Y(III) Sorption at the Orthoclase (001) Surface Measured by X-ray Reflectivity.

Interactions of heavy metals with charged mineral surfaces control their mobility in the environment. Here, we investigate the adsorption of Y(III) onto the orthoclase (001) basal plane, the former as a representative of rare earth elements and an analogue of trivalent actinides and the latter as a representative of naturally abundant K-feldspar minerals. We apply in situ high-resolution X-ray reflectivity to determine the sorption capacity and molecular distribution of adsorbed Y species as a function of the Y3+ concentration, [Y3+], at pH 7 and 5. With [Y3+] ≥ 1 mM at pH 7, we observe an inner-sphere (IS) sorption complex at a distance of ∼1.5 Å from the surface and an outer-sphere (OS) complex at 3-4 Å. Based on the adsorption height of the IS complex, a bidentate, binuclear binding mode, in which Y3+ binds to two terminal oxygens, is proposed. In contrast, mostly OS sorption is observed at pH 5. The observed maximum Y coverage is ∼1.3 Y3+/AUC (AUC: area of the unit cell = 111.4 Å2) for all the investigated pH values and Y concentrations, which is in the expected range based on the estimated surface charge of orthoclase (001).

Structure and Surface Complexation at the Calcite(104)-Water Interface.

Calcite is the most stable polymorph of calcium carbonate (CaCO3) under ambient conditions and is ubiquitous in natural systems. It plays a major role in controlling pH in environmental settings. Electrostatic phenomena at the calcite-water interface and the surface reactivity of calcite in general have important environmental implications. They may strongly impact nutrient and contaminant mobility in soils and other subsurface environments, they control oil recovery from limestone reservoirs, and they may impact the safety of nuclear waste disposal sites. Besides the environmental relevance, the topic is significant for industrial applications and cultural heritage preservation. In this study, the structure of the calcite(104)-water interface is investigated on the basis of a new extensive set of crystal truncation rod data. The results agree with recently reported structures and resolve previous ambiguities with respect to the coordination sphere of surface Ca ions. These structural features are introduced into an electrostatic three-plane surface complexation model, describing ion adsorption and charging at the calcite-water interface. Inner surface potential data for calcite, as measured with a calcite single-crystal electrode, are used as constraints for the model in addition to zeta potential data. Ion adsorption parameters are compared with molecular dynamics simulations. All model parameters, including protonation constants, ion-binding parameters, and Helmholtz capacitances, are within physically and chemically plausible ranges. A PhreeqC version of the model is presented, which we hope will foster application of the model in environmental studies.

Fast identification of mineral inclusions in diamond at GSECARS using synchrotron X-ray microtomography, radiography and diffraction.

Mineral inclusions in natural diamond are widely studied for the insight that they provide into the geochemistry and dynamics of the Earth's interior. A major challenge in achieving thorough yet high rates of analysis of mineral inclusions in diamond derives from the micrometre-scale of most inclusions, often requiring synchrotron radiation sources for diffraction. Centering microinclusions for diffraction with a highly focused synchrotron beam cannot be achieved optically because of the very high index of refraction of diamond. A fast, high-throughput method for identification of micromineral inclusions in diamond has been developed at the GeoSoilEnviro Center for Advanced Radiation Sources (GSECARS), Advanced Photon Source, Argonne National Laboratory, USA. Diamonds and their inclusions are imaged using synchrotron 3D computed X-ray microtomography on beamline 13-BM-D of GSECARS. The location of every inclusion is then pinpointed onto the coordinate system of the six-circle goniometer of the single-crystal diffractometer on beamline 13-BM-C. Because the bending magnet branch 13-BM is divided and delivered into 13-BM-C and 13-BM-D stations simultaneously, numerous diamonds can be examined during coordinated runs. The fast, high-throughput capability of the methodology is demonstrated by collecting 3D diffraction data on 53 diamond inclusions from Juína, Brazil, within a total of about 72 h of beam time.

Competitive Adsorption of ZrO2 Nanoparticle and Alkali Cations (Li+-Cs+) on Muscovite (001).

We studied the adsorption behavior of ZrO2 nanoparticles on a muscovite (001) surface in the presence of cations from the alkali series (Li+, Na+, K+, Rb+, and Cs+). The results of X-ray reflectivity, i.e., specular crystal truncation rod and resonant anomalous X-ray reflectivity in combination with AFM images, show that the sorption of ZrO2 nanoparticles is significantly affected by the binding mode of alkali ions on the muscovite (001) surface. From solutions containing alkali ions binding as outer sphere surface complexes (i.e., Li+ and Na+), higher uptake of Zr4+ is observed corresponding to the binding of larger nanoparticles, which relatively easily replace the loosely bound alkali ions. However, Zr4+ uptake in solutions containing alkali ions binding as inner sphere surface complexes (i.e., K+, Rb+, and Cs+) is significantly lower, and smaller nanoparticles are found at the interface. In addition, the uptake of Zr4+ in the presence of inner sphere bound cations displays a strong linear relationship with the hydration energy of the coexisting alkali ion. The linear trend can be interpreted as competitive adsorption between ZrO2 nanoparticles and inner sphere bound alkali cations, which are replaced on the surface and undergo rehydration after release to the solution. The rehydration of alkali ions gives rise to a large energy gain, which dominates the reaction energy of the competitive adsorption process. The competitive adsorption mechanism of ZrO2 nanoparticles and alkali ions is discussed comprehensively to highlight the potential relationship between the hydration effect of alkali ions and the effect of charge density of the nanoparticles.

Dynamic Stabilization of Metal Oxide-Water Interfaces.

The interaction of water with metal oxide surfaces plays a crucial role in the catalytic and geochemical behavior of metal oxides. In a vast majority of studies, the interfacial structure is assumed to arise from a relatively static lowest energy configuration of atoms, even at room temperature. Using hematite (α-Fe2O3) as a model oxide, we show through a direct comparison of in situ synchrotron X-ray scattering with density functional theory-based molecular dynamics simulations that the structure of the (11̅02) termination is dynamically stabilized by picosecond water exchange. Simulations show frequent exchanges between terminal aquo groups and adsorbed water in locations and with partial residence times consistent with experimentally determined atomic sites and fractional occupancies. Frequent water exchange occurs even for an ultrathin adsorbed water film persisting on the surface under a dry atmosphere. The resulting time-averaged interfacial structure consists of a ridged lateral arrangement of adsorbed water molecules hydrogen bonded to terminal aquo groups. Surface pKa prediction based on bond valence analysis suggests that water exchange will influence the proton-transfer reactions underlying the acid/base reactivity at the interface. Our findings provide important new insights for understanding complex interfacial chemical processes at metal oxide-water interfaces.

Oxidative Corrosion of the UO2 (001) Surface by Nonclassical Diffusion.

Uranium oxide is central to every stage of the nuclear fuel cycle, from mining through fuel fabrication and use, to waste disposal and environmental cleanup. Its chemical and mechanical stability are intricately linked to the concentration of interstitial O atoms within the structure and the oxidation state of U. We have previously shown that, during corrosion of the UO2 (111) surface under either 1 atm of O2 gas or oxygenated water at room temperature, oxygen interstitials diffuse into the substrate to form a superlattice with three-layer periodicity. In the current study, we present results from surface X-ray scattering that reveal the structure of the oxygen diffusion profile beneath the (001) surface. The first few layers below the surface oscillate strongly in their surface-normal lattice parameters, suggesting preferential interstitial occupation of every other layer below the surface, which is geometrically consistent with the interstitial network that forms below the oxidized (111) surface. Deeper layers are heavily contracted and indicate that the oxidation front penetrates ∼52 Šbelow the (001) surface after 21 days of dry O2 gas exposure at ambient pressure and temperature. X-ray photoelectron spectroscopy indicates U is present as U(IV), U(V), and U(VI).

Quantifying small changes in uranium oxidation states using XPS of a shallow core level.

The U 4f line is commonly used to determine uranium oxidation states with X-ray photoelectron spectroscopy (XPS). In contrast, the XPS of the shallow core-levels of uranium are rarely recorded. Nonetheless, theory has shown that the U 5d (and 5p) multiplet structure is very sensitive to oxidation state. In this contribution we extracted the U(iv) and U(v) 5d XPS peak shapes from near stoichiometric and oxidized UO2 single crystal samples, respectively, where the oxidation state of U was constrained by fitting the 4f line. The empirically extracted 5d spectra were similar to the theoretically determined multiplet structures and were used, along with the relatively simple U(vi) component that was constrained by theory, to determine the oxidation states of UO2+x samples. The results showed a very strong correlation between oxidation states determined by the 5d and 4f line and suggested that the 5d might be more sensitive to minor amounts of oxidation than the 4f. Limitations of the methodology, as well as advantages of using the 5d relative to the 4f line are discussed.

Spatially Resolved Elemental Analysis, Spectroscopy and Diffraction at the GSECARS Sector at the Advanced Photon Source.

X-ray microprobes (XRM) coupled with high-brightness synchrotron X-ray facilities are powerful tools for environmental biogeochemistry research. One such instrument, the XRM at the Geo Soil Enviro Center for Advanced Radiation Sources Sector 13 at the Advanced Photon Source (APS; Argonne National Laboratory, Lemont, IL) was recently improved as part of a canted undulator geometry upgrade of the insertion device port, effectively doubling the available undulator beam time and extending the operating energy of the branch supporting the XRM down to the sulfur K edge (2.3 keV). Capabilities include rapid, high-resolution, elemental imaging including fluorescence microtomography, microscale X-ray absorption fine structure spectroscopy including sulfur K edge capability, and microscale X-ray diffraction. These capabilities are advantageous for (i) two-dimensional elemental mapping of relatively large samples at high resolution, with the dwell times typically limited only by the count times needed to obtain usable counting statistics for low concentration elements, (ii) three-dimensional imaging of internal elemental distributions in fragile hydrated specimens, such as biological tissues, avoiding the need for physical slicing, (iii) spatially resolved speciation determinations of contaminants in environmental materials, and (iv) identification of contaminant host phases. In this paper, we describe the XRM instrumentation, techniques, applications demonstrating these capabilities, and prospects for further improvements associated with the proposed upgrade of the APS.

A Comparison of Adsorption, Reduction, and Polymerization of the Plutonyl(VI) and Uranyl(VI) Ions from Solution onto the Muscovite Basal Plane.

X-ray scattering techniques [in situ resonant anomalous X-ray reflectivity (RAXR) and specular crystal truncation rods (CTR)] were used to compare muscovite (001) surfaces in contact with solutions containing either 0.1 mM plutonyl(VI) or 1 mM uranyl(VI) at pH = 3.2 ± 0.2, I(NaCl) = 0.1 M, as well as in situ grazing-incidence X-ray absorption near-edge structure (GI XANES) spectroscopy and ex situ alpha spectrometry. Details of the surface coverage are found to be very different. In the case of Pu, alpha spectrometry finds a surface coverage of 8.3 Pu/AUC (AUC = 46.72 Å2, the unit cell area), far in excess of the 0.5 Pu/AUC expected for ionic adsorption of PuO22+. GI XANES results show that Pu is predominantly tetravalent on the surface, and the CTR/RAXR results show that the adsorbed Pu is broadly distributed. Taken together with previous findings, the results are consistent with adsorption of Pu in the form of Pu(IV)-oxo-nanoparticles. In contrast, uranyl shows only negligible, if any, adsorption according to all methods applied. These results are discussed and compared within the context of known Pu and U redox chemistry.

UO(2) Oxidative Corrosion by Nonclassical Diffusion.

Using x-ray scattering, spectroscopy, and density-functional theory, we determine the structure of the oxidation front when a UO(2) (111) surface is exposed to oxygen at ambient conditions. In contrast to classical diffusion and previously reported bulk UO(2+x) structures, we find oxygen interstitials order into a nanoscale superlattice with three-layer periodicity and uranium in three oxidation states: IV, V, and VI. This oscillatory diffusion profile is driven by the nature of the electron transfer process, and has implications for understanding the initial stages of oxidative corrosion in materials at the atomistic level.

Structure-charge relationship - the case of hematite (001).

We present a multidisciplinary study on the hematite (001)-aqueous solution interface, in particular the relationship between surface structure (studied via surface diffraction in a humid atmosphere) and the macroscopic charging (studied via surface- and zeta-potential measurements in electrolyte solutions as a function of pH). Upon aging in water changes in the surface structure are observed, that are accompanied by drastic changes in the zeta-potential. Surprisingly the surface potential is not accordingly affected. We interpret our results by increasing hydration of the surface with time and enhanced reactivity of singly-coordinated hydroxyl groups that cause the isoelectric point of the surface to shift to values that are reminiscent of those typically reported for hematite particles. In its initial stages after preparation the hematite surface is very flat and only weakly hydrated. Our model links the entailing weak water structure with the observed low isoelectric point reminiscent of hydrophobic surfaces. The absence of an aging effect on the surface potential vs. pH curves is interpreted as domination of the surface potential by the doubly coordinated hydroxyls, which are present on both surfaces.

Diagnosing new-onset asthma in a paediatric clinical trial setting in school-age children.

Asthma is a common chronic disease in children. It is a dynamic condition-symptoms change over time, and the outcome of diagnostic tests can vary. Consequently, evaluating the onset of asthma at a single point in time, perhaps when patients are asymptomatic with limited impairment of the lung function, may result in false diagnostic conclusions. The absence of consistent gold-standard diagnostic criteria in children challenges the ability of any study to ascertain an effect of treatment on asthma prevention. A comprehensive review of the diagnostic criteria used for new-onset asthma in school-age children was conducted based on existing recommendations from published clinical guidance, alongside evidence from paediatric asthma prevention trials. Findings from the review were used to propose suggestions for diagnosing new-onset asthma in future asthma prevention trials. Despite an overall lack of consensus in the published clinical guidance, there are similarities between the various recommendations for diagnosing asthma in children, which typically involve assessing the variable symptoms and supplementing the medical history with objective measures of lung function. For future paediatric asthma prevention trials, we suggest that paediatric clinical trials should use a new-onset asthma definition that incorporates the concepts of "possible", "probable" and "confirmed" asthma. "Possible" asthma would capture self-reported features of chronic symptoms and symptom relief with ß2-agonist bronchodilator (suggesting reversibility). "Probable" asthma would include symptom chronicity, self-reported symptom relief with ß2-agonist bronchodilator, and objective features of asthma (reversibility or bronchial hyper-responsiveness). A "confirmed" diagnosis would be made only if there is a positive response to controller therapy. These suggestions aim to improve the diagnosis of new-onset childhood asthma in clinical trials, which will be useful in the design and conduct of future paediatric asthma prevention trials.

Identifying critical features of iron phosphate particle for lithium preference.

One-dimensional (1D) olivine iron phosphate (FePO4) is widely proposed for electrochemical lithium (Li) extraction from dilute water sources, however, significant variations in Li selectivity were observed for particles with different physical attributes. Understanding how particle features influence Li and sodium (Na) co-intercalation is crucial for system design and enhancing Li selectivity. Here, we investigate a series of FePO4 particles with various features and revealed the importance of harnessing kinetic and chemo-mechanical barrier difference between lithiation and sodiation to promote selectivity. The thermodynamic preference of FePO4 provides baseline of selectivity while the particle features are critical to induce different kinetic pathways and barriers, resulting in different Li to Na selectivity from 6.2 × 102 to 2.3 × 104. Importantly, we categorize the FePO4 particles into two groups based on their distinctly paired phase evolutions upon lithiation and sodiation, and generate quantitative correlation maps among Li preference, morphological features, and electrochemical properties. By selecting FePO4 particles with specific features, we demonstrate fast (636 mA/g) Li extraction from a high Li source (1: 100 Li to Na) with (96.6 ± 0.2)% purity, and high selectivity (2.3 × 104) from a low Li source (1: 1000 Li to Na) with (95.8 ± 0.3)% purity in a single step.

Reaction Layer Formation on MgO in the Presence of Humidity.

Mineralization by MgO is an attractive potential strategy for direct air capture (DAC) of CO2 due to its tendency to form carbonate phases upon exposure to water and CO2. Hydration of MgO during this process is typically assumed to not be rate limiting, even at ambient temperatures. However, surface passivation by hydrated phases likely reduces the CO2 capture capacity. Here, we examine the initial hydration reactions that occur on MgO(100) surfaces to determine whether they could potentially impact CO2 uptake. We first used atomic force microscopy (AFM) to explore changes in reaction layers in water (pH = 6 and 12) and MgO-saturated solution (pH = 11) and found the reaction layers on MgO are heterogeneous and nonuniform. To determine how relative humidity (R.H.) affects reactivity, we reacted samples at room temperature in nominally dry N2 (∼11-12% R.H.) for up to 12 h, in humid (>95% R.H.) N2 for 5, 10, and 15 min, and in air at 33 and 75% R.H. for 8 days. X-ray reflectivity and electron microscopy analysis of the samples reveal that hydrated phases form rapidly upon exposure to humid air, but the growth of the hydrated reaction layer slows after its initial formation. Reaction layer thickness is strongly correlated with R.H., with denser reaction layers forming in 75% R.H. compared with 33% R.H. or nominally dry N2. The reaction layers are likely amorphous or poorly crystalline based on grazing incidence X-ray diffraction measurements. After exposure to 75% R.H. in air for 8 days, the reaction layer increases in density as compared to the sample reacted in humid N2 for 5-15 min. This may represent an initial step toward the crystallization of the reaction layer. Overall, high R.H. favors the formation of a hydrated, disordered layer on MgO. Based on our results, DAC in a location with a higher R.H. will be favorable, but growth may slow significantly from initial rates even on short timescales, presumably due to surface passivation.

Competitive sorption of Pb(II) and Zn(II) on polyacrylic acid-coated hydrated aluminum-oxide surfaces.

Natural organic matter (NOM) often forms coatings on minerals. Such coatings are expected to affect metal-ion sorption due to abundant sorption sites in NOM and potential modifications to mineral surfaces, but such effects are poorly understood in complex multicomponent systems. Using poly(acrylic acid) (PAA), a simplified analog of NOM containing only carboxylic groups, Pb(II) and Zn(II) partitioning between PAA coatings and α-Al2O3 (1-102) and (0001) surfaces was investigated using long-period X-ray standing wave-florescence yield spectroscopy. In the single-metal-ion systems, PAA was the dominant sink for Pb(II) and Zn(II) for α-Al2O3(1-102) (63% and 69%, respectively, at 0.5 µM metal ions and pH 6.0). In equi-molar mixed-Pb(II)-Zn(II) systems, partitioning of both ions onto α-Al2O3(1-102) decreased compared with the single-metal-ion systems; however, Zn(II) decreased Pb(II) sorption to a greater extent than vice versa, suggesting that Zn(II) outcompeted Pb(II) for α-Al2O3(1-102) sorption sites. In contrast, >99% of both metal ions sorbed to PAA when equi-molar Pb(II) and Zn(II) were added simultaneously to PAA/α-Al2O3(0001). PAA outcompeted both α-Al2O3 surfaces for metal sorption but did not alter their intrinsic order of reactivity. This study suggests that single-metal-ion sorption results cannot be used to predict multimetal-ion sorption at NOM/metal-oxide interfaces when NOM is dominated by carboxylic groups.

Surface-mediated formation of Pu(IV) nanoparticles at the muscovite-electrolyte interface.

The formation of Pu(IV)-oxo-nanoparticles from Pu(III) solutions by a surface-enhanced redox/polymerization reaction at the muscovite (001) basal plane is reported, with a continuous increase in plutonium coverage observed in situ over several hours. The sorbed Pu extends >70 Å from the surface with a maximum concentration at 10.5 Å and a total coverage of >9 Pu atoms per unit cell area of muscovite (0.77 µg Pu/cm(2)) (determined independently by in situ resonant anomalous X-ray reflectivity and by ex-situ alpha-spectrometry). The presence of discrete nanoparticles is confirmed by high resolution atomic force microscopy. We propose that the formation of these Pu(IV) nanoparticles from an otherwise stable Pu(III) solution can be explained by the combination of a highly concentrated interfacial Pu-ion species, the Pu(III)-Pu(IV) redox equilibrium, and the strong proclivity of tetravalent Pu to hydrolyze and form polymeric species. These results are the first direct observation of such behavior of plutonium on a naturally occurring mineral, providing insights into understanding the environmental transport of plutonium and other contaminants capable of similar redox/polymerization reactions.

Metastatic Colon Cancer - An Effective Treatment Protocol of Integrative Therapies Including Electromagnetic Field Frequencies: A Case Report.

Introduction: Colorectal cancer is the third most common cancer worldwide, with 25% of patients being diagnosed with metastatic disease, mostly in the liver, resulting in poor survival. Standard treatment of stage-IV colorectal cancer consists of primary tumour resection followed by chemotherapy. Case Presentation: Here, we report on the treatment effectiveness using integrative therapies in a 52-year-old male with metastatic colon cancer and liver lesions to achieve stable partial remission with an overall high level of wellbeing. After surgical removal of the primary tumour, the 8-month integrative treatment regime consisted of standard anti-angiogenesis treatment, as well as multiple non-standard but evidence-based therapies, including high-dose intravenous nutrients and herbal therapies, oral intake of repurposed medication and nutritional supplements, and a 4-month targeted electromagnetic field/Rife frequency therapy. Conclusion: The integrative therapies used in this case study were highly tolerable and effective in the treatment of metastatic colon cancer with liver lesions, achieving substantial tumour response and stable partial remission with a high level of wellbeing.

Imaging of the electronic bonding of diamond at pressures up to 2 million atmospheres.

Diamond shows unprecedented hardness. Because hardness is a measure of resistance of chemical bonds in a material to external indentation, the electronic bonding nature of diamond beyond several million atmospheres is key to understanding the origin of hardness. However, probing the electronic structures of diamond at such extreme pressure has not been experimentally possible. The measurements on the inelastic x-ray scattering spectra for diamond up to 2 million atmospheres provide data on the evolution of its electronic structures under compression. The mapping of the observed electronic density of states allows us to obtain a two-dimensional image of the bonding transitions of diamond undergoing deformation. The spectral change near edge onset is minor beyond a million atmospheres, while its electronic structure displays marked pressure-induced electron delocalization. Such electronic responses indicate that diamond's external rigidity is supported by its ability to reconcile internal stress, providing insights into the origins of hardness in materials.

Guideline on allergen immunotherapy in IgE-mediated allergic diseases: S2K Guideline of the German Society of Allergology and Clinical Immunology (DGAKI), Society of Pediatric Allergology and Environmental Medicine (GPA), Medical Association of German Allergologists (AeDA), Austrian Society of Allergology and Immunology (ÖGAI), Swiss Society for Allergology and Immunology (SSAI), German Dermatological Society (DDG), German Society of Oto-Rhino-Laryngology, Head and Neck Surgery (DGHNO-KHC), German Society of Pediatrics and Adolescent Medicine (DGKJ), Society of Pediatric Pulmonology (GPP), German Respiratory Society (DGP), German Professional Association of Otolaryngologists (BVHNO), German Association of Paediatric and Adolescent Care Specialists (BVKJ), Federal Association of Pneumologists, Sleep and Respiratory Physicians (BdP), Professional Association of German Dermatologists (BVDD).

Not available.

Probing Ag nanoparticle surface oxidation in contact with (in)organics: an X-ray scattering and fluorescence yield approach.

Characterizing interfacial reactions is a crucial part of understanding the behavior of nanoparticles in nature and for unlocking their functional potential. Here, an advanced nanostructure characterization approach to study the corrosion processes of silver nanoparticles (Ag-Nps), currently the most highly produced nanoparticle for nanotechnology, is presented. Corrosion of Ag-Nps under aqueous conditions, in particular in the presence of organic matter and halide species common to many natural environments, is of particular importance because the release of toxic Ag(+) from oxidation/dissolution of Ag-Nps may strongly impact ecosystems. In this context, Ag-Nps capped with polyvinolpyrrolidone (PVP) in contact with a simple proxy of organic matter in natural waters [polyacrylic acid (PAA) and Cl(-) in solution] has been investigated. A combination of synchrotron-based X-ray standing-wave fluorescence yield- and X-ray diffraction-based experiments on a sample consisting of an approximately single-particle layer of Ag-Nps deposited on a silicon substrate and coated by a thin film of PAA containing Cl revealed the formation of a stable AgCl corrosion product despite the presence of potential surface stabilizers (PVP and PAA). Diffusion and precipitation processes at the Ag-Nps-PAA interface were characterized with a high spatial resolution using this new approach.