Resolution Fluorescence Detected X-ray Absorption Research Articles

Tantalum in hydrothermal fluids

Understanding the behaviour of tantalum (Ta) in hydrothermal systems is pivotal for understanding its geochemical enrichment processes and economic extraction via hydrometallurgy. Yet, its behaviour in hydrothermal systems remains poorly characterised. This study investigates the coordination chemistry, speciation, and solubility of pentavalent Ta(V) in fluoride (F) − and chloride (Cl) −rich hydrothermal solutions up to 413 °C and 800 bar, utilising in-situ High Energy Resolution Fluorescence Detected X-ray Absorption Spectroscopy (HERFD-XAS). The results reveal the stability of high order fluoridotantalate complexes in fluoride-rich fluids solutions up to the highest investigated temperature, highlighting fluoride’s paramount role in enhancing Ta solubility through the formation of stable complexes in aqueous solutions. A transition from nonafluoridotantalate tetraanion (TaF94−) to heptafluoridotantalate dianion (TaF72−) complexes was observed as a function of temperature in solutions containing ≥1 m fluoride. Conversely, our findings indicate a negligible role for chloride in Ta complexation even in high Cl (∼6 m) aqueous solutions, suggesting that Ta chloride complexes do not contribute significantly to Ta transport in hydrothermal systems. Existing solubility data were reinterpreted based on an updated speciation model that integrates the in-situ XAS results. This confirms that Ta(OH)5(aq) predominates in solutions containing <0.02 m fluoride; oxyfluoridotantalate anions such as [TaF3(OH)3−] dominate in solutions containing intermediate fluoride concentrations (0.02–1 m), and the fluoridotantalate anions [TaF94− to TaF72−] occur in more concentrated fluoride solutions (>1 m) at hydrothermal conditions (∼100–400 °C). Derived thermodynamic data for these species enable better understanding and geochemical modelling of Ta transport in hydrothermal fluids, highlighting the potential of F-rich fluids to transport significant amounts of Ta.

Comparison between Co(II) and Ni(II) cycling at goethite-water interfaces: Interplay with Fe(II)-catalyzed recrystallization

Cobalt (Co) and nickel (Ni) are critical metals for modern renewable energy technologies as well as essential micronutrients for terrestrial plant health and marine primary production. Both metals are commonly surface-adsorbed onto and/or structurally-incorporated into iron (oxyhydr)oxide minerals, such as goethite (α-FeOOH), that are ubiquitously present in soils and sediments at the Earth’s surface. In sub- and anoxic environments, aqueous ferrous iron (Fe(II)) generated from dissimilatory Fe(III) reduction can induce the recrystallization of goethite and subsequently influences the speciation and mobilization of associated metals, e.g., Co(III) being reduced to Co(II). While it is generally considered that divalent Co and Ni behave similarly at goethite-water interfaces, there lacks a direct comparison of their cycling through goethite in response to Fe(II)-catalyzed recrystallization. Here, under circumneutral anoxic conditions with and without addition of aqueous Fe(II), we performed batch reaction experiments on Co(II)-substituted goethite and Co(II) and Ni(II) sorption experiments on pure goethite. The redox state and coordination environment of Co associated with goethite were determined using high energy resolution fluorescence detected X-ray absorption spectroscopy at the Co K-edge, and the distribution of solid-bound Co and Ni in goethite following sorption was revealed by sequential dissolution. Our results show that substitution of Co(II) for Fe(III) in goethite has less negative feedback on Fe(II)-catalyzed recrystallization than Ni(II), which may be related to their differing structural distortions as evidenced by EXAFS. In the absence of Fe(II), aqueous Co(II) is more favourably adsorbed onto and incorporated deeper into goethite than Ni(II), suggesting that Co(II) is more structurally compatible with goethite. The presence of Fe(II) markedly enhances the structural incorporation of both Co(II) and Ni(II) as a result of goethite recrystallization, which in turn can be inhibited by the accumulation of metals at the mineral surface. Furthermore, structurally-incorporated Co(II) is more difficult to be released back into solution (i.e. sum of aqueous and extract fractions) than Ni(II) during Fe(II)-catalyzed goethite recrystallization. Overall, our work highlights the significant differences between Co(II) and Ni(II) in their cycling at goethite-water interfaces and intricate interplay with Fe(II)-catalyzed recrystallization. This improves our understanding of their mobilization and distribution in anoxic goethite-rich systems and can provide useful insights for their enrichment and extraction from natural and artificial laterites generated from the enhanced weathering of ultramafic mine tailings.

(Invited) Evolution of Single Atom Catalysts during CO2 Electrocatalytic Reduction

The re-utilization of CO2 via its electrocatalytic reduction (CO2RR) into value-added chemicals and fuels is a promising avenue to minimize the impact of existing technologies on the climate change. This requires the development of low cost, efficient, selective and durable electrocatalysts based of their rational understanding. Moreover, it should be considered that even morphologically and chemically well-defined pre-catalysts can be susceptible to drastic modifications under operation, especially when the reaction conditions themselves change dynamically.This talk will address the transformations that Metal-N-C catalysts (M=Cu, Ni, Co, Fe, Sn, Zn) experience during static and pulsed CO2RR using operando quick X-ray absorption spectroscopy (XAS) and Raman spectroscopy. In particular, I will illustrate the astonishing behaviordisplayed by Cu-N-C catalystsduring CO2RR, featuring reversible transformations from single atom sites towards Cu nanoparticles. The switchable nature of these species that can be achieved by applying different potential pulses holds the key for the on-demand control of the distribution of the CO2RR products and thus, a wide-spread adoption of this process.Moreover, I will elucidate the nature of the ligands forming under CO2RR at singly dispersed Ni sites in Ni-N-C catalysts, which are currently drawing great attention for their high performances in the CO formation. This will be achieved by a synergistic combination of conventional XAS, high energy resolution fluorescence detected X-ray absorption near edge structure (HERFD-XANES) spectroscopy, and X-ray emission spectroscopy (XES) coupled with unsupervised and supervised machine learning methodologies and density functional theory.Overall, my lecture will feature the importance of operando characterization of electrocatalysts in order to unveil structure/composition-reactivity correlations during CO2RR.

Probing the Long- and Short-Range Structural Chemistry in the C-Type Bixbyite Oxides Th0.40Nd0.48Ce0.12O1.76, Th0.47Nd0.43Ce0.10O1.785, and Th0.45Nd0.37Ce0.18O1.815 via Synchrotron X-ray Diffraction and Absorption Spectroscopy.

The long- and short-range structural chemistry of the C-type bixbyite compounds Th0.40Nd0.48Ce0.12O1.76, Th0.47Nd0.43Ce0.10O1.785, and Th0.45Nd0.37Ce0.18O1.815 is systematically examined using synchrotron X-ray powder diffraction (S-PXRD), high-energy resolution fluorescence detection X-ray absorption near edge (HERFD-XANES), and extended X-ray absorption fine structure spectroscopy (EXAFS) measurements supported by electronic structure calculations. S-PXRD measurements revealed that the title compounds all form classical C-type bixbyite structures in space group Ia3̅ that have disordered cationic crystallographic sites with further observation of characteristic superlattice reflections corresponding to oxygen vacancies. Despite the occurrence of oxygen vacancies, HERFD-XANES measurements on the Ce L3-edge revealed that Ce incorporates as Ce4+ into the structures but involves local distortion that resembles cluster behavior and loss of nearest-neighbors. In comparison, HERFD-XANES measurements on the Nd L3-edge supported by electronic structure calculations reveal that Nd3+ adopts a local coordination environment similar to the long-range C-type structure while providing charge balancing for the formation of oxygen defects. Th L3-edge EXAFS analysis reveals shorter average Th-O distances in the title compounds in comparison to pristine ThO2 in addition to shorter Th-O and Th-Ce distances compared to Th-Th or Ce-Ce in the corresponding F-type binary oxides (ThO2 and CeO2). These distances are further found to decrease with the increased Nd content of the structures despite simultaneous observation of the overall lattice structure progressively expanding. Linear combination calculations of the M-O bond lengths are used to help explain these observations, where the role of oxygen defects, via Nd3+ incorporation, induces local bond contraction and enhanced Th cation valence, leading to the observed increased lattice expansion with progressive Nd3+ incorporation. Overall, the investigation points to the significance of dissimilar cations exhibiting variable short-range chemical behavior and how it can affect the long-range structural chemistry of complex oxides.

Operando double-edge high-resolution X-ray absorption spectroscopy study of BiVO4 photoanodes.

High energy resolution fluorescence detected X-ray absorption spectroscopy is a powerful method for probing the electronic structure of functional materials. The X-ray penetration depth and photon-in/photon-out nature of the method allow operando experiments to be performed, in particular in electrochemical cells. Here, operando high-resolution X-ray absorption measurements of a BiVO4 photoanode are reported, simultaneously probing the local electronic states of both cations. Small but significant variations of the spectral lineshapes induced by the applied potential were observed and an explanation in terms of the occupation of electronic states at or near the band edges is proposed.

Structural insights and electronic state analysis of PtNi nanowire catalysts by operando high-energy resolution fluorescence detection X-ray absorption spectroscopy

Operando conventional and high-energy resolution fluorescence detection X-ray absorption spectroscopy were used to study the oxidation states and Pt–Pt bond length changes in PtNi nanowire catalysts under oxygen reduction reaction conditions.

In-Situ Observation of Adsorption Species on Platinum Catalyst in Oxygen Reduction Reaction Using High Energy Resolution XAFS

The oxygen reduction reaction (ORR) on Pt surfaces, for examples, Pt single crystals, polycrystalline Pt electrodes, Pt nanoparticles (NPs), Pt-based alloys, and core–shell Pt nanostructures, has been discussed in the last few decades.In polymer electrolyte fuel cells (PEFCs), hydrogen peroxide and its radicals are known to be fatal attacking species not only for electrode catalysts but also for carbon materials and polymer membranes.A thorough understanding of ORR schemes has led to the development of seamless four-electron reduction cathodes, contributing to improved endurance reliability of both anion-exchange membrane (AEM) and proton-exchange membrane (PEM) fuel cells.In this study, the reaction pathway, and intermediate species such as molecular oxygen, in the ORR were investigated in alkaline and acidic environments, respectively.In this work, High Energy Resolution Fluorescence Detection X-ray Absorption Spectroscopy (HERFD-XAS) at the Pt L III-edge, which enhances resolution by partially collecting fluorescent X-ray was employed.X-ray absorption fine structure (XAFS) can detect the electronic structure of Pt, and its high energy resolution makes it possible to distinguish between different adsorption species on the surface of Pt nanoparticles.In addition, photon-in photon-out experiments using hard X-ray with high penetrating ability make it relatively easy to perform in-situ/operando measurements in potential controlled solutions.Carbon-supported Pt nanoparticles as powder catalysts were used for measurement as more realistic conditions, and the species adsorbed on the Pt nanoparticles were analyzed while controlling under the potentials both in acidic and basic electrolyte solutions with N2 or O2 gas bubbling.In N2-saturated solutions, the XANES spectra of the Pt LIII-edge reflected the presence of the adsorption species such as Pt-O (*O), Pt-OH (*OH), Pt-H (*H), as well as PtO2 oxide and Pt metallic states without any adsorption, during the ORR with the potential change.In O2-saturated solutions, one additional adsorption species of molecular oxygen was observed in both acidic and basic electrolyte solutions. It was analyzed that the intermediate species adsorbed to platinum in a side-on configuration as a superoxide anion in an alkaline environment.This intermediate species is identified as hydrogen superoxide, also known as hydroperoxyl radical, with the chemical formula HO2 by being protonated in an acidic environment.The results of research on adsorption species using HERFD-XAS have provided important knowledge for designing catalysts that enable seamless four-electron reduction.The preferred cathode catalyst design will be discussed in detail in an oral presentation at the 244th ECS Meeting. Acknowledgments: The synchrotron radiation experiments were performed at the BL11XU in the SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal Numbers of 2012B3506, 2013A3506, 2014A3506, 2014B3506, 2015B3506, 2016A3556 2019A3508, 2019B3508, 2020A3508, 2021A3508, 2021B3508, 2022A3508 and 2022B3597 at BL11XU). This work was supported by JSPS KAKENHI Grant Number JP22H02188). Figure 1

Synchrotron speciation of umbilical cord mercury and selenium after environmental exposure in Niigata

The insidious and deadly nature of mercury’s organometallic compounds is informed by two large scale poisonings due to industrial mercury pollution that occurred decades ago in Minamata and Niigata, Japan. The present study examined chemical speciation for both mercury and selenium in a historic umbilical cord sample from a child born to a mother who lived near the Agano River in Niigata. The mother had experienced mercury exposure leading to more than 50 ppm mercury measured in her hair and was symptomatic 9 years prior to the birth. We sought to determine the mercury and selenium speciation in the child’s cord using Hg Lα1 and Se Kα1 high-energy resolution fluorescence detected X-ray absorption spectroscopy, the chemical speciation of mercury was found to be predominantly organometallic and coordinated to a thiolate. The selenium was found to be primarily in an organic form and at levels higher than those of mercury, with no evidence of mercury-selenium chemical species. Our results are consistent with mercury exposure at Niigata being due to exposure to organometallic mercury species.

Nature of S-States in the Oxygen-Evolving Complex Resolved by High-Energy Resolution Fluorescence Detected X-ray Absorption Spectroscopy.

Photosystem II, the water splitting enzyme of photosynthesis, utilizes the energy of sunlight to drive the four-electron oxidation of water to dioxygen at the oxygen-evolving complex (OEC). The OEC harbors a Mn4CaO5 cluster that cycles through five oxidation states Si (i = 0-4). The S3 state is the last metastable state before the O2 evolution. Its electronic structure and nature of the S2 → S3 transition are key topics of persisting controversy. Most spectroscopic studies suggest that the S3 state consists of four Mn(IV) ions, compared to the Mn(III)Mn(IV)3 of the S2 state. However, recent crystallographic data have received conflicting interpretations, suggesting either metal- or ligand-based oxidation, the latter leading to an oxyl radical or a peroxo moiety in the S3 state. Herein, we utilize high-energy resolution fluorescence detected (HERFD) X-ray absorption spectroscopy to obtain a highly resolved description of the Mn K pre-edge region for all S-states, paying special attention to use chemically unperturbed S3 state samples. In combination with quantum chemical calculations, we achieve assignment of specific spectroscopic features to geometric and electronic structures for all S-states. These data are used to confidently discriminate between the various suggestions concerning the electronic structure and the nature of oxidation events in all observable catalytic intermediates of the OEC. Our results do not support the presence of either peroxo or oxyl in the active configuration of the S3 state. This establishes Mn-centered storage of oxidative equivalents in all observable catalytic transitions and constrains the onset of the O-O bond formation until after the final light-driven oxidation event.

Investigating Degradation Mechanisms in PtCo Alloy Catalysts: The Role of Co Content and a Pt-Rich Shell Using Operando High-Energy Resolution Fluorescence Detection X-ray Absorption Spectroscopy.

Low Pt-based alloy catalysts are regarded as an efficient strategy in achieving high activity for the oxygen reduction reaction (ORR) in proton-exchange membrane fuel cells (PEMFCs). However, the desired durability for the low Pt-based catalysts, such as the Pt1Co3 catalyst, has still been considered a great challenge for PEMFCs. In this study, we investigate sub-2.5 nm PtxCoy alloy catalysts with varying Co content and Pt1Co3@Pt core-shell (CS) nanostructure catalysts obtained through a simple displacement reaction. The Pt1Co3@Pt_H catalysts showed a high mass activity (MA) of 1.46 A/mgPt at 0.9 V and 14% MA loss after 10k accelerated degradation test (ADT) cycles, which suggested the improved stability compared with Pt1Co3 catalysts (52% MA loss). To clarify the degradation mechanism, operando high-energy resolution fluorescence detection X-ray absorption spectroscopy (XAS) was applied in addition to conventional advanced measurement techniques, including operando conventional XAS, to analyze the electronic state and structure changes during operation potentials. We found that introducing Co improves the catalysts' activity mainly from the strain effect, but an excessive amount of Co leads to increased Pt-oxidation, which accelerates the degradation of the catalysts. The Pt1Co3@Pt_H catalyst shows high tolerance to Pt-oxidation, benefiting both the stability and activity. Our findings demonstrate an in-depth understanding of the degradation mechanism and the importance of designing PtCo CS nanostructures with optimal Co content for enhanced performance in PEMFCs.

High-Resolution X-ray Absorption and Emission Spectroscopy for Detailed Analysis of New CO2 Methanation Catalysts.

A new approach for the characterization of CO2 methanation catalysts prepared by thermal decomposition of a nickel MOF by hard X-ray photon-in/photon-out spectroscopy in form of high energy resolution fluorescence detected X-ray absorption near edge structure spectroscopy (HERFD-XANES) and valence-to-core X-ray emission (VtC-XES) is presented. In contrast to conventional X-ray absorption spectroscopy, the increased resolution of both methods allows a more precise phase determination of the final catalyst, which is influenced by the conditions during MOF decomposition.

Mapping the Initial Stages of a Protective Pathway that Enhances Catalytic Turnover by a Lytic Polysaccharide Monooxygenase.

Oxygenase and peroxygenase enzymes generate intermediates at their active sites which bring about the controlled functionalization of inert C-H bonds in substrates, such as in the enzymatic conversion of methane to methanol. To be viable catalysts, however, these enzymes must also prevent oxidative damage to essential active site residues, which can occur during both coupled and uncoupled turnover. Herein, we use a combination of stopped-flow spectroscopy, targeted mutagenesis, TD-DFT calculations, high-energy resolution fluorescence detection X-ray absorption spectroscopy, and electron paramagnetic resonance spectroscopy to study two transient intermediates that together form a protective pathway built into the active sites of copper-dependent lytic polysaccharide monooxygenases (LPMOs). First, a transient high-valent species is generated at the copper histidine brace active site following treatment of the LPMO with either hydrogen peroxide or peroxyacids in the absence of substrate. This intermediate, which we propose to be a CuII-(histidyl radical), then reacts with a nearby tyrosine residue in an intersystem-crossing reaction to give a ferromagnetically coupled (S = 1) CuII-tyrosyl radical pair, thereby restoring the histidine brace active site to its resting state and allowing it to re-enter the catalytic cycle through reduction. This process gives the enzyme the capacity to minimize damage to the active site histidine residues "on the fly" to increase the total turnover number prior to enzyme deactivation, highlighting how oxidative enzymes are evolved to protect themselves from deleterious side reactions during uncoupled turnover.

Comparing neutron and helium ion irradiation damage of REBa2Cu3O coated conductor using x-ray absorption spectroscopy

Understanding the effects of high energy neutron damage on REBa2Cu3O (REBCO) coated conductor is of vital importance for the design of the magnetic confinement systems for compact nuclear fusion power plants. However, neutron irradiation campaigns can only be carried out in a few facilities, and the experiments are very slow and expensive partly because the samples become radioactive. Ion irradiation provides an easily accessible alternative route to studying the effects of radiation on high temperature superconductors, which not only increases the volume of technical data that can be obtained but also enables more complex experiments such as in situ cryogenic irradiation. The question is, does ion damage offer a good proxy for neutrons? Here we use high energy resolution fluorescence detected x-ray absorption spectroscopy to probe the effects of fast neutron irradiation on the local environment around the copper ions in the REBCO layer of coated conductor tapes. We find that the spectral changes are similar to those induced by helium ion irradiation, suggesting that both projectiles produce the same types of structural defect in the REBCO lattice, although there is some evidence of an additional type of defect present in the sample heavily damaged by He+ ion irradiation. It is also shown that the linear degradation of superconducting transition temperature (T c ) of coated conductors with the calculated number of displacements per atom occurs at the same rate for neutrons and helium ions. Together these results provide new evidence suggesting that helium ions can emulate neutron point defect damage in REBCO high temperature superconductor reasonably well, increasing confidence that helium ions could be used as a useful proxy for neutrons in future experiments.

Unraveling the Dynamic Structural Evolution of Phthalocyanine Catalysts during CO2 Electroreduction

Understanding the atomic and electronic changes of active sites promotes the whole new sight into electrochemical carbon dioxide reduction reaction (CO2RR), which provides a feasible strategy to achieve carbon neutrality. Here we employ operando high-energy resolution fluorescence-detected X-ray absorption spectroscopy (HERFD-XAS) to track the structural evolution of Ni(II) phthalocyanine (NiPc), considered as the model catalysts with uniform Ni-N4-C8 moiety, during the CO2RR. The HERFD-XAS method is in favor of elucidating the interaction of the reactant/catalyst interface from the atomic electronic structure dimension, facilitating the establishment of the catalytic mechanism and the dynamic structure changes. Based on operando measurement, surface sensitive difference spectra (Δµ) and spectroscopy simulation, the interfacial interactions between the active sites of NiPc and reactants are monitored and the Ni species gradually reduced by increasing the applied potential is discovered. HERFD-XAS method offers an advanced and powerful tool for elucidating the complex catalytic mechanism in further various systems.

Deconvoluting Cr states in Cr-doped UO2 nuclear fuels via bulk and single crystal spectroscopic studies

Cr-doped UO2 is a leading accident tolerant nuclear fuel where the complexity of Cr chemical states in the bulk material has prevented acquisition of an unequivocal understanding of the redox chemistry and mechanism for incorporation of Cr in the UO2 matrix. To resolve this, we have used electron paramagnetic resonance, high energy resolution fluorescence detection X-ray absorption near energy structure and extended X-ray absorption fine structure spectroscopic measurements to examine Cr-doped UO2 single crystal grains and bulk material. Ambient condition measurements of the single crystal grains, which have been mechanically extracted from bulk material, indicated Cr is incorporated substitutionally for U+4 in the fluorite lattice as Cr+3 with formation of additional oxygen vacancies. Bulk material measurements reveal the complexity of Cr states, where metallic Cr (Cr0) and oxide related Cr+2 and Cr+32O3 were identified and attributed to grain boundary species and precipitates, with concurrent (Cr+3xU+41-x)O2-0.5x lattice matrix incorporation. The deconvolution of chemical states via crystal vs. powder measurements enables the understanding of discrepancies in literature whilst providing valuable direction for safe continued use of Cr-doped UO2 fuels for nuclear energy generation.

Bacterial Metabolites and Particle Size Determine Cerium Oxide Nanomaterial Biotransformation.

Soil is a major receptor of manufactured nanomaterials (NMs) following unintentional releases or intentional uses. Ceria NMs have been shown to undergo biotransformation in plant and soil organisms with a partial Ce(IV) reduction into Ce(III), but the influence of environmentally widespread soil bacteria is poorly understood. We used high-energy resolution fluorescence-detected X-ray absorption spectroscopy (HERFD-XAS) with an unprecedented detection limit to assess Ce speciation in a model soil bacterium (Pseudomonas brassicacearum) exposed to CeO2 NMs of different sizes and shapes. The findings revealed that the CeO2 NM's size drives the biotransformation process. No biotransformation was observed for the 31 nm CeO2 NMs, contrary to 7 and 4 nm CeO2 NMs, with a Ce reduction of 64 ± 14% and 70 ± 15%, respectively. This major reduction appeared quickly, from the early exponential bacterial growth phase. Environmentally relevant organic acid metabolites secreted by Pseudomonas, especially in the rhizosphere, were investigated. The 2-keto-gluconic and citric acid metabolites alone were able to induce a significant reduction in 4 nm CeO2 NMs. The high biotransformation measured for <7 nm NMs would affect the fate of Ce in the soil and biota.

Metal-insulator transition in CuIr2S4 observed by Cu Kα resonant x-ray emission spectroscopy

We have investigated the Cu-derived electronic structure of iridium spinel compound ${\mathrm{CuIr}}_{2}{\mathrm{S}}_{4}$ with a metal-insulator transition (MIT) at ${T}_{\mathrm{MIT}}\ensuremath{\sim}230$ K by means of high-energy resolution fluorescence-detected x-ray absorption spectroscopy (HERFD-XAS) and Cu $K\ensuremath{\alpha}$ resonant x-ray emission spectroscopy (RXES) around the Cu $K$ absorption edge. The Cu $K$ HERFD-XAS spectrum in the metallic phase exhibits a peak in the pre-edge region at an incident photon energy of $h{\ensuremath{\nu}}_{\mathrm{in}}=8981$ eV. The peak is ascribed to the Cu $1s--3d$ quadrupole transition and is abruptly shifted to higher energy by about 0.5 eV on going from metallic to insulating phases. The energy shift of the unoccupied Cu $3d$ states is related to the insulator gap formation of ${\mathrm{CuIr}}_{2}{\mathrm{S}}_{4}$ via the hybridization with the Ir $5d$--S $3p$ bands. A hysteresis behavior is observed in the Cu $1s--3d$ peak intensity between cooling and heating processes around ${T}_{\mathrm{MIT}}$, consistent with those observed in the transport properties. The abrupt change in the unoccupied Cu $3d$ states across MIT is also clearly detected in the Cu $K\ensuremath{\alpha}$ RXES spectra.

Biological Samples Preparation for Speciation at Cryogenic Temperature using High-Resolution X-Ray Absorption Spectroscopy.

The study of elements with X-ray absorption spectroscopy (XAS) is of particular interest when studying the role of metals in biological systems. Sample preparation is a key and often complex procedure, particularly for biological samples. Although X-ray speciation techniques are widely used, no detailed protocol has been yet disseminated for users of the technique. Further, chemical state modification is of concern, and cryo-based techniques are recommended to analyze the biological samples in their near-native hydrated state to provide the maximum preservation of chemical integrity of the cells or tissues. Here, we propose a cellular preparation protocol based on cryo-preserved samples. It is demonstrated in a high energy resolution fluorescence detected X-ray absorption spectroscopy study of selenium in cancer cells and a study of iron in phytoplankton. This protocol can be used with other biological samples and other X-ray techniques that can be damaged by irradiation.

Molecular Fates of Organometallic Mercury in Human Brain.

Mercury is ubiquitous in the environment, with rising levels due to pollution and climate change being a current global concern. Many mercury compounds are notorious for their toxicity, with the potential of organometallic mercury compounds for devastating effects on the structures and functions of the central nervous system being of particular concern. Chronic exposure of human populations to low levels of methylmercury compounds occurs through consumption of fish and other seafood, although the health consequences, if any, from this exposure remain controversial. We have used high energy resolution fluorescence detected X-ray absorption spectroscopy to determine the speciation of mercury and selenium in human brain tissue. We show that the molecular fate of mercury differs dramatically between individuals who suffered acute organometallic mercury exposure (poisoning) and individuals with chronic low-level exposure from a diet rich in marine fish. For long-term low-level methylmercury exposure from fish consumption, mercury speciation in brain tissue shows methylmercury coordinated to an aliphatic thiolate, resembling the coordination environment observed in marine fish. In marked contrast, for short-term high-level exposure, we observe the presence of biologically less available mercuric selenide deposits, confirmed by X-ray fluorescence imaging, as well as mercury(II)-bis-thiolate complexes, which may be signatures of severe poisoning in humans. These differences between low-level and high-level exposures challenge the relevance of studies involving acute exposure as a proxy for low-level chronic exposure.

High-Energy Resolution Fluorescence Detected X-ray Absorption Spectroscopy for the Speciation of Fe in Aerosol Samples

In this study, we compared the high-energy resolution X-ray fluorescence X-ray absorption near-edge structure (HERFD-XANES) and normal XANES spectra of various iron (Fe) species and Fe in atmospheric aerosol samples to explore the advantages of Fe K-edge HERFD-XANES for Fe speciation in aerosols using the linear combination fitting (LCF) of XANES spectra. We also conducted Fe extraction experiments to validate the LCF-XANES. In the HERFD-XANES spectra, the pre-edge region showed specific structures absent in normal XANES. HERFD-XANES also produced more distinctive shoulders within each spectrum than normal XANES. HERFD-XANES was applied to an aerosol sample (MT21-S2) collected in Tokyo, Japan. Normal XANES identified ferrihydrite, biotite, and montmorillonite, whereas HERFD-XANES clearly detected goethite as a fourth component. Normal XANES did not distinguish between ferrihydrite and goethite in LCF because of their similar structures. A similar trend was observed in the pre-edge region, and the Fe extraction experiment result was consistent with the LCF result in the pre-edge region. Thus, LCF of HERFD-XANES, in particular for the pre-edge region, can be a powerful tool for Fe speciation in aerosols.