X-ray Absorption Near-edge Structure Spectroscopy Research Articles

Stable Metal–Halide Perovskite Colloids in Protic Ionic Liquid

Stable Metal–Halide Perovskite Colloids in Protic Ionic Liquid

Elucidating the Formation and Structural Evolution of Platinum Single-Site Catalysts for the Hydrogen Evolution Reaction.

Platinum single-site catalysts (SSCs) are a promising technology for the production of hydrogen from clean energy sources. They have high activity and maximal platinum-atom utilization. However, the bonding environment of platinum during operation is poorly understood. In this work, we present a mechanistic study of platinum SSCs using operando, synchrotron-X-ray absorption spectroscopy. We synthesize an atomically dispersed platinum complex with aniline and chloride ligands onto graphene and characterize it with ex-situ electron microscopy, X-ray diffractometry, X-ray photoelectron spectroscopy, X-ray absorption near-edge structure spectroscopy (XANES), and extended X-ray absorption fine structure spectroscopy (EXAFS). Then, by operando EXAFS and XANES, we show that as a negatively biased potential is applied, the Pt–N bonds break first followed by the Pt–Cl bonds. The platinum is reduced from platinum(II) to metallic platinum(0) by the onset of the hydrogen-evolution reaction at 0 V. Furthermore, we observe an increase in Pt–Pt bonding, indicating the formation of platinum agglomerates. Together, these results indicate that while aniline is used to prepare platinum SSCs, the single-site complexes are decomposed and platinum agglomerates at operating potentials. This work is an important contribution to the understanding of the evolution of bonding environment in SSCs and provides some molecular insights into how platinum agglomeration causes the deactivation of SSCs over time.

Aerosol iron speciation and seasonal variation of iron oxidation state over the western Antarctic Peninsula

The iron (Fe) speciation and oxidation state have been considered critical factors affecting Fe solubility in the atmosphere and bioavailability in the surface ocean. In this study, elemental composition and Fe speciation in aerosol samples collected at the Palmer Station in the West Antarctic Peninsula were determined using synchrotron-based X-ray fluorescence (XRF) and X-ray Absorption Near-Edge Structure (XANES) spectroscopy. The elemental composition of coarse-mode (>1 μm) Fe-containing particles suggests that the region's crustal emission is the primary source of aerosol Fe. The Fe minerals in these aerosol particles were predominantly hematite and biotite, but minor fractions of pyrite and ilmenite were observed as well. The Fe oxidation state showed an evident seasonal variation. The Fe(II) content accounted for 71% of the total Fe in the austral summer, while this fraction dropped to 60% in the austral winter. Multivariate linear models involving meteorological parameters suggested that the wind speed, relative humidity, and solar irradiance were the factors that significantly controlled the percentage of Fe(II) in the austral summer. On the contrary, no relationship was found between these factors and the Fe(II) percentage in the austral winter, suggesting that atmospheric photoreduction and regional dust emission were limited. Moreover, the snow depth was significantly (p < 0.05) correlated with the aerosol Fe concentration, confirming the limiting effect of snow/ice cover on the regional dust emission. Given that the Antarctic Peninsula has experienced rapid warming during recent decades, the ice-free areas in the Antarctic Peninsula may act as potential dust sources.

Molecular Insights into Roles of Dissolved Organic Matter in Cr(III) Immobilization by Coprecipitation with Fe(III) Probed by STXM-Ptychography and XANES Spectroscopy.

The coprecipitation of heavy metals (HMs) with Fe(III) in the presence of dissolved organic matter (DOM) is a crucial process to control the mobility of HMs in the environment, but its underlying immobilization mechanisms are unclear. In this study, Cr(III) immobilization by coprecipitation with Fe(III) in the presence of straw-derived DOMs under different Fe/C molar ratios, pHs, and ionic strengths was investigated using scanning transmission X-ray microscopy (STXM) and ptychography and X-ray absorption near-edge structure (XANES) spectroscopy. The results showed that Cr(III) retention was enhanced in the presence of DOM, a maximum of which was achieved at an Fe/C molar ratio of 0.5. The increase of pH and ionic strength could also promote Cr(III) immobilization. Cr K-edge XANES results indicated that Fe (oxy)hydroxide fractions, instead of organics, provided the predominant binding sites for Cr(III), which was directly confirmed by high spatial resolution STXM-ptychography analysis at the sub-micron- and nanoscales. Moreover, organics could indirectly facilitate Cr immobilization by improving the aggregation and deposition of coprecipitate particles through DOM bridging or electrostatic interactions. Additionally, C K-edge XANES analysis further indicated that the carboxylic groups of DOM were complexed with Fe (oxy)hydroxides, which probably contributed to DOM bridging. This study provides a new insight into Cr(III) immobilization mechanisms in its coprecipitation with Fe(III) and DOM, which could have important implications on the management of Cr(III)-enriched soils, particularly with crop straw returning.

Bromine K-Edge X-Ray Absorption Near-Edge Structure Analysis on Hydrobromide-Salt Crystals and the Solid Dispersion of Active Pharmaceutical Ingredients.

Bromine K-edge X-ray absorption near-edge structure (XANES) spectroscopy analyses were used to evaluate the crystals of the active pharmaceutical ingredients, eletriptan hydrobromide, dextromethorphan hydrobromide and scopolamine hydrobromide salts and the solid dispersion of eletriptan hydrobromide. The crystals and the solid dispersion of the active pharmaceutical ingredient (API) salts could be discriminated based on the shape of the XANES spectra. The differences in the shape of XANES spectra was ascribable to the differences in the interatomic interactions of the bromine ions based on the crystal structures. Ratio of the eletriptan hydrobromide α-form crystal in mixed powders of α-form and monohydrate crystals could be quantified by the linear-combination fitting using their XANES spectra. These results indicated that the XANES spectroscopy are a potent method for evaluating the APIs of pharmaceutical formulations even at the higher energy region around the bromine K-edge of 13470 eV.

Benchmarking Plane Waves Quantum Mechanical Calculations of Iron(II) Tris(2,2′-bipyridine) Complex by X-ray Absorption Spectroscopy

In this work, we used, for the first time, a computational Self-Consistent Field procedure based on plane waves to describe the low and high spin conformational states of the complex [Fe(bpy)3]2+. The results obtained in the study of the minimum energy structures of this complex, a prototype of a wide class of compounds called Spin Cross Over, show how the plane wave calculations are in line with the most recent studies based on gaussian basis set functions and, above all, reproduce within acceptable errors the experimental spectra of X-ray absorption near-edge structure spectroscopy (XANES). This preliminary study shows the capabilities of plane wave methods to correctly describe the molecular structures of metal-organic complexes of this type and paves the way for future even complex computational simulations based on the energy gradient, such as Nudge Elastic Band or ab-initio Born-Oppenheimer molecular dynamics.

Soft X-ray Spectroscopy Simulations with Multiconfigurational Wave Function Theory: Spectrum Completeness, Sub-eV Accuracy, and Quantitative Reproduction of Line Shapes.

Multireference methods are known for their ability to accurately treat states of very different nature in many molecular systems, facilitating high-quality simulations of a large variety of spectroscopic techniques. Here, we couple the multiconfigurational restricted active space self-consistent field RASSCF/RASPT2 method (of the CASSCF/CASPT2 methods family) to the displaced harmonic oscillator (DHO) model, to simulate soft X-ray spectroscopy. We applied such an RASSCF/RASPT2+DHO approach at the K-edges of various second-row elements for a set of small organic molecules that have been recently investigated at other levels of theory. X-ray absorption near-edge structure (XANES) and X-ray photoelectron spectroscopy (XPS) are simulated with a sub-eV accuracy and a correct description of the spectral line shapes. The method is extremely sensitive to the observed spectral shifts on a series of differently fluorinated ethylene systems, provides spectral fingerprints to distinguish between stable conformers of the glycine molecule, and accurately captures the vibrationally resolved carbon K-edge spectrum of formaldehyde. Differences with other theoretical methods are demonstrated, which show the advantages of employing a multireference/multiconfigurational approach. A protocol to systematically increase the number of core-excited states considered while maintaining a contained computational cost is presented. Insight is eventually provided for the effects caused by removing core–electrons from a given atom in terms of bond rearrangement and influence on the resulting spectral shapes within a unitary orbital-based framework for both XPS and XANES spectra.

Interpreting the Operando X-ray Absorption Near-Edge Structure of Supported Cu and CuPd Clusters in Conditions of Oxidative Dehydrogenation of Propane: Dynamic Changes in Composition and Size

Supported subnano-cluster catalysts are highly dynamic, developing true active sites only under the pressures and temperatures of reaction conditions. Operando X-ray absorption near-edge structure (XANES) spectroscopy can track changes in the oxidation state and the local environment of cluster atoms, providing insight into the development of these active sites. While bulk metal, oxide, and hydroxide standards are often used for fitting experimental XANES spectra to obtain average oxidation states, we recently showed that computed cluster standards of relevant compositions are a more suitable basis, producing more accurate fits. Here, we theoretically interpret the operando XANES of supported Cu3Pd and Cu4 clusters during temperature-programmed reaction (TPRx) of oxidative dehydrogenation of propane. We use an expanded basis set including both globally optimized computed clusters and bulk standards. Not only can we track reversible composition/oxidation state change with temperature, but also the irreversible growth of the bulk fraction upon heating, which we attribute to cluster sintering. This has important implications for the mechanism of the catalyzed reaction and the nature of the available active sites. We propose that operando XANES provides most significant insight into the nature of supported cluster catalysts in reaction conditions when interpreted using mixed computed cluster and bulk standards.

An ab-initio study on the thermodynamics of disulfide, sulfide, and bisulfide incorporation into apatite and the development of a more comprehensive temperature, pressure, pH, and composition-dependent model for ionic substitution in minerals

AbstractThe mineral apatite, Ca10(PO4)6(F,OH,Cl)2, incorporates sulfur (S) during crystallization from S-bearing hydrothermal fluids and silicate melts. Our previous studies of natural and experimental apatite demonstrate that the oxidation state of S in apatite varies systematically as a function of oxygen fugacity (fO2). The S oxidation states –1 and –2 were quantitatively identified in apatite crystallized from reduced, S-bearing hydrothermal fluids and silicate melts by using sulfur K-edge X-ray absorption near-edge structure spectroscopy (S-XANES) where S 6+/ΣS in apatite increases from ~0 at FMQ-1 to ~1 at FMQ+2, where FMQ refers to the fayalite-magnetite-quartz fO2 buffer. In this study, we employ quantum-mechanical calculations to investigate the atomistic structure and energetics of S(-I) and S(-II) incorporated into apatite and elucidate incorporation mechanisms.One S(-I) species (disulfide, S22−) and two S(-II) species (bisulfide, HS−, and sulfide, S2−) are investigated as possible forms of reduced S species in apatite. In configuration models for the simulation, these reduced S species are positioned along the c-axis channel, originally occupied by the column anions F, Cl, and OH in the end-member apatites. In the lowest-energy configurations of S-incorporated apatite, disulfide prefers to be positioned halfway between the mirror planes at z = 1/4 and 3/4. In contrast, the energy-optimized bisulfide is located slightly away from the mirror planes by ~0.04 fractional units in the c direction. The energetic stability of these reduced S species as a function of position along the c-axis can be explained by the geometric and electrostatic constraints of the Ca and O planes that constitute the c-axis channel.The thermodynamics of incorporation of disulfide and bisulfide into apatite is evaluated by using solid-state reaction equations where the apatite host and a solid S-bearing source phase (pyrite and Na2S2(s) for disulfide; troilite and Na2S(s) for sulfide) are the reactants, and the S-incorporated apatite and an anion sink phase are the products. The Gibbs free energy (ΔG) is lower for incorporation with Na-bearing phases than with Fe-bearing phases, which is attributed to the higher energetic stability of the iron sulfide minerals as a source phase for S than the sodium sulfide phases. The thermodynamics of incorporation of reduced S is also evaluated by using reaction equations involving dissolved disulfide and sulfide species [HnS(aq)(2−n) and HnS(aq)(2−n); n = 0, 1, and 2] as a source phase. The ΔG of S-incorporation increases for fluorapatite and chlorapatite, and decreases for hydroxylapatite, as these species are protonated (i.e., as n changes from 0 to 2). These thermodynamic results demonstrate that the presence of reduced S in apatite is primarily controlled by the chemistry of magmatic and hydrothermal systems where apatite forms (e.g., an abundance of Fe; solution pH). Ultimately, our methodology developed for evaluating the thermodynamics of S incorporation in apatite as a function of temperature, pH, and composition is highly applicable to predicting the trace and volatile element incorporation in minerals in a variety of geological systems. In addition to solid-solid and solid-liquid equilibria treated here at different temperatures and pH, the methodology can be easily extended to different pressure conditions by just performing the quantum-mechanical calculations at elevated pressures.

Implementation of cryogenic tender X-ray HR-XANES spectroscopy at the ACT station of the CAT-ACT beamline at the KIT Light Source.

The ACT experimental station of the CAT-ACT wiggler beamline at the Karlsruhe Institute of Technology (KIT) Light Source is dedicated to the investigation of radionuclide materials with radioactivities up to 1000000 times the exemption limit by various speciation techniques applying monochromatic X-rays. In this article, the latest technological developments at the ACT station that enable high-resolution X-ray absorption near-edge structure (HR-XANES) spectroscopy for low radionuclide loading samples are highlighted - encompassing the investigation of actinide elements down to 1 p.p.m. concentration - combined with a cryogenic sample environment reducing beam-induced sample alterations. One important part of this development is a versatile gas tight plexiglass encasement ensuring that all beam paths in the five-analyzer-crystal Johann-type X-ray emission spectrometer run within He atmosphere. The setup enables the easy exchange between different experiments (conventional X-ray absorption fine structure, HR-XANES, high-energy or wide-angle X-ray scattering, tender to hard X-ray spectroscopy) and opens up the possibility for the investigation of environmental samples, such as specimens containing transuranium elements from contaminated land sites or samples from sorption and diffusion experiments to mimic the far field of a breached nuclear waste repository.

Long-term straw addition promotes moderately labile phosphorus formation, decreasing phosphorus downward migration and loss in greenhouse vegetable soil

Phosphorus (P) leaching is a major problem in greenhouse vegetable production with excessive P fertilizer application. Substitution of inorganic P fertilizer with organic fertilizer is considered a potential strategy to reduce leaching, but the effect of organic material addition on soil P transformation and leaching loss remains unclear. The X-ray absorption near-edge structure (XANES) spectroscopy technique can determine P speciation at the molecular level. Here, we integrated XANES and chemical methods to explore P speciation and transformation in a 10-year field experiment with four treatments: 100% chemical fertilizer (4CN), 50% chemical N and 50% manure N (2CN+2MN), 50% chemical N and 50% straw N (2CN+2SN), and 50% chemical N and 25% manure N plus 25% straw N (2CN+2MSN). Compared with the 4CN treatment, the organic substitution treatments increased the content of labile P by 13.7–54.2% in the 0–40 cm soil layers, with newberyite and brushite being the main constituents of the labile P. Organic substitution treatments decreased the stable P content; hydroxyapatite was the main species and showed an increasing trend with increasing soil depth. Straw addition (2CN+2SN and 2CN+2MSN) resulted in a higher moderately labile P content and a lower labile P content in the subsoil (60–100 cm). Moreover, straw addition significantly reduced the concentrations and amounts of total P, dissolved inorganic P (DIP), and particulate P in leachate. DIP was the main form transferred by leaching and co-migrated with dissolved organic carbon. Partial least squares path modeling revealed that straw addition decreased P leaching by decreasing labile P and increasing moderately labile P in the subsoil. Overall, straw addition is beneficial for developing sustainable P management strategies due to increasing labile P in the upper soil layer for the utilization of plants, and decreasing P migration and leaching.

Enhanced light harvesting and charge separation of carbon and oxygen co-doped carbon nitride as excellent photocatalyst for hydrogen evolution reaction

Solar-driven water splitting has been regarded as a promising strategy for renewable hydrogen production. Among many semiconductor photocatalysts, graphitic carbon nitride (g-C3N4) has received tremendous attention due to its two-dimensional structure, appropriate band gap and decent photocatalytic activity. However, it suffers severe charge recombination problems, affecting its practical performance. In this work, we demonstrated that dual heteroatoms (C and O) doped g-C3N4 can exhibit about 3 times higher catalytic performance for hydrogen evolution than that of the normal g-C3N4 with a hydrogen evolution rate reaching 2595.4 umol g−1h−1 and an apparent quantum efficiency at 420 nm of 16.6%. The heteroatoms (C and O) doped g-C3N4 photocatalyst also exhibited superior removal performance when removing Rhodamine B (RhB) . X-ray photoelectron spectroscopy (XPS), solid-state nuclear magnetic resonance (ssNMR) and X-ray absorption near-edge structure (XANES) spectroscopy reveal that the carbon and oxygen dopants replace the sp2 nitrogen and bridging N atom, respectively. DFT calculations demonstrate the codoping of carbon and oxygen- induced the generation of mid-gap state, leading to the improvement of light harvesting and charge separation.

Investigation of per- and polyfluoroalkyl substances (PFAS) in soils and sewage sludges by fluorine K-edge XANES spectroscopy and combustion ion chromatography

For the first time, fluorine K-edge X-ray absorption near-edge structure (XANES) spectroscopy was applied to detect per- and polyfluoroalkyl substances (PFAS) in various soil and sewage sludge samples. The method can be used to determine the speciation of inorganic and organic fluorides, without pre-treatment of solid samples. Therefore, XANES spectra of several inorganic fluorides as well as selected fluorinated organic compounds were recorded. While inorganic fluorides partially exhibit a variety of sharp spectral features in the XANES spectrum, almost all inspected organofluorine compounds show two distinct broad features at 688.5 and 692.0 eV. Moreover, the peak intensity ratio 688.5 eV/692.0 eV in the PFAS XANES spectrum can be inversely correlated to the chain length of the perfluoro sulfonic acid group. The detection of targeted PFAS by bulk-XANES spectroscopy in combination with linear combination fitting in soils and sewage sludges was not applicable due to the low organic fluorine to total fluorine ratio of the samples (0.01–1.84%). Nonetheless, direct analysis of pure PFAS revealed that analysis of organofluorine species might be achieved in higher concentrated samples. Furthermore, quantitative measurements by combustion ion chromatography (CIC) evaluated as sum parameters extractable organically bound fluorine (EOF) and total fluorine (TF) emphasize that besides soils, sewage sludges are a significant source of organic fluorine in agriculture (154–7209 µg/kg).

Investigation of Physical Properties of Disodium Etidronate Tetrahydrate and Application of Phosphorus K-Edge X-Ray Absorption Near-Edge Structure Spectroscopy.

Disodium etidronate is a bisphosphonate, compounds that are widely used in the treatment of bone disorders such as osteoporosis and Paget's disease. We investigated the physical properties of disodium etidronate tetrahydrate crystal, form I. We used X-ray powder diffraction (XRPD), thermal analysis, dynamic vapor sorption (DVS), X-ray single crystal structure analysis, and phosphorus K-edge X-ray absorption near-edge structure (XANES) spectroscopy for the first time. XRPD and thermal analyses demonstrated that form I was dehydrated and transformed to an amorphous form, to a crystalline form II, and finally to a form III by heating. DVS measurements revealed that the amorphous form, form II, and form III were rehydrated to form I by humidification, and form I was stable even at 0% relative humidity. These results indicate that form I is the most stable solid-state under ambient conditions and is suitable as an API for manufacture in solid formulations. The phosphorus K-edge XANES spectra differed among form I, the amorphous form, and form II, which may be ascribed to the difference in the coordinate bond schemes between the phosphate moieties and sodium ions. The results demonstrated that the phosphorus K-edge XANES spectroscopy could be applied to the identification or the discrimination of crystal forms of the APIs containing phosphate moieties. Acquired information about physical properties are crucial for manufacturing of solid formulations of disodium etidronate. XANES spectroscopy is a promising alternative method for evaluating the solid-state forms of APIs.

Occurrence of titanium dioxide nanoparticle in Taihu Lake (China) and its removal at a full-scale drinking water treatment plant.

The occurrence of titanium dioxide nanoparticle (TNP), an emerging contaminant, in Taihu Lake of China was investigated. Ti was present at a concentration of 224 ± 59 μg/L in the water samples collected from a water source in east Taihu Lake. Approximately 0.19% of the Ti-containing matter was at the nano-scale. Scanning Electron Microscope analysis verified the existence of Ti-containing components, such as TiOx and FeTiOx. Furthermore, Ti K-edge X-ray absorption near-edge structure spectroscopy was used to detect the phase composition of nano-scaled Ti-containing matter. The spectra showed the three characteristic peaks of TiO2 in the samples, suggesting the occurrence of TNP in Taihu Lake. A least-squares linear combination fitting analysis indicated that the TNP concentration in the water source was ~0.77 μg/L in water and ~0.85 μg/g-dry in sediment. The removal performance of the TNP at a full-scale conventional drinking water treatment plant indicated that ~61% of TNP was removed via coagulation/sediment, sand filtration, and disinfection/clear water reservoir. The coagulation/sediment process accounted for approximately 70% of the total removed TNP. The finished water contained ~ 0.30 μg/L TNP. This study is the first that reported the presence and transport of TNP in a full-scale drinking water treatment system.

Determination of the through-plane profile of vanadium species in hydrated Nafion studied with micro X-ray absorption near-edge structure spectroscopy - proof of concept.

Vanadium-ion transport through the polymer membrane results in a significant decrease in the capacity of vanadium redox flow batteries. It is assumed that five vanadium species are involved in this process. Micro X-ray absorption near-edge structure spectroscopy (micro-XANES) is a potent method to study chemical reactions during vanadium transport inside the membrane. In this work, protocols for micro-XANES measurements were developed to enable through-plane characterization of the vanadium species in Nafion 117 on beamline P06 of the PETRA III synchrotron radiation facility (DESY, Hamburg, Germany). A Kapton tube diffusion cell with a diameter of 3 mm was constructed. The tube diameter was chosen in order to accommodate laminar flow for cryogenic cooling while allowing easy handling of the cell components by hand. A vertical step size of 2.5 µm and a horizontal step size of 5 µm provided sufficient resolution to resolve the profile and good statistics after summing up horizontal rows of scan points. The beam was confined in the horizontal plane to account for the waviness of the membrane. The diffusion of vanadium ions during measurement was inhibited by the cryogenic cooling. Vanadium oxidation, e.g. by water radiolysis (water percentage in the hydrated membrane ∼23 wt%), was mitigated by the cryogenic cooling and by minimizing the dwell time per pixel to 5 ms. Thus, the photo-induced oxidation of V3+ in the focused beam could be limited to 10%. In diffusion experiments, Nafion inside the diffusion cell was exposed on one side to V3+ electrolyte and on the other side to VO2+. The ions were allowed to diffuse across the through-plane orientation of the membrane during one of two short defrost times (200 s and 600 s). Subsequent micro-XANES measurements showed the formation of VO2+ from V3+ and VO2+ inside the water body of Nafion. This result proves the suitability of the experimental setup as a powerful tool for the determination of the profile of vanadium species in Nafion and other ionomeric membranes.

Consistent controls on trace metal micronutrient speciation in wetland soils and stream sediments

Trace metal are essential for microbially-mediated biogeochemical processes occurring in anoxic wetland soils and stream bed sediments, but low availability of these elements may inhibit anaerobic element cycling and transformations. Solid-phase speciation is likely a critical control on trace metal availability but has seen limited study in anoxic systems having concentrations similar to geological background levels, where metal limitations may be most prevalent. We have investigated trace metal concentrations and solid-phase speciation in three freshwater subsurface aquatic systems: marsh wetland soils, riparian wetland soils, and the sediments of a streambed. These systems displayed low solid-phase trace metal concentrations, generally at or below geological background levels, which generally followed the trend Zn > Cu ≈ Ni > Co and showed no correlation with major element compositions. All soils and sediments were dominated by quartz but varied in clay mineralogy as well as the organic matter, total sulfur, and total iron contents. X-ray absorption near-edge structure (XANES) spectroscopy shows that sulfur speciation in both wetlands is dominated by organic sulfur. Elemental sulfur and iron sulfides together made up <25% of the sulfur in the wetland soils, but the distribution between inorganic and organic forms was reversed in the stream sediments. Ferrous and ferric iron in clay minerals were common species identified by both XANES and extended X-ray absorption fine structure (EXAFS) spectroscopies at all sites. Iron(III) oxides were substantial components in all but the marsh wetland soils. Quantitative analysis of copper, nickel, and zinc XANES spectra revealed similar metal speciation across all sites. Copper speciation was dominated by sulfides, adsorbed species, and minor amounts of copper bound to organic matter; no metallic copper was detected. Nickel speciation also varied little and was dominated by nickel in clay mineral octahedral sheets and nickel sulfide, with adsorbed species also present. Zinc speciation was slightly more varied, with the marsh wetland soils and stream bed sediments containing adsorbed species, zinc associated with clay mineral structures, and zinc bound to reduced sulfur groups on organic matter, whereas the riparian wetland soils lacked clay-associated zinc but contained zinc sulfide. Trace metals bound to reduced sulfur occurred at every site, with a greater sulfur-bound fraction for copper. The fractional abundance of sulfur-bound species showed no relationship with soil or sediment total sulfur content, which varied by two orders of magnitude. More broadly, the observations in this study suggest that trace metal speciation in freshwater wetland soils and stream sediments is consistently dominated by a small set of recurring components which are distinct for each metal. This may represent a general geochemical phenomenon in anoxic soils and sediments containing trace metals at background concentrations (as low as 3 µg g−1) that was not predicted from systems that are contaminated with or naturally-enriched in copper, nickel, or zinc.

In situ X-ray absorption spectroscopic studies of TiO2 photocatalytic active sites for degradation of trace CHCl3 in drinking water.

Toxic disinfection byproducts such as trihalomethanes (e.g. CHCl3) are often found after chlorination of drinking water. It has been found that photocatalytic degradation of trace CHCl3 in drinking water generally lacks an expected relationship with the crystalline phase, band-gap energy or the particle sizes of the TiO2-based photocatalysts used such as nano TiO2 on SBA-15 (Santa Barbara amorphous-15), TiO2 clusters (TiO2-SiO2) and atomic dispersed Ti [Ti-MCM-41 (Mobil Composition of Matter)]. To engineer capable TiO2 photocatalysts, a better understanding of their photoactive sites is of great importance and interest. Using in situ X-ray absorption near-edge structure (XANES) spectroscopy, the A1 (4969 eV), A2 (4971 eV) and A3 (4972 eV) sites in TiO2 can be distinguished as four-, five- and six- coordinated Ti species, respectively. Notably, the A2 Ti sites that are the main photocatalytic species of TiO2 are shown to be accountable for about 95% of the photocatalytic degradation of trace CHCl3 in drinking water (7.2 p.p.m. CHCl3 gTiO2-1 h-1). This work reveals that the A2 Ti species of a TiO2-based photocatalyst are mainly responsible for the photocatalytic reactivity, especially in photocatalytic degradation of CHCl3 in drinking water.

“A spectroscopic picture paints 1000 words” mapping iron speciation in brain tissue with “full spectrum per pixel” X-ray absorption near-edge structure spectroscopy

Coordination chemistry enables a variety of vital functions in biological systems; however, characterising the chemical form of metal ions in cells and tissue is notoriously difficult. One technique that is gaining substantial momentum in this research area is X-ray absorption near-edge structure (XANES) spectroscopy. The XANES spectrum can be a rich source of information with respect to the coordination environment of metal ions. Further, XANES spectroscopy is compatible with microscopy mapping protocols as the spectra are recorded across a relatively narrow range of data points (typically 50–100). Although the potential of XANES spectroscopy to study metal ion coordination chemistry has long been known, data collection speed has only relatively recently reached the state in which maps can be collected with a full spectrum per pixel. The realisation of this capability now places XANES spectroscopic mapping among a suite of other spectroscopic imaging techniques, such as Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy, which are available to characterise biochemical composition, in situ within cells and tissue. Herein, we report a proof-of-concept application of XANES spectroscopic mapping to begin exploration of Fe speciation in brain tissue, which demonstrates the potential of this method for the biomedical sciences, and identifies important areas for consideration with respect to future protocol developments.

Characterization of unique aerosol pollution episodes in urban areas using TXRF and TXRF-XANES

Identifying sources of unique, short-time aerosol pollution episodes in urban areas is a difficult task since they could last only for a couple of hours. With the combination of size-fractioned sampling with May-type cascade impactor and total-reflection X-ray fluorescence (TXRF) in addition to X-ray absorption near-edge structure spectroscopy various sources could be identified in samples collected in Budapest (Hungary) and Cassino (Italy). Using short-time (1–4 h), size-fractionated (70 nm up to 10 μm into 7 stages) sampling method, TXRF is capable of detecting transition metals in the order of 0.1 ng/m3. The present study discusses pollution episodes with Cu and Br concentrations in the range of 1–40 ng/m3. The contribution of both exhaust and non-exhaust type traffic-related emission sources were found to be dominant in the Cu species. Wear products of brake system were identified in coarse particles in addition to resuspension of roadside dust. The ratio of organic/inorganic Br could be determined for a pollution episode with elevated Br concentration.