal Fe-ores have never been considered for W recovery but could play an important role to fight a potential supply risk of W as a high-technology metal.

The phase purity of a series of ZnAl

The phase purity of a series of ZnAl 4(OH) 12SO 4· nH 2O layered double hydroxides (ZnAl 4-LDH) obtained from a reaction of bayerite (Al(OH) 3) with an excess of zinc(II) sulfate under hydrothermal conditions was investigated as a function of the reaction temperature, the duration of the hydrothermal treatment, and the zinc(II) concentration. The product quality, i.e., crystalline impurities, Al impurities, and bulk Zn:Al ratio, were assessed by powder X-ray diffraction (PXRD), 27Al MAS NMR, and elemental analysis. Structural characterization of a stoichiometric ZnAl 4-LDH (120 °C, 9 days, and 2.8 M Zn(II)) showed a well-defined structure of the metal ion layer as evidenced by a single, well-defined Zn environment: i.e., no Zn substitution on the Al sites according to Zn k-edge EXAFS and PXRD. Furthermore, nearly all of the 12 different 1H atoms in the -OH groups and 4 27Al resonances could be assigned using 1H, 27Al NMR correlation experiments recorded with ultrafast MAS. The interlayer water content is variable on the basis of thermogravimetric analysis and changes in the 1H MAS NMR spectra with temperature. A composition of ZnAl 4(OH) 12(SO 4)·2.6H 2O was obtained from a combination of these techniques and confirmed that ZnAl 4-LDH is isostructural with the mineral nickelalumite (NiAl 4(OH) 12SO 4·3H 2O).

Selenium is of special interest in different research fields due to its narrow range between beneficial and toxic effects. On a global scale, Se deficiency is more widespread. Biofortification measures have successfully been applied to specifically increase Se concentrations in food crops. Still not much is known about the behaviour and long-term fate of externally supplied Se. Over many years, natural but external selenate is regularly introduced into the soil-plant system via irrigation at our study sites in Punjab which makes it also an ideal natural analogue to investigate the long term effect of biofortification. For our study, we combined total and species specific analysis of Se in soil and plant material. Selenium is clearly enriched in all investigated topsoils (0-15 cm) with concentrations of 1.5-13.0 mg kg-1 despite similar background Se concentrations (0.5 ± 0.1 mg kg-1) below 15 cm depth. Irrigation is indicated to be the primary source of excess Se. Processes like Se species transformation, uptake by plants and plant material decomposition further influence both the Se speciation and extent of Se enrichment in the soils. The Se concentration in different plants and plant parts is alarmingly high showing concentrations of up to 738 mg kg-1 in wheat. Irrigation induced selenate can be considered as an easily available short term pool of Se for plants and thus strongly controls their total Se concentration and speciation. The long-term pool of Se in the topsoil mainly consists of selenite and organic Se species. These species are readily retained but still sufficiently mobile to be taken up by plants. The formation of elemental Se can be considered as a non-available Se pool and is thus, the major cause of Se immobilization and long-term enrichment of Se in the soils. Our study clearly shows that biofortification with selenate, despite its effectiveness, bears the risk of easily increasing Se levels in plants to toxic levels and producing food with less favourable inorganic Se species if not done with care. Excess selenate is either lost due to biomethylation or immobilized within the soil which has to be considered as highly negative from both an economic and ecological point of few.

This study investigates redox transitions associated with the adsorption of Cr(VI) on commonly occurring soil components (silicates, oxides and humic acids) and their synthetic mixtures by coupling the mechanistic surface complexation modeling with spectroscopic and isotopic analyses. The mixtures of soil components were prepared to reflect the composition of the real anthroposol sample, determined by X-ray Powder Diffraction (XRD), total organic carbon (TOC) measurement and extraction methods. The effect of different initial Cr(VI) concentrations (2×10−2, 5×10−4, 10−4, 10−5, and 10−6M), background electrolyte (10−3, 10−2, and 10−1M KNO3), pH values (3–9), and sorbate/sorbent ratios (2g/L - 20g/L) were investigated. Maghemite and ferrihydrite were confirmed to be the main phases controlling Cr(VI) adsorption with increasing Cr(VI) concentration. Humic acids were primarily responsible for Cr(VI) reduction, especially at low pH values. The reduction of Cr(VI) was also proved in case of illite and kaolinite by XAS and isotopic analyses. Illite revealed higher reduction capacity in comparison with kaolinite based on XAS measurements. Chromium isotopic fractionation, resulting from Cr(VI) reduction, was the highest in the case of humic acids, followed by kaolinite and illite. However, a dissolution of intrinsic Cr originally present within kaolinite and illite might affect the final Cr isotopic composition of the supernatants due to its different Cr isotopic signature. In general, the combination of three different approaches was confirmed to offer more comprehensive information about Cr(VI) adsorption and/or reduction in soils. Detailed studies using soil mixtures can help to predict how the soil components affect Cr(VI) behavior in natural soils and possibly could improve the environmental remediation processes. Keywords: Chromate reduction, Soil component mixtures, Adsorption modeling, Cr isotopes, X-ray absorption spectroscopy

Lunar mare basalts are a product of partial melting of the lunar mantle under more reducing conditions when compared to those expected for the Earth’s upper mantle. Alongside Fe, Ti can be a major redox sensitive element in lunar magmas, and it can be enriched by up to a factor of ten in lunar basaltic glasses when compared to their terrestrial counterparts. Therefore, to better constrain the oxidation state of Ti and its coordination chemistry during lunar magmatic processes, we report new X-ray absorption near edge structure (XANES) spectroscopy measurements for a wide range of minerals (pyroxene, olivine, Fe–Ti oxides) and basaltic melt compositions involved in partial melting of the lunar mantle. Experiments were conducted in 1 bar gas-mixing furnaces at temperatures between 1100 and 1300 °C and oxygen fugacities (fO2) that ranged from air to two orders of magnitude below the Fe–FeO redox equilibrium. Run products were analysed via electron microprobe and XANES Ti K-edge. Typical run products had large (> 100 µm) crystals in equilibrium with quenched silicate glass. Ti K-edge XANES spectra show a clear shift in energy of the absorption edge features from oxidizing to reducing conditions and yield an average valence for Fe–Ti oxides (armalcolite and ilmenite) of 3.6, i.e., a 40% of the overall Ti is Ti3+ under fO2 conditions relevant to lunar magmatism (IW − 1.5 to − 1.8). Pyroxenes and olivine have average Ti valence of 3.75 (i.e., 25% of the overall Ti is trivalent), while in silicate glasses Ti is exclusively tetravalent. Pre-edge peak intensities also indicate that the coordination number of Ti varies from an average V-fold in silicate glass to VI-fold in the Fe–Ti oxides and a mixture between IV and VI-fold coordination in the pyroxenes and olivine, with up to 82% [IV]Ti4+ in the pyroxene. In addition, our results can help to better constrain the Ti3+/∑Ti of the lunar mantle phases during magmatic processes and are applied to provide first insights into the mechanisms that may control Ti mass-dependent equilibrium isotope fractionation in lunar mare basalts.

The development of iridium-free, yet efficient emitters with thermally activated delayed fluorescence (TADF) was an important step towards mass production of organic light-emitting diodes (OLEDs). Progress is currently impeded by the low solubility and low chemical stability of the materials. Herein, we present a CuI -based TADF emitter that is sufficiently chemically stable under ambient conditions and can be processed by printing techniques. The solubility is drastically enhanced (to 100 g L-1 ) in relevant printing solvents. The integrity of the complex is preserved in solution, as was demonstrated by X-ray absorption spectroscopy and other techniques. In addition, it was found that the optoelectronic properties are not affected even when partly processing under ambient conditions. As a highlight, we present a TADF-based OLED device that reached an efficiency of 11±2 % external quantum efficiency (EQE).

Tooeleite, nominally Fe63+(As3+O3)4(SO4)(OH)4·4H2O, is a relatively uncommon mineral of some acid-mine drainage systems. Yet, if it does occur, it does so in large quantities, indicating that some specific conditions favor the formation of this mineral in the system Fe-As-S-O-H. In this contribution, we report the thermodynamic properties of synthetic tooeleite. The sample was characterized by powder X-ray diffraction, scanning electron microscopy, extended X-ray absorption fine-structure spectroscopy, and Mossbauer spectroscopy. These methods confirmed that the sample is pure, devoid of amorphous impurities of iron oxides, and that the oxidation state of arsenic is 3+. Using acid-solution calorimetry, the enthalpy of formation of this mineral from the elements at the standard conditions was determined as −6196.6 ± 8.6 kJ mol−1. The entropy of tooeleite, calculated from low-temperature heat capacity data measured by relaxation calorimetry, is 899.0 ± 10.8 J mol−1 K−1. The calculated standard Gibbs free energy of formation is −5396.3 ± 9.3 kJ mol−1. The log Ksp value, calculated for the reaction Fe6(AsO3)4(SO4)(OH)4·4H2O + 16H+ = 6Fe3+ + 4H3AsO3 + SO42− + 8H2O, is −17.25 ± 1.80. Tooeleite has stability field only at very high activities of aqueous sulfate and arsenate. As such, it does not appear to be a good candidate for arsenic immobilization at polluted sites. An inspection of speciation diagrams shows that the predominance field of Fe3+ and As3+ overlap only at strongly basic conditions. The formation of tooeleite, therefore, requires strictly selective oxidation of Fe2+ to Fe3+ and, at the same time, firm conservation of the trivalent oxidation state of arsenic. Such conditions can be realized only by biological systems (microorganisms) which can selectively oxidize one redox-active element but leave the other ones untouched. Hence, tooeleite is the first example of an “obligatory” biomineral under the conditions prevailing at or near the Earth's surface because its formation under these conditions necessitates the action of microorganisms.

Phosphosiderite (FePO4⋅2H2O) is the monoclinic (P21/n) polymorph of orthorhombic strengite (Pbca), which is isostructural to scorodite (FeAsO4⋅2H2O). While the structural incorporation of As5+ into strengite can be attributed to a fractional miscibility between strengite and scorodite, the incorporation of As5+ into phosphosiderite and its dehydration product FePO4 (P 21/n) has never been investigated until now. Phosphosiderite, synthesized under hydrothermal conditions at 200 °C in the presence of arsenic, incorporates 0.044±0.001, 0.084±0.001, 0.165±0.002, 0.425±0.004 and 0.844±0.014 wt.% As at initial molar As/Fe solution ratios of 0.05, 0.1, 0.2, 0.5 and 1, respectively. With increasing As content, the P concentration in phosphosiderite decreases by 1.02 to 1.58 P atoms for each incorporated As. The unit-cell parameters a, b, c and β increase from As-free phosphosiderite with 5.326(6) A, 9.793(8) A, 8.709(3) A and 90.54(0)° to 5.329(0) A, 9.797(5) A, 8.713(7) A and 90.56(7)°, respectively, for phosphosiderite synthesized at an initial molar As/Fe solution ratio of 1. Single crystal X-ray diffraction indicates that the P position in phosphosiderite is occupied by As with about 2 %. X-ray absorption spectroscopy displays only As5+, which resides on the P position in phosphosiderite in a local coordination similar to strengite and scorodite, indicating the structural incorporation of As5+ into a strengite/scorodite-like arrangement.

The local electronic structure of purified Mo 6 S (9 − x ) I x ( x = 6, 4.5) nanowires is investigated by X-ray absorption and fluorescence spectroscopies. The nanowires are found to be metallic with the density of states altered in both the conduction and the valence band depending on the stoichiometry. First-principle theoretical calculations suggest that the changes can be mainly attributed to the effect of strong Mo S hybridization in the nanowires. The atomic chain structure of the nanowires is confirmed and the effect of increasing sulphur content is investigated.

Author(s): Issenmann, D; Eon, S; Bracht, H; Hettich, M; Dekorsy, T; Buth, G; Steininger, R; Baumbach, T; Lundsgaard Hansen, J; Nylandsted Larsen, A; Ager, JW; Haller, EE; Plech, A | Abstract: Isotopically modulated silicon and germanium multilayers are analyzed by means of femtosecond spectroscopy and pulsed X-ray scattering for determining thermal conductivity and phonon modes. Isotopic modulation decreases thermal conductivity stronger than expected from a band bending model in the coherent phonon transport regime, in particular for silicon. Femtosecond spectroscopy and X-ray scattering resolve zone-folded vibration modes, which are located at the edge of the new, smaller Brillouin zone due to the multilayer periodicity. These modes can contribute to the reduction of thermal conductivity by Umklapp processes within the zone-folded mini-bands. Color-coded increase in ultrafast X-ray scattering in vicinity to the mini-zone boundary of a germanium multilayer.

Wildfires can be responsible for significant mercury (Hg) emissions especially in contaminated areas. Here, we investigated the Hg distribution in topsoils and vegetation samples and temperature-dependent Hg mobilization from biomass-rich topsoils collected near a copper (Cu) smelter in Tsumeb (semi-arid Namibia), where Hg-rich Cu concentrates are processed. The thermo-desorption (TD) experiments conducted on representative biomass-rich topsoils (3.9–7.7 mg Hg/kg) indicated that more than 91% of the Hg was released at ∼340 °C, which corresponds to the predominant grassland-fire conditions. The mineralogical investigation indicated that the Hg comes mainly from the deposited smelter emissions because no distinct Hg-rich microparticles corresponding to the windblown dust from the nearby disposal sites of the technological materials (concentrates, slags, tailings) were found. A comparison with the TD curves of the Hg reference compounds confirmed that the Hg in the biomass-rich topsoils occurs as a mixture of Hg bound to the organic matter and metacinnabar (black HgS), which exhibits similarities with the TD pattern of smelter flue dust residue. Despite the installation of a sulfuric acid plant in the smelter in 2015 and a calculated drop in the estimated Hg emissions (from 1301 ± 457 kg/y for the period 2004–2015 to 67 ± 5 kg/y after 2015), the Hg legacy pool in the smelter surroundings can potentially be re-emitted back to the atmosphere by wildfire. Using the Hg spatial distribution data in the area (184 km2), the estimates indicate that up to 303 kg and 1.3 kg can be remobilized from the topsoils and vegetation, respectively.

The efficacy of in vitro Cr(VI) reduction by green rust sulfate suggests that this mineral is potentially useful for remediation of Cr-contaminated groundwater. Previous investigations studied this reaction but did not sufficiently characterize the intermediates and end products at chromate (CrO42&minus, ) concentrations typical of contaminant plumes, hindering identification of the dominant reaction mechanisms under these conditions. In this study, batch reactions at varying chromate concentrations and suspension densities were performed and the intermediate and final products of this reaction were analyzed using X-ray absorption spectroscopy and electron microscopy. This reaction produces particles that maintain the initial hexagonal morphology of green rust but have been topotactically transformed into a poorly crystalline Fe(III) oxyhydroxysulfate and are coated by a Cr (oxy) hydroxide layer that results from chromate reduction at the surface. Recent studies of the behavior of Cr(III) (oxy) hydroxides in soils have revealed that reductive transformation of CrO42&minus, is reversible in the presence of Mn(IV) oxides, limiting the applicability of green rust for Cr remediation in some soils. The linkage of Cr redox speciation to existing Fe and Mn biogeochemical cycles in soils implies that modification of green rust particles to produce an insoluble, Cr(III)-bearing Fe oxide product may increase the efficacy of this technique.

Al

We investigated the speciation and extractability of Tl in soil developed from mineralized carbonate rock. Total Tl concentrations in topsoil (0-20 cm) of 100-1000 mg/kg are observed in the most affected area, subsoil concentrations of up to 6000 mg/kg Tl in soil horizons containing weathered ore fragments. Using synchrotron-based microfocused X-ray fluorescence spectrometry (μ-XRF) and X-ray absorption spectroscopy (μ-XAS) at the Tl L3-edge, partly Tl(I)-substituted jarosite and avicennite (Tl2O3) were identified as Tl-bearing secondary minerals formed by the weathering of a Tl-As-Fe-sulfide mineralization hosted in the carbonate rock from which the soil developed. Further evidence was found for the sequestration of Tl(III) into Mn-oxides and the uptake of Tl(I) by illite. Quantification of the fractions of Tl(III), Tl(I)-jarosite and Tl(I)-illite in bulk samples based on XAS indicated that Tl(I) uptake by illite was the dominant retention mechanism in topsoil materials. Oxidative Tl(III)uptake into Mn-oxides was less relevant, probably because the Tl loadings of the soil exceeded the capacity of this uptake mechanism. The concentrations of Tl in 10 mM CaCl2-extracts increased with increasing soil Tl contents and decreasing soil pH, but did not exhibit drastic variations as a function of Tl speciation. With respect to Tl in contaminated soils, this study provides first direct spectroscopic evidence for Tl(I) uptake by illite and indicates the need for further studies on the sorption of Tl to clay minerals and Mn-oxides and its impact on Tl solubility in soils.

The advantage of the new generation IV iron preparations ferric carboxymaltose (FCM), ferumoxytol (FMX), and iron isomaltoside 1000 (IIM) is that they can be administered in relatively high doses in a short period of time. We investigated the physico-chemical properties of these preparations and compared them with those of the older preparations iron sucrose (IS), sodium ferric gluconate (SFG), and low molecular weight iron dextran (LMWID). Mossbauer spectroscopy, X-ray diffraction, and Fe K-edge X-ray absorption near edge structure spectroscopy indicated akaganeite structures (β-FeOOH) for the cores of FCM, IIM and IS, and a maghemite (γ-Fe2O3) structure for that of FMX. Nuclear magnetic resonance studies confirmed the structure of the carbohydrate of FMX as a reduced, carboxymethylated, low molecular weight dextran, and that of IIM as a reduced Dextran 1000. Polarography yielded significantly different fingerprints of the investigated compounds. Reductive degradation kinetics of FMX was faster than that of FCM and IIM, which is in contrast to the high stability of FMX towards acid degradation. The labile iron content, i.e. the amount of iron that is only weakly bound in the polynuclear iron core, was assessed by a qualitative test that confirmed decreasing labile iron contents in the order SFG ≈ IS > LMWID ≥ FMX ≈ IIM ≈ FCM. The presented data are a step forward in the characterization of these non-biological complex drugs, which is a prerequisite to understand their cellular uptake mechanisms and the relationship between the structure and physiological safety as well as efficacy of these complexes.

The substitution of rare metals such as iridium and platinum in light-emitting materials is a key step to enable low-cost mass-production of organic light-emitting diodes (OLEDs). Here, it is demonstrated that using a solution-processed, fully bridged dinuclear Cu(I)-complex can yield very high efficiencies. An optimized device gives a maximum external quantum efficiency of 23 ± 1% (73 ± 2 cd A(-1) ).

The concentration, distribution, and speciation of selenium in different parts of wheat and Indian mustard, grown in a seleniferous area in Punjab, were investigated using synchrotron based (XAS) and classical acid digestion and extraction methods. The analyses revealed a high Se enrichment in all investigated plant parts, with Se levels in the range of 133-931 mg/kg (dry weight, dw). Such high Se enrichment is mainly due to the considerable amounts of easily available Se detected in the soil, which are renewed on a yearly basis to some extent via irrigation. Speciation analysis in soil and plants indicated selenate and organic Se as major Se species taken up by plants, with a minor presence of selenite. The analyses also revealed that the highest Se enrichment occurs in the upper plant parts, in agreement with the high uptake rate and mobility of selenate within plants. In both wheat and mustard, highest Se enrichments were found in leaves (387 mg/kg·dw in wheat and 931 mg/kg·dw in mustard). Organic species (dimethylselenide and methylselenocysteine) were found in different parts of both plants, indicating that an active detoxification response to the high Se uptake is taking place through methylation and/or volatilization. The high proportion of selenate in wheat and mustard leaves (47% and 70%, respectively) is the result of the inability of the plant metabolism to completely transform selenate to non-toxic organic forms, if oversupplied. Methylselenocysteine, a common Se species in accumulating plants, was detected in wheat, suggesting that, in the presence of high Se concentration, this plant develops similar response mechanisms to accumulator plants.