Local and regional museums often rely on cost-effective handheld equipment to undertake non-destructive pigment assessment. When preserved colourants are only microscopic, however, these methods’ limits may be encountered. This becomes acute with fragile objects, as is often the case for organic materials. Using a reconstructed decorated ostrich eggshell vessel, an elite grave good in 7th–6th C BCE Etruria, this study compares the efficacy of portable X-ray fluorescence spectrometry; handheld Fourier-transform infrared spectroscopy; Raman spectroscopy; visible-induced luminescence imaging; multispectral multi-light reflectance analysis; synchrotron radiation X-ray fluorescence; and X-ray absorption near edge structure analysis to distinguish microscopic pigment traces. The portable device results were inconclusive, but Egyptian blue and malachite were positively identified via synchrotron analyses. This outcome supports museums to further develop protocols regarding minimal pigment residue identifications on fragile objects, including assessing risk with external analysis, and informs our understanding of pigments used on organic objects during this period.

Dental caries is the most prevalent oral disease that causes structural and compositional changes of the dental hard tissues due to a chronic demineralisation (combined with possible phases of remineralisation) process. Though considerable efforts have been directed at studying natural and artificial carious lesions, most characterisations remain either constrained to 2D analyses or have been unable to achieve fine resolution in 3D due to limited field of view. To overcome this challenge, the present study combined X-ray diffraction (XRD) and scanning transmission X-ray microscopy (STXM) tomography techniques to analyse the mineral density, scattering intensity, and crystallite size in normal, carious, 30 % artificially demineralised, and 50 % artificially demineralised dentine. Combined XRD and STXM tomography was performed on the I18 beamline at Diamond Light Source, using a 15 keV monochromatic beam with 2 × 2 µm spotsize and scanning with translation steps of 2 µm, providing a reconstructed voxel size of 2 × 2 × 2 µm. Natural carious dentine showed a reduction in hydroxyapatite (HAp) crystallite size due to chronic demineralisation. This was unlike artificially demineralised dentine samples that underwent short, continuous demineralisation, which created a zone of fully demineralised dentine, near the sample surface, and a zone of partially demineralised dentine that had a reduced mineral density but an increased average crystallite size.

Some of the largest Mexican uranium (U) deposits are located in Chihuahua. The most important is in Sierra Peña Blanca, northwest of the capital, which was explored and partially exploited in the 1980s. After the closure of activities, the mining projects were left exposed to weathering. To characterize the spread of U minerals towards the neighboring Laguna del Cuervo, sediment samples were collected in the main streams of the drainage pattern of the largest deposits. The U mineral fragments from the fine sand portion were extracted using fluorescence light at 365 nm. The morphology and elemental composition of these particles were analyzed by focused ion beam microscopy (FIB) and scanning transmission electron microscopy (STEM). The particle density in samples close to the U sources was quantified using gamma spectrometry. The highest density was 2500 part./g, and the lowest was 124 part./g. X-ray absorption spectroscopy (XAS) allowed us to establish via XANES the speciation of U in the U particles, confirming the U(VI) oxidation state, while the exploitation of the EXAFS spectrum put in evidence of the presence of uranophane. Finally, the Fe, Sr, and U distributions in the particle and its matrix were obtained via X-ray fluorescence microtomography (XRF-µCT). It was concluded that the particle is composed of uranophane, imbricated with quartz and other oxides.

We demonstrate a portable fs laser system, used for optical-pump Xray-probe experiments in Diamond Light Source and its application in the areas of coordination chemistry and photo-induced linkage isomerization using X-ray spectroscopy and diffraction. © 2023 The Author(s)

We use time resolved Xray-absorption near-edge structure spectroscopy, tr-XANES, in the hard Xray regime, to monitor electronic and structural changes occurring in photocatalytic materials and organometallic compounds followed ultraviolet and visible pump excitation.

A free-standing and compact reaction cell for combined in situ/operando x-ray spectroscopy, scattering, and imaging measurements at high pressures and high temperatures is described. The cell permits measurements under realistic operating conditions (up to 50 bar and 1000 degrees C), under static and flow conditions (up to 100 ml/min), over a wide range of hard x-ray energies, variable detection modes (transmission, fluorescence, and scattering), and at all angles of rotation. An operando XAS, x-ray fluorescence, x-ray computed tomography, and x-ray diffraction computed tomography case study on the reduction of a heterogeneous catalyst is presented to illustrate the performance of the reaction cell.

AbstractPhoto(electro)catalysts use sunlight to drive chemical reactions such as water splitting. A major factor limiting photocatalyst development is physicochemical heterogeneity which leads to spatially dependent reactivity. To link structure and function in such systems, simultaneous probing of the electrochemical environment at microscopic length scales and a broad range of timescales (ns to s) is required. Here, we address this challenge by developing and applying in-situ (optical) microscopies to map and correlate local electrochemical activity, with hole lifetimes, oxygen vacancy concentrations and photoelectrode crystal structure. Using this multi-modal approach, we study prototypical hematite (α-Fe2O3) photoelectrodes. We demonstrate that regions of α-Fe2O3, adjacent to microstructural cracks have a better photoelectrochemical response and reduced back electron recombination due to an optimal oxygen vacancy concentration, with the film thickness and extended light exposure also influencing local activity. Our work highlights the importance of microscopic mapping to understand activity, in even seemingly homogeneous photoelectrodes.

Using operando X-ray absorption spectroscopy in a continuous-flow microfluidic cell, we have investigated the nucleation of platinum nanoparticles from aqueous hexachlor-oplatinate solution in the presence of the reducing agent ethylene glycol. By adjusting flow rates in the microfluidic channel, we resolved the temporal evolution of the reaction system in the first few seconds, generating the time profiles for speciation, ligand exchange, and reduction of Pt. Detailed analysis of the X-ray absorption near-edge structure and extended X-ray absorption fine structure spectra with multivariate data analysis shows that at least two reaction intermediates are involved in the transformation of the precursor H2PtCl6 to metallic platinum nanoparticles, including the formation of clusters with Pt-Pt bonding before complete reduction to Pt nanoparticles.

(Photo)electrocatalysts capture sunlight and use it to drive chemical reactions such as water splitting to produce H2. A major factor limiting photocatalyst development is their large heterogeneity which spatially modulates reactivity and precludes establishing robust structure-function relationships. To make such links requires simultaneously probing of the electrochemical environment at microscopic length scales (nm to um) and broad timescales (ns to s). Here, we address this challenge by developing and applying in-situ steady-state and transient optical microscopies to directly map and correlate local electrochemical activity with hole lifetimes, oxygen vacancy concentration and the photoelectrodes crystal structure. Using this combined approach alongside spatially resolved X-Ray absorption measurements, we study microstructural and point defects in prototypical hematite (Fe2O3) photoanodes. We demonstrate that regions of Fe2O3, adjacent to microstructural cracks have a better photoelectrochemical response and reduced back electron recombination due to an optimal oxide vacancy concentration, with the film thickness and carbon impurities also dramatically influencing activity in a complex manner. Our work highlights the importance of microscopic mapping to understand activity and the impact of defects in even, seemingly, homogeneous solid-state metal oxide photoelectrodes.

Uptake of uranium (U) by secondary minerals, such as carbonates and iron (Fe)-sulfides, that occur ubiquitously on Earth, may be substantial in deep anoxic environments compared to surficial settings due to different environment-specific conditions. Yet, knowledge of U reductive removal pathways and related fractionation between 238 U and 235 U isotopes in deep anoxic groundwater systems remain elusive. Here we show bacteria-driven degradation of organic constituents that influences formation of sulfidic species facilitating reduction of geochemically mobile U(VI) with subsequent trapping of U(IV) by calcite and Fe-sulfides. The isotopic signatures recorded for U and Ca in fracture water and calcite samples provide additional insights on U(VI) reduction behaviour and calcite growth rate. The removal efficiency of U from groundwater reaching 75% in borehole sections in fractured granite, and selective U accumulation in secondary minerals in exceedingly U-deficient groundwater shows the potential of these widespread mineralogical sinks for U in deep anoxic environments.

Caries, a major global disease associated with dental enamel demineralization, remains insufficiently understood to devise effective prevention or minimally invasive treatment. Understanding the ultrastructural changes in enamel is hampered by a lack of nanoscale characterization of the chemical spatial distributions within the dental tissue. This leads to the requirement to develop techniques based on various characterization methods. The purpose of the present study is to demonstrate the strength of analytic methods using a correlative technique on a single sample of human dental enamel as a specific case study to test the accuracy of techniques to compare regions in enamel. The science of the different techniques is integrated to genuinely study the enamel. The hierarchical structures within carious tissue were mapped using the combination of focused ion beam scanning electron microscopy with synchrotron X-ray tomography. The chemical changes were studied using scanning X-ray fluorescence (XRF) and X-ray wide-angle and small-angle scattering using a beam size below 80 nm for ångström and nanometer length scales. The analysis of XRF intensity gradients revealed subtle variations of Ca intensity in carious samples in comparison with those of normal mature enamel. In addition, the pathways for enamel rod demineralization were studied using X-ray ptychography. The results show the chemical and structural modification in carious enamel with differing locations. These results reinforce the need for multi-modal approaches to nanoscale analysis in complex hierarchically structured materials to interpret the changes of materials. The approach establishes a meticulous correlative characterization platform for the analysis of biomineralized tissues at the nanoscale, which adds confidence in the interpretation of the results and time-saving imaging techniques. The protocol demonstrated here using the dental tissue sample can be applied to other samples for statistical study and the investigation of nanoscale structural changes. The information gathered from the combination of methods could not be obtained with traditional individual techniques.

The Cretaceous-Paleogene (KPg) boundary is demarked by two critical and intimately linked events: a global-scale impact caused by a massive extraterrestrial body, and a resultant catastrophic planet-wide mass-extinction, with pivotal long-term consequences for life on Earth. The site of impact has been identified as the ~180 km wide Chicxulub crater complex [Yucatan peninsula, Mexico] based on strong geochemical, sedimentological, and temporal evidence. However, the impactor, which was obliterated on contact during the cratering process, has eluded identification. Previous studies struggled to identify the projectile based on scant geochemical and isotopic traces admixed with the ejecta and melt-rock, plus a single heavily altered microscopic fragment possibly from the impactor. While those efforts helped to rule out some potential sources and narrowed down the best potential candidates to a CM, CR, or CO carbonaceous chondrite, the data was insufficient to provide an incontrovertible diagnosis, and the identity of the Chicxulub projectile remained a critical missing detail. Here we describe new, exceptionally-preserved fragments of cosmic origin that were directly associated with Chicxulub impact ejecta from a temporally constrained KPg boundary site in North Dakota (U.S.A.). The fragments occur as inclusions within unaltered glassy ejecta spherules, which likely protected them against chemical and physical degradation, leading to their marked preservation. The spherules themselves were also uniquely preserved in amber, which inhibited their usual breakdown to smectitic clay. Geochemical examination of the inclusions were undertaken using electron microprobe, laser-ablation inductively-coupled-plasma-mass-spectroscopy, and synchrotron X-ray techniques. Results provide multiple lines of evidence that support a cosmic origin and chemistry indicative of a CM subtype carbonaceous chondrite, offering new support of prior hypotheses. The data is also in agreement with projectile residues from the Chicxulub impact fallout. In addition to its utility in reconstructing the dynamics of the Chicxulub event, this data helps provide extra dimension to our understanding of major impact processes and their effects on Earth.

Mineral dust is the largest source of aerosol iron (Fe) to the offshore global ocean, but acidic processing of coal fly ash (CFA) in the atmosphere could be an important source of soluble aerosol Fe. Here, we determined the Fe speciation and dissolution kinetics of CFA from Aberthaw (United Kingdom), Krakow (Poland), and Shandong (China) in solutions which simulate atmospheric acidic processing. In CFA PM10 fractions, 8 %–21.5 % of the total Fe was found to be hematite and goethite (dithionite-extracted Fe), and 2 %–6.5 % was found to be amorphous Fe (ascorbate-extracted Fe), while magnetite (oxalate-extracted Fe) varied from 3 %–22 %. The remaining 50 %–87 % of Fe was associated with other Fe-bearing phases, possibly aluminosilicates. High concentrations of ammonium sulfate ((NH4)2SO4), often found in wet aerosols, increased Fe solubility of CFA up to 7 times at low pH (2–3). The oxalate effect on the Fe dissolution rates at pH 2 varied considerably, depending on the samples, from no impact for Shandong ash to doubled dissolution for Krakow ash. However, this enhancement was suppressed in the presence of high concentrations of (NH4)2SO4. Dissolution of highly reactive (amorphous) Fe was insufficient to explain the high Fe solubility at low pH in CFA, and the modelled dissolution kinetics suggest that other Fe-bearing phases such as magnetite may also dissolve relatively rapidly under acidic conditions. Overall, Fe in CFA dissolved up to 7 times faster than in a Saharan dust precursor sample at pH 2. Based on these laboratory data, we developed a new scheme for the proton- and oxalate-promoted Fe dissolution of CFA, which was implemented into the global atmospheric chemical transport model IMPACT (Integrated Massively Parallel Atmospheric Chemical Transport). The revised model showed a better agreement with observations of Fe solubility in aerosol particles over the Bay of Bengal, due to the initial rapid release of Fe and the suppression of the oxalate-promoted dissolution at low pH. The improved model enabled us to predict sensitivity to a more dynamic range of pH changes, particularly between anthropogenic combustion and biomass burning aerosols.

Mineral dust is the largest source of aerosol iron (Fe) to the offshore global ocean, but acidic processing of coal fly ash (CFA) in the atmosphere could be an important source of soluble aerosol Fe. Here, we determined the Fe speciation and dissolution kinetics of CFA from Aberthaw (United Kingdom), Krakow (Poland), and Shandong (China) in solutions which simulate atmospheric acidic processing. In CFA PM10 fractions, 8 %-21.5 % of the total Fe was found to be hematite and goethite (dithionite-extracted Fe), and 2%-6.5 % was found to be amorphous Fe (ascorbate-extracted Fe), while magnetite (oxalate-extracted Fe) varied from 3 %-22 %. The remaining 50 %-87 % of Fe was associated with other Fe-bearing phases, possibly aluminosilicates. High concentrations of ammonium sulfate ((NH4)(2)SO4), often found in wet aerosols, increased Fe solubility of CFA up to 7 times at low pH (2-3). The oxalate effect on the Fe dissolution rates at pH 2 varied considerably, depending on the samples, from no impact for Shandong ash to doubled dissolution for Krakow ash. However, this enhancement was suppressed in the presence of high concentrations of (NH4)(2)SO4. Dissolution of highly reactive (amorphous) Fe was insufficient to explain the high Fe solubility at low pH in CFA, and the modelled dissolution kinetics suggest that other Fe-bearing phases such as magnetite may also dissolve relatively rapidly under acidic conditions. Overall, Fe in CFA dissolved up to 7 times faster than in a Saharan dust precursor sample at pH 2. Based on these laboratory data, we developed a new scheme for the proton- and oxalate-promoted Fe dissolution of CFA, which was implemented into the global atmospheric chemical transport model IMPACT (Integrated Massively Parallel Atmospheric Chemical Transport). The revised model showed a better agreement with observations of Fe solubility in aerosol particles over the Bay of Bengal, due to the initial rapid release of Fe and the suppression of the oxalate-promoted dissolution at low pH. The improved model enabled us to predict sensitivity to a more dynamic range of pH changes, particularly between anthropogenic combustion and biomass burning aerosols.

Natural uranium (U) in deep groundwater has been extensively studied in connection to the search for suitable locations for final disposal of spent nuclear fuel (SNF).[1] The U removal process depends on environmental and geochemical conditions and is often associated with fractionation of the main ‘stable’ isotopes, 238U and 235U (δ238U). The latter thus serves as an important tracer for redox specific scenarios, in local to global temporal and spatial scales. In this contribution, one specific borehole drilled at 415 m depth into Paleoproterozoic granitoid rock at the Äspö Hard Rock Laboratory (HRL), Sweden, is investigated after 17-year experiment period (1995-2012).[2] The HRL is built and operated by the Swedish Nuclear Fuel and Waste Management Co. and serves as a full-scale tunnel as a test-facility for the actual SNF repository to be built at Forsmark. We show how various micro-analytical techniques, modelling methods, and isotope analyses can be utilized to reveal U speciation and removal pathways, associated redox changes and related U isotope fractionations in the deep aquifer and during U mineralogical trapping. Spectroscopic techniques reveal that calcite precipitated on the borehole equipment contains intermittent highly elevated U, occurring as U(IV), and thus serves as a sink for U. Thermodynamic modelling shows that aqueous Fe(II) is the main driving force for the reduction of U(VI) in the borehole water, alongside sulfides formed from bacterial sulfate reduction. The bacteria-driven degradation of technical polymer constituents present in the borehole equipment is central to processes forming the sulfides and carbonates that facilitate reduction of U(VI) and subsequent immobilisation of U(IV) into the calcite. We use δ238U to show that U undergoes several redox events in granitic rock aquifers, involving mineralogical and microbial pathways. The recorded δ238U provides evidence for reductive removal of U from fracture water, presumably taking place along redox fronts in the fracture network. The obtained data on U(IV) removal by calcite provide important insights for the assessment of the geochemical behaviour of U and other redox-sensitive species in deep anoxic aquifers, that is relevant for trace metal mobility and long-term storage of SNF and nuclear waste. References [1]. J. Suksi et al., (2021), Chemical Geology 584: 120551. [2]. H. Drake et al., (2018), Environmental Science & Technology 52(2): 493-502.

Optical fiber technology has revolutionized the telecommunications industry, though is still under‐utilized in chemistry. Optical fibers open many avenues for introducing, and containing, light in chemical reactions, as part of a photoreactor. This work shows, for the first time, a design strategy for incorporating a photocatalytic, nanoporous framework (Co ZIF‐67) within the internal capillaries of an optical fiber, in doing so creating an all‐in‐one, plug‐in‐and‐play photoreactor. This system improves the reactivity of the photocatalyst, relative to the powdered form, for CH activation leading to CC bond formation, a significant process in pharmaceutical and organic synthesis. Performing this reaction using solar energy, and low temperature demonstrates the clear potential for these systems for large scale industrial applications.

Ashless dialkyldithiophosphate (DDP) antiwear additives are good candidates to replace the widely used metallic DDPs such as zinc dialkyldithiophosphate (ZDDP), which are less environmentally friendly. A newly designed insitu tribological rig was utilised to perform in-situ synchrotron X-ray absorption spectroscopy (XAS) in order to examine the decomposition reactions of two types of DDPs; acidic and neutral. The tribological experiments showed that the two DDP additives decomposed to form protective tribofilms on the steel surface, which provided better antiwear protection than ZDDP regardless of the tribofilm thickness. The neutral DDP formed a thinner tribofilm (about 33 nm) than ZDDP (about 41 nm), whereas the tribofilm of the acidic DDP had a much lower thickness (<7 nm) but more superior antiwear protection. The two DDPs also provided lower friction coefficient (<0.1) than the 0.12 provided by ZDDP. The XAS experiments suggest that the DDPs decompose to form initially iron sulphate, which is quickly reduced to sulphide before forming the phosphate layers of the protective tribofilm. These layers consisted initially of iron phosphate of short chains but as rubbing continued organic phosphate with long chains started to form.