Assessing Arsenic Species in Foods Using Regularized Linear Regression of the Arsenic K-edge X-ray Absorption Near Edge Structure.

The toxicity and bioavailability of arsenic is heavily dependent on its speciation. Therefore, robust and accurate methods are needed to determine arsenic speciation profiles for materials related to public health initiatives, such as food safety. Here, X-ray spectroscopies are attractive candidates as they provide in situ, nondestructive analyses of solid samples without perturbation to the arsenic species therein. This work provides a speciation analysis for three certified reference materials for the food chemistry community, whose assigned values may be used to assess the merit of the X-ray spectroscopy results. Furthermore, extracts of SRM 3232 Kelp Powder, which is value-assigned for arsenic species, are measured to provide further evidence of its efficacy. These analyses are performed on the results of As K-edge X-ray Absorption Near Edge Structure (XANES) measurements collected on each sample. Notably, such analyses have traditionally relied on linear combination fitting of a minimal subset of empirical standards selected by stepwise regression. This is known to be problematic for compounds with meaningfully collinear spectra and can yield overestimates of the accuracy of the analysis. Therefore, the least absolute shrinkage and selection operator (lasso) regression method is used to reduce the risk of overfitting and increase the interpretability of statistical inferences. As this is a biased statistical method, results and uncertainties are estimated using a bootstrap method accounting for the dominant sources of variability. Finally, this method does not separate model and data selection from regression analysis. Indeed, a survey of many spectral influences is presented including changes in the: state of methylation, state of protonation, oxidation state, coordination geometry, and sample phase. These compounds were all included in the model's training set, preventing model over-simplification and enabling high-throughput and robust analyses.

Probing Sulfur Chemical and Electronic Structure with Experimental Observation and Quantitative Theoretical Prediction of Kα and Valence-to-Core Kß X-ray Emission Spectroscopy.

An extensive experimental and theoretical study of the Kα and Kß high-resolution X-ray emission spectroscopy (XES) of sulfur-bearing systems is presented. This study encompasses a wide range of organic and inorganic compounds, including numerous experimental spectra from both prior published work and new measurements. Employing a linear-response time-dependent density functional theory (LR-TDDFT) approach, strong quantitative agreement is found in the calculation of energy shifts of the core-to-core Kα as well as the full range of spectral features in the valence-to-core Kß spectrum. The ability to accurately calculate the sulfur Kα energy shift supports the use of sulfur Kα XES as a bulk-sensitive tool for assessing sulfur speciation. The fine structure of the sulfur Kß spectrum, in conjunction with the theoretical results, is shown to be sensitive to the local electronic structure including effects of symmetry, ligand type and number, and, in the case of organosulfur compounds, to the nature of the bonded organic moiety. This agreement between theory and experiment, augmented by the potential for high-access XES measurements with the latest generation of laboratory-based spectrometers, demonstrates the possibility of broad analytical use of XES for sulfur and nearby third-row elements. The effective solution of the forward problem, i.e., successful prediction of detailed spectra from known molecular structure, also suggests future use of supervised machine learning approaches to experimental inference, as has seen recent interest for interpretation of X-ray absorption near-edge structure (XANES).

A mail-in and user facility for X-ray absorption near-edge structure: the CEI-XANES laboratory X-ray spectrometer at the University of Washington.

There are more than 100 beamlines or endstations worldwide that frequently support X-ray absorption fine-structure (XAFS) measurements, thus providing critical enabling capability for research across numerous scientific disciplines. However, the absence of a supporting tier of more readily accessible, lower-performing options has caused systemic inefficiencies, resulting in high oversubscription and the omission of many scientifically and socially valuable XAFS applications that are incompatible with the synchrotron facility access model. To this end, this work describes the design, performance and uses of the Clean Energy Institute X-ray absorption near-edge structure (CEI-XANES) laboratory spectrometer and its use as both a user-present and mail-in facility. Such new additions to the XAFS infrastructure landscape raise important questions about the most productive interactions between synchrotron radiation and laboratory-based capabilities; this can be discussed in the framework of five categories, only one of which is competitive. The categories include independent operation on independent problems, use dictated by convenience, pre-synchrotron preparatory use of laboratory capability, post-synchrotron follow-up use of laboratory capability, and parallel use of both synchrotron radiation and laboratory systems.

Interface Engineering V2 O5 Nanofibers for High-Energy and Durable Supercapacitors.

A local electric field is induced to engineer the interface of vanadium pentoxide nanofibers (V2 O5 -NF) to manipulate the charge transport behavior and obtain high-energy and durable supercapacitors. The interface of V2 O5 -NF is modified with oxygen vacancies (Vö) in a one-step polymerization process of polyaniline (PANI). In the charge storage process, the local electric field deriving from the lopsided charge distribution around Vö will provide Coulombic forces to promote the charge transport in the resultant Vö-V2 O5 /PANI nanocable electrode. Furthermore, an ≈7 nm porous PANI coating serves as the external percolated charge transport pathway. As the charge transfer kinetics are synergistically enhanced by the dual modifications, Vö-V2 O5 /PANI-based supercapacitors exhibit an excellent specific capacitance (523 F g-1 ) as well as a long cycling lifespan (110% of capacitance remained after 20 000 cycles). This work paves an effective way to promote the charge transfer kinetics of electrode materials for next-generation energy storage systems.

Tailoring Energy and Power Density through Controlling the Concentration of Oxygen Vacancies in V2O5/PEDOT Nanocable-Based Supercapacitors.

Oxygen vacancies (Vö) play a crucial role in energy storage materials. Oxygen-vacancy-enriched vanadium pentoxide/poly(3,4-ethylenedioxythiophene) (Vö-V2O5/PEDOT) nanocables were prepared through the one-pot oxidative polymerization of PEDOT. PEDOT is used to create tunable concentrations of Vö in the surface layer of V2O5, which has been confirmed by X-ray absorption near edge structure (XANES) analysis and X-ray photoelectron spectroscopy (XPS) measurements. Applied as electrode materials for supercapacitors, the electrochemical performance of Vö-V2O5/PEDOT is improved by the synergistic effects of Vö in V2O5 cores and PEDOT shells with rapid charge transfer and fast Na+ ion diffusion; however, it is compromised subsequently by excessive Vö in consuming more V5+ cations for Faradic reactions. Consequently, the specific capacitance and the energy density of Vö-V2O5/PEDOT nanocables are significantly enhanced when the overall concentration of Vö is 1.3%. The migration of Vö renders an increased capacitance (105% retention) after 10 000 cycles, which is verified and corroborated with density functional theory simulations and XANES analysis. This work provides an illumination for the fabrication of high-performance electrode materials in the energy storage field through Vö.

An improved laboratory-based x-ray absorption fine structure and x-ray emission spectrometer for analytical applications in materials chemistry research.

X-ray absorption fine structure (XAFS) and x-ray emission spectroscopy (XES) are advanced x-ray spectroscopies that impact a wide range of disciplines. However, unlike the majority of other spectroscopic methods, XAFS and XES are accompanied by an unusual access model, wherein the dominant use of the technique is for premier research studies at world-class facilities, i.e., synchrotron x-ray light sources. In this paper, we report the design and performance of an improved XAFS and XES spectrometer based on the general conceptual design of Seidler et al. [Rev. Sci. Instrum. 85, 113906 (2014)]. New developments include reduced mechanical degrees of freedom, much-increased flux, and a wider Bragg angle range to enable extended x-ray absorption fine structure (EXAFS) measurement and analysis for the first time with this type of modern laboratory XAFS configuration. This instrument enables a new class of routine applications that are incompatible with the mission and access model of the synchrotron light sources. To illustrate this, we provide numerous examples of x-ray absorption near edge structure (XANES), EXAFS, and XES results for a variety of problems and energy ranges. Highlights include XAFS and XES measurements of battery electrode materials, EXAFS of Ni with full modeling of results to validate monochromator performance, valence-to-core XES for 3d transition metal compounds, and uranium XANES and XES for different oxidation states. Taken en masse, these results further support the growing perspective that modern laboratory-based XAFS and XES have the potential to develop a new branch of analytical chemistry.

Vacuum formed temporary spherically and toroidally bent crystal analyzers for x-ray absorption and x-ray emission spectroscopy.

We demonstrate that vacuum forming of 10-cm diameter silicon wafers of various crystallographic orientations under an x-ray permeable, flexible window can easily generate spherically bent crystal analyzers and toroidally bent crystal analyzers with ∼1-eV energy resolution and a 1-m major radius of curvature. In applications at synchrotron light sources, x-ray free electron lasers, and laboratory spectrometers, these characteristics are generally sufficient for many x-ray absorption fine structure (XAFS), x-ray emission spectroscopy (XES), and resonant inelastic x-ray scattering applications in the chemical sciences. Unlike existing optics manufacturing methods using epoxy or anodic bonding, vacuum forming without adhesive is temporary in the sense that the bent wafer can be removed when vacuum is released and exchanged for a different orientation wafer. Therefore, the combination of an x-ray compatible vacuum-forming chamber, a library of thin wafers, and a small number of forms having different secondary curvatures can give extreme flexibility in spectrometer energy range. As proof of this method, we determine the energy resolution and reflectivity for several such vacuum-formed bent crystal analyzers in laboratory-based XAFS and XES studies using a conventional x-ray tube. For completeness, we also show x-ray images collected on the detector plane to characterize the resulting focal spots and optical aberrations.

Determination of Hexavalent Chromium Fractions in Plastics Using Laboratory-Based, High-Resolution X-ray Emission Spectroscopy.

Cr(VI) is a well-known human carcinogen with many water-soluble moieties. Its presence in both natural and man-made substances poses a risk to public health, especially when contamination of groundwater is possible. This has led the European Union and other jurisdictions to include Cr(VI) in restriction of hazardous substances regulations. However, for several important industrial and commercial purposes, analytical capability to characterize Cr(VI) is known to be insufficient for regulatory purposes. For example, advanced X-ray spectroscopies, particularly synchrotron-based X-ray absorption fine structure (XAFS) studies, have shown that species interconversion and under-extraction can be difficult to prevent in many existing liquid extraction protocols when applied to plastics, mining ores and tailings, and paint sludges. Here, we report that wavelength dispersive X-ray fluorescence spectroscopy taken at energy resolutions close to the theoretical limit imposed by the core-hole lifetime, generally called X-ray emission spectroscopy (XES) in the synchrotron community, can be used in the laboratory setting for noninvasive, analytical characterization of the Cr(VI)/Cr ratio in plastics. The selected samples have been part of ongoing efforts by standards development organizations to create improved Cr(VI) testing protocols, and the present work provides a direct proof-of-principle for the use of such extremely high-resolution laboratory WDXRF as an alternative to liquid extraction methods for regulatory compliance testing of Cr(VI) content. As a practical application of this work, we report a value for the Cr(VI) mass fraction of the new NIST Standard Reference Material 2859 Restricted Elements in Polyvinyl Chloride.