Search

Tomographic coherent imaging requires the reconstruction of a series of two-dimensional projections of the object. We show that using the solution for the image of one projection as the starting point for the reconstruction of the next projection offers a reliable and rapid approach to the image reconstruction. The method is demonstrated on simulated and experimental data. This technique also simplifies reconstructions using data with curved incident wavefronts.

We demonstrate use of a complex constraint based on the interaction of x-rays with matter for reconstructing images from coherent X-ray diffraction. We show the complementary information provided by the phase and magnitude of the reconstructed wavefield greatly improves the quality of the resulting estimate of the transmission function of an object without the need for a priori information about the object composition.

This paper analyzes and evaluates various denoising techniques, including Wavelet Transform and Moving Average Filter methods for removing ocular and motion artifacts from EEG signals. The performance of each technique is benchmarked in terms of signal-to-noise ratio (SNR) and normalized mean squared error (NMSE) on available EEG databases, including Bonn and Motion-Artifact Contaminated EEG databases. Simulation results show that the Wavelet Transform using the SURE Shrink algorithm with the hard thresholding rule has the best performance for removing ocular artifacts in intracranial EEG. In contrast, the Wavelet Transform using the universal threshold shrinkage rule with hard thresholding is the preferred method for removing motion artifacts in scalp EEGs. This study is an essential step toward more advanced work to achieve real-time, and low-cost denoising methods for energy-constrained devices.

Atomic-level understanding of the active sites and transformation mechanisms under realistic working conditions is a prerequisite for rational design of high-performance photocatalysts. Here, by using correlated scanning fluorescence X-ray microscopy and environmental transmission electron microscopy at atmospheric pressure, in operando, we directly observe that the (110) facet of a single Cu2O photocatalyst particle is photocatalytically active for CO2 reduction to methanol while the (100) facet is inert. The oxidation state of the active sites changes from Cu(i) towards Cu(ii) due to CO2 and H2O co-adsorption and changes back to Cu(i) after CO2 conversion under visible light illumination. The Cu2O photocatalyst oxidizes water as it reduces CO2. Concomitantly, the crystal lattice expands due to CO2 adsorption then reverts after CO2 conversion. The internal quantum yield for unassisted wireless photocatalytic reduction of CO2 to methanol using Cu2O crystals is ~72%. Photocatalytic reduction of CO2 to methanol offers a promising route to storage of solar energy in the form of chemical fuels. Here, Wu et al. use in operando microscopy to identify the active facets for CO2 reduction on Cu2O and exploit this to obtain high conversion efficiency and selectivity to methanol.

Crystallization from an amorphous precursor presents a new route to control the properties of complex oxides by selecting their nanoscale morphology. A key challenge in crystal growth from the amor...

Nanoporous metals fabricated by dealloying have a unique bi-continuous, sponge-like porous structure with ultra-high surface area. The unique properties of these materials, especially nanoporous gold, have numerous potential applications in sensors and actuators and in energy-related applications such as catalytic materials, super-capacitors, and battery supports. The degree of porosity and size of the metal ligaments are critical parameters that determine many properties and thus govern the functionalities of nanoporous metals in many applications including energy storage and conversion. We used Fresnel coherent diffractive imaging combined with tomographic reconstruction to quantify the nanoscale three-dimensional spatial distribution and homogeneity of the porosity and ligament size within a bulk sample of nanoporous gold. The average porosity and its standard deviation along the axial direction through the sample were determined, as well as the characteristic feature size and its standard deviation. The result shows that free corrosion is an effective way to create homogeneous nanoporous metals with sample sizes on the order of 1 µm.

Imaging the dynamical response of materials following ultrafast excitation can reveal energy transduction mechanisms and their dissipation pathways, as well as material stability under conditions far from equilibrium. Such dynamical behavior is challenging to characterize, especially operando at nanoscopic spatiotemporal scales. In this letter, we use X-ray coherent diffractive imaging to show that ultrafast laser excitation of a ZnO nanocrystal induces a rich set of deformation dynamics including characteristic "hard" or inhomogeneous and "soft" or homogeneous modes at different time scales, corresponding respectively to the propagation of acoustic phonons and resonant oscillation of the crystal. By integrating the 3D nanocrystal structure obtained from the ultrafast X-ray measurements with a continuum thermo-electro-mechanical finite element model, we elucidate the deformation mechanisms following laser excitation, in particular, a torsional mode that generates a 50% greater electric potential gradient than that resulting from the flexural mode. Understanding of the time-dependence of these mechanisms on ultrafast scales has significant implications for development of new materials for nanoscale power generation.

Precise management of soil phosphorus (P) to meet competing demands of agriculture and environmental protection can benefit from more comprehensive characterization of P speciation in soils. Our objectives were to provide spatial context for spectroscopic analyses of soil P speciation in relation to molecular-scale species and landscape-scale management of P, and to compare soil P-species diversity from spectroscopic measurements at submicron and millimeter scales. The spatial range of ∼26 orders of magnitude between atomic and field scales presents a challenge to upscaling and downscaling information from spectroscopic analyses of soils. Scanning fluorescence X-ray microscopy images of a 50-μm × 45-μm area of an organic soil sample showed heterogeneous distributions of P, Al, and Si. Microscale X-ray absorption near edge structure (μ-XANES) spectra collected at the P K-edge from 12 spots on the soil sample exhibited diverse features that indicated variations in highly localized P speciation. Linear combination fitting analysis of the μ-XANES spectra included various proportions of three standards that appeared in fits for most spots and five standards that appeared in fits for one spot each. The fit to a bulk-soil spectrum was dominated by two of the common standards in the μ-XANES fits, and a fit to the sum of μ-XANES spectra included four of the standards. These results illustrate a gain in P species sensitivity from spatially resolved XANES analysis. Integrating spectroscopic analyses from multiple scales determines soil P species diversity and will ultimately help connect speciation to the chemical reactivity and mobility of P in soils.

Visualizing the dynamical response of material heterointerfaces is increasingly important for the design of hybrid materials and structures with tailored properties for use in functional devices. In situ characterization of nanoscale heterointerfaces such as metal-semiconductor interfaces, which exhibit a complex interplay between lattice strain, electric potential, and heat transport at subnanosecond time scales, is particularly challenging. In this work, we use a laser pump/X-ray probe form of Bragg coherent diffraction imaging (BCDI) to visualize in three-dimension the deformation of the core of a model core/shell semiconductor-metal (ZnO/Ni) nanorod following laser heating of the shell. We observe a rich interplay of radial, axial, and shear deformation modes acting at different time scales that are induced by the strain from the Ni shell. We construct experimentally informed models by directly importing the reconstructed crystal from the ultrafast experiment into a thermo-electromechanical continuum model. The model elucidates the origin of the deformation modes observed experimentally. Our integrated imaging approach represents an invaluable tool to probe strain dynamics across mixed interfaces under operando conditions.

We report evidence of spontaneous formation of a heterogeneous network of superdomains in two-dimensional square artificial spin ice nanostructures in externally applied magnetic fields. The magnetic heterogeneity is locally disordered but has a zig-zag texture at longer length scales. Resonant coherent soft-x-ray scattering off such textures give rise to unique internal structure in Bragg peaks. Our result shows that the macroscopic magnetic texture is derived from the microscopic structure of the Dirac strings., Main text: 5 pages, 4 figures. Supplemental: 13 pages, 11 figures

We studied the evolution of dealloying-induced strain along the {111} in a Ag-Au nano-crystal in situ, during formation of nanoporous gold at the initial stage of dealloying using Bragg coherent X-ray diffractive imaging. The strain magnitude with maximum probability in the crystal doubled in 10 s of dealloying. Although formation of nano-pores just began at the surface, the greatest strain is located 60-80 nm deep within the crystal. Dealloying induced a compressive strain in this region, indicating volume shrinkage occurred during pore formation. The crystal interior showed a small tensile strain, which can be explained by tensile stresses induced by the non-dealloyed region upon the dealloyed region during volume reduction. A surface strain relaxation developed, attributed to atomic rearrangement during dealloying. This clearer understanding of the role of strain in the initial stages of formation of nanoporous gold by dealloying can be exploited for development of new sensors, battery electrodes, and materials for catalysis.

Multi-keV X-ray microscopy has been particularly successful in bridging the resolution gap between optical and electron microscopy. However, resolutions below 20 nm are still considered challenging, as high throughput direct imaging methods are limited by the availability of suitable optical elements. In order to bridge this gap, we present a new type of Fresnel zone plate lenses aimed at the sub-20 and the sub-10 nm resolution range. By extending the concept of double-sided zone plate stacking, we demonstrate the doubling of the effective line density and thus the resolution and provide large aperture, singlechip optical devices with 15 and 7 nm smallest zone widths. The detailed characterization of these lenses shows excellent optical properties with focal spots down to 7.8 nm. Beyond wave front characterization, the zone plates also excel in typical imaging scenarios, verifying their resolution close to their diffraction limited optical performance., published version, peerReviewed

Phase-diverse X-ray coherent diffractive imaging (CDI) provides a route to high sensitivity and spatial resolution with moderate radiation dose. It also provides a robust solution to the well-known phase-problem, making on-line image reconstruction feasible. Here we apply phase-diverse CDI to a cellular sample, obtaining images of an erythrocyte infected by the sexual stage of the malaria parasite, Plasmodium falciparum, with a radiation dose significantly lower than the lowest dose previously reported for cellular imaging using CDI. The high sensitivity and resolution allow key biological features to be identified within intact cells, providing complementary information to optical and electron microscopy. This high throughput method could be used for fast tomographic imaging, or to generate multiple replicates in two-dimensions of hydrated biological systems without freezing or fixing. This work demonstrates that phase-diverse CDI is a valuable complementary imaging method for the biological sciences and ready for immediate application.

Biological productivity in many ocean regions is controlled by the availability of the nutrient phosphorus. In the Mediterranean Sea, aerosol deposition is a key source of phosphorus and understanding its composition is critical for determining its potential bioavailability. Aerosol phosphorus was investigated in European and North African air masses using phosphorus near-edge X-ray fluorescence spectroscopy (P-NEXFS). These air masses are the main source of aerosol deposition to the Mediterranean Sea. We show that European aerosols are a significant source of soluble phosphorus to the Mediterranean Sea. European aerosols deliver on average 3.5 times more soluble phosphorus than North African aerosols and furthermore are dominated by organic phosphorus compounds. The ultimate source of organic phosphorus does not stem from common primary emission sources. Rather, phosphorus associated with bacteria best explains the presence of organic phosphorus in Mediterranean aerosols.

Nanoporous gold has many potential applications in various fields, including energy storage, catalysis, sensing and actuating. Dealloying of Ag–Au alloys under free corrosion conditions is a simple method to fabricate nanoporous gold. Here, we systematically investigate the dealloying rate of Ag–xAu alloy for a range of alloy compositions (x = 20–40 at.%) and nitric acid concentration (7.3–14.9 M) using in situ transmission X-ray microscopy. High-resolution in situ X-ray projections and ex situ tomographic reconstructions allow imaging of the dealloying front position during dealloying. The dealloying front velocity is constant with time, and depends exponentially on the alloy Ag/Au atomic ratio and the acid molar concentration. Only the leanest alloy, Ag–20 Au, shows a large macroscopic shrinkage in sample diameter (∼38%) after dealloying, which leads to crack nucleation and growth observed in real time during dealloying. Finite element modeling is used to estimate dealloying-induced stresses and strains, and sheds light on the cracks created by the diameter shrinkage.

The dealloying process is directly imaged, for the first time, by using transmission X-ray microscopy for the case of an Ag–30 at.% Au wire dealloyed under free corrosion in nitric acid. The propagation of a sharp dealloying front separating the alloy from nanoporous Au was observed by two-dimensional real-time in situ imaging at 30 nm resolution and measured in detail in three dimensions by an ex situ nanotomography technique at fixed time intervals. The rate of the dealloying front propagation is independent of the dealloying time up to a 3 μm depth, indicating that the dealloying process to this depth is dominated by interfacial effects (i.e. gold surface diffusion and/or silver dissolution) rather than long-range transport effects (i.e. diffusion of acid and corrosion product in and out of the porous layer). The constant dealloying rate corresponds to a constant silver flux and a constant current density, even though the potential might be fluctuating under free corrosion conditions and the interfacial area is shrinking as a function of time. Free corrosion in this system generates a high current density, implying it is driven by a chemical potential difference that is much higher than the critical potential.

We propose a new approach to robustly retrieve the exit wave of an extended sample from its coherent diffraction pattern by exploiting sparsity of the sample’s edges. This approach enables imaging of an extended sample with a single view, without ptychography. We introduce nonlinear optimization methods that promote sparsity, and we derive update rules to robustly recover the sample’s exit wave. We test these methods on simulated samples by varying the sparsity of the edge-detected representation of the exit wave. Our tests illustrate the strengths and limitations of the proposed method in imaging extended samples.

The performance of a diamond X-ray phase retarder to enable the production of circularly polarized X-rays has been quantitatively measured and magnetic dichroism contrast in transmission and diffraction geometries has been demonstrated. Feasibility tests for dichroic Bragg coherent diffractive imaging experiments were performed and showed that the diamond X-ray phase retarder does not produce significant distortions to the X-ray wavefront and that Bragg coherent diffractive imaging reconstructions are achievable., Recent progress in the development of dichroic Bragg coherent diffractive imaging, a new technique for simultaneous three-dimensional imaging of strain and magnetization at the nanoscale, is reported. This progress includes the installation of a diamond X-ray phase retarder at beamline 34-ID-C of the Advanced Photon Source. The performance of the phase retarder for tuning X-ray polarization is demonstrated with temperature-dependent X-ray magnetic circular dichroism measurements on a gadolinium foil in transmission and on a Gd5Si2Ge2 crystal in diffraction geometry with a partially coherent, focused X-ray beam. Feasibility tests for dichroic Bragg coherent diffractive imaging are presented. These tests include (1) using conventional Bragg coherent diffractive imaging to determine whether the phase retarder introduces aberrations using a nonmagnetic gold nanocrystal as a control sample, and (2) collecting coherent diffraction patterns of a magnetic Gd5Si2Ge2 nanocrystal with left- and right-circularly polarized X-rays. Future applications of dichroic Bragg coherent diffractive imaging for the correlation of strain and lattice defects with magnetic ordering and inhomogeneities are considered.

Operando characterization of gas-solid reactions at the atomic scale is of great importance for determining the mechanism of catalysis. This is especially true in the study of heterostructures because of structural correlation between the different parts. However, such experiments are challenging and have rarely been accomplished. In this work, atomic scale redox dynamics of Ag/AgCl heterostructures have been studied using in situ environmental transmission electron microscopy (ETEM) in combination with density function theory (DFT) calculations. The reduction of Ag/AgCl to Ag is likely a result of the formation of Cl vacancies while Ag(+) ions accept electrons. The oxidation process of Ag/AgCl has been observed: rather than direct replacement of Cl by O, the Ag/AgCl nanocatalyst was first reduced to Ag, and then Ag was oxidized to different phases of silver oxide under different O2 partial pressures. Ag2O formed at low O2 partial pressure, whereas AgO formed at atmospheric pressure. By combining in situ ETEM observation and DFT calculations, this structural evolution is characterized in a distinct nanoscale environment.

The three-dimensional evolution of nanoligaments of nanoporous gold created by Ag–Au dealloying was studied during isothermal coarsening by X-ray nanotomography and microbeam Laue diffraction. The surface normal orientation, curvature and size of the gold nanoligaments were measured as a function of coarsening time (from 2 to 320 min). The following observations were made at 550, 600 and 650 °C. First, the distribution of orientations for the surfaces of the nanoligaments becomes more anisotropic with coarsening time, with an increasing area of the surfaces having a low surface energy, consistent with the growth of facets. Second, the curvature distribution of the nanoligaments (scaled by their size) also evolves during coarsening. The evolution of both surface orientation and scaled surface curvature indicates that coarsening does not occur in a self-similar manner, i.e. the interfacial shape distribution of the gold nanoligaments is not self-similar over time as they coarsen. This is consistent with the ligament size not being described by a classical temporal power law for coarsening systems. All three effects, and in particular the increased prevalence of surfaces with a low surface energy at long coarsening times, may affect the surface functionalities and properties of nanoporous gold in various applications, e.g. as catalysts, sensors and actuators.

In recent years, the relevance of physico-chemical heterogeneity patterns in soils at the micron and submicron scale for the regulation of biogeochemical processes has become increasingly evident. For an organic surface soil horizon from a forested Histosol in Germany, microspatial patterns of element distribution (sulfur, phosphorus, aluminium, silicon) and S speciation were investigated by synchrotron-based X-ray spectromicroscopy. Microspatial patterns of S, P, Al and Si contents in the organic topsoil were assessed for a sample region of 50 μm × 30 μm by spatially resolving μ-XRF. Sulfur speciation at four microsites was investigated by focused X-ray absorption near edge structure (μ-XANES) spectroscopy at the S K -edge. The results show a heterogeneous distribution of the investigated elements on the (sub)micron scale, allowing the identification of diatoms, aluminosilicate mineral particles and sulfide minerals in the organic soil matrix. Evaluation of the S K -edge μ-XANES spectra acquired at four different microsites by linear combination fitting revealed a substantial microspatial heterogeneity of S speciation, characterized by the presence of distinct enrichment zones of inorganic sulfide and zones with dominant organic disulfide S within a few micrometers distance, and coexistence of different S species (e.g. reduced inorganic and organic S compounds) at a spatial scale below the resolution of the instrument (60 nm × 60 nm; X-ray penetration depth: 30 μm).

We report a novel experimental approach to derive quantitative concentration map of light elements in whole cells by combining two complementary nano-probe methods: X-ray fluorescence microscopy (XRFM) and atomic force microscopy (AFM). The concentration is derived by normalizing point-by-point the elemental (here Mg) spatial distribution obtained by XRFM, by the thickness measured using AFM. The considerable difference between the elemental distribution and the concentration maps indicates that this procedure is essential to obtain reliable information on the role and function of elements in whole cells. (C) 2011 Elsevier B.V. All rights reserved.

The desmid green alga Closterium moniliferum belongs to a small number of organisms that form barite (BaSO(4)) or celestite (SrSO(4)) biominerals. The ability to sequester Sr in the presence of an excess of Ca is of considerable interest for the remediation of (90)Sr from the environment and nuclear waste. While most cells dynamically regulate the concentration of the second messenger Ca(2+) in the cytosol and various organelles, transport proteins rarely discriminate strongly between Ca, Sr, and Ba. Herein, we investigate how these ions are trafficked in C. moniliferum and how precipitation of (Ba,Sr)SO(4) crystals occurs in the terminal vacuoles. Towards this goal, we simultaneously visualize intracellular dynamics of multiple elements using X-ray fluorescence microscopy (XFM) of cryo-fixed/freeze-dried samples. We correlate the resulting elemental maps with ultrastructural information gleaned from freeze-fracture cryo-SEM of frozen-hydrated cells and use micro X-ray absorption near edge structure (micro-XANES) to determine sulfur speciation. We find that the kinetics of Sr uptake and efflux depend on external Ca concentrations, and Sr, Ba, and Ca show similar intracellular localization. A highly ion-selective cross-membrane transport step is not evident. Based on elevated levels of sulfate detected in the terminal vacuoles, we propose a "sulfate trap" model, where the presence of dissolved barium leads to preferential precipitation of (Ba,Sr)SO(4) due to its low solubility relative to SrSO(4) and CaSO(4). Engineering the sulfate concentration in the vacuole may thus be the most direct way to increase the Sr sequestered per cell, an important consideration in using desmids for phytoremediation of (90)Sr.

High-resolution X-ray imaging techniques using optical elements such as zone plates are widely used for viewing the internal structure of samples in exquisite detail. The resolution attainable is ultimately limited by the manufacturing tolerances for the optics. Combining ideas from crystallography and holography, this limit may be surpassed by the method of coherent diffractive imaging (CDI) 1 . Although CDI shows particular promise in applications involving X-ray free-electron lasers 2 , it is also emerging as an important new technique for imaging at third-generation synchrotrons. The limited coherent output of these sources, however, is a significant barrier to obtaining shorter exposure times. A fundamental assumption of coherent diffractive imaging is that the incident light is well-approximated by a single optical frequency. In this Letter, we demonstrate the first experimental realization of ‘polyCDI’, using a broadband source to achieve a factor of 60 reduction in the exposure time over quasi-monochromatic coherent diffractive imaging. Over the past decade, the extension of crystallographic techniques to the high-resolution imaging of non-crystalline objects 3 has proved enormously successful in a wide variety of applications 4 . Iterative retrieval of the phase of the far-field diffraction pattern permits reconstruction of the diffracting object with a spatial resolution that is limited, in principle, only by the wavelength of the incident illumination. In crystallography, the periodic arrangement of atoms amplifies the signal diffracted from the unit cell, making detection of the Bragg peaks straightforward. A main goal for coherent diffractive imaging (CDI) is to develop it into a form of highspatial-resolution microscopy that can be routinely applied using synchrotron sources. In this endeavour it must compete with the very successful results obtained using zone-plate-based full-field transmission X-ray microscopy 5 . A fundamental issue for both forms of imaging is that higher spatial resolution requires that the sample be illuminated with a greater number of photons per resolution element, scaling approximately as the fourth power of the desired spatial resolution 6 . Although it has been asserted that CDI is able to achieve equivalent resolution to zone plate microscopy, but with fewer photons 7 , the two techniques are limited to precisely the same degree by the spectral bandwidth (longitudinal coherence length) of the incident light. Significant increases in the spatial resolution require brighter sources, much longer exposure times or the capacity to increase the acceptable limits on the bandwidth. A pathway to achromatic zone plates has been proposed 8 that

Several non‐destructive imaging techniques offer the possibility to observe rapid phenomena in real time, yet most of these techniques fail when it comes to bulky samples and micrometer precision in three dimensions. Therefore there is clearly a need to develop approaches that address such conditions. We identified the large potential that lies in synchrotron‐based x‐rays as a probe and developed a direct‐space tomographic instrument suitable to provide sub‐second temporal resolution with several‐micrometers spatial resolution. Selected applications from the field of biology and material science are shown in order to demonstrate the unique capabilities in generating three‐dimensional images with very high quality making image segmentation and analysis possible for samples that could, until now, only be studied in two dimensions due to the occurrence of rapid structural changes.

Phosphorus K-edge XANES spectra are presented for a diverse set of 44 phosphate minerals., Phosphorus K-edge X-ray absorption near-edge structure (XANES) spectroscopy was performed on phosphate mineral specimens including (a) twelve specimens from the apatite group covering a range of compositional variation and crystallinity; (b) six non-apatite calcium-rich phosphate minerals; (c) 15 aluminium-rich phosphate minerals; (d) ten phosphate minerals rich in either reduced iron or manganese; (e) four phosphate minerals rich in either oxidized iron or manganese; (f) eight phosphate minerals rich in either magnesium, copper, lead, zinc or rare-earth elements; and (g) four uranium phosphate minerals. The identity of all minerals examined in this study was independently confirmed using X-ray powder diffraction. Minerals were distinguished using XANES spectra with a combination of pre-edge features, edge position, peak shapes and post-edge features. Shared spectral features were observed in minerals with compositions dominated by the same specific cation. Analyses of apatite-group minerals indicate that XANES spectral patterns are not strongly affected by variations in composition and crystallinity typical of natural mineral specimens.

X-ray fluorescence tomography promises to map elemental distributions in unstained and unfixed biological specimens in three dimensions at high resolution and sensitivity, offering unparalleled insight in medical, biological, and environmental sciences. X-ray fluorescence tomography of biological specimens has been viewed as impractical—and perhaps even impossible for routine application—due to the large time required for scanning tomography and significant radiation dose delivered to the specimen during the imaging process. Here, we demonstrate submicron resolution X-ray fluorescence tomography of a whole unstained biological specimen, quantifying three-dimensional distributions of the elements Si, P, S, Cl, K, Ca, Mn, Fe, Cu, and Zn in the freshwater diatom Cyclotella meneghiniana with 400-nm resolution, improving the spatial resolution by over an order of magnitude. The resulting maps faithfully reproduce cellular structure revealing unexpected patterns that may elucidate the role of metals in diatom biology and of diatoms in global element cycles. With anticipated improvements in data acquisition and detector sensitivity, such measurements could become routine in the near future.

For a toposequence with increasing groundwater influence (Cambisol, Stagnosol, Histosol) and with different groundwater regimes (Histosols 1 and 2) in a forested watershed in the Fichtelgebirge (Germany), the speciation of sulfur (S) and iron (Fe) in the soils was assessed by X-ray absorption near-edge spectroscopy (XANES) after anoxic and conventional oxic sample pretreatments. For samples with anoxic pretreatment, the contribution of reduced inorganic S compounds (monosulfide, pyrite) to total S increased with soil depth for the Cambisol and the Stagnosol, but decreased for the Histosols; the opposite trend was noticed for the contribution of reduced organic S (organic mono- and disulfides, thiols). The contribution of reduced S to the soil S pool increased and the contribution of oxidized S compounds decreased in the sequence Cambisol–Stagnosol–Histosol 1 (permanently anoxic). Histosol 2 (seasonally oxic) showed a markedly larger contribution of oxidized and intermediate S compounds to total S than Histosol 1. The dominating Fe-bearing phases in the Cambisol were Fe(III) oxyhydroxides; the contribution of sulfide-bound Fe was 2 during the entire period between sampling and analysis is crucial for a correct S and Fe speciation. Only after appropriate sample preparation, clear relationships between the mean oxidation states of S and Fe (MOFe) on one hand and soil hydrological conditions on the other become evident: a concomitant systematic decrease of MOS and MOFe from the well-aerated Cambisol to the permanently anoxic Histosol 1, and larger MOS and MOFe in the seasonally oxic Histosol 2 than in Histosol 1 indicate a close coupling of S and Fe cycling in the soils. Finally, the results of our study suggest that in organic horizons of wetland soils inorganic sulfide S is overestimated and reduced organic S is underestimated by S K -edge XANES, if a significant portion of the thiol groups in reduced organic S is complex-bound to Fe 2+ or other chalcophilic metal cations. This is supported by the observation that synthetic organic compounds (cysteine; 1,3,5-trimer-captotriazine [TMT]; ferredoxin) after addition of Fe show spectra with pre-edge peaks at energies

In forested catchments, retention and remobilization of S in soils and wetlands regulate soil and water acidification. The prediction of long-term S budgets of forest ecosystems under changing environmental conditions requires a precise quantification of all relevant soil S pools, comprising S species with different remobilization potential. In this study, the S speciation in topsoil horizons of a soil toposequence with different groundwater influence and oxygen availability was assessed by synchrotron-based X-ray absorption near-edge spectroscopy (XANES). Our investigation was conducted on organic (O, H) and mineral topsoil (A, AE) horizons of a Cambisol–Stagnosol–Histosol catena. We studied the influence of topography (i.e., degree of groundwater influence) and oxygen availability on the S speciation. Soil sampling and pretreatment were conducted under anoxic conditions. With increasing groundwater influence and decreasing oxygen availability in the sequence Cambisol–Stagnosol–Histosol, the C : S ratio in the humic topsoil decreased, indicating an enrichment of soil organic matter in S. Moreover, the contribution of reduced S species (inorganic and organic sulfides, thiols) increased systematically at the expense of intermediate S species (sulfoxide, sulfite, sulfone, sulfonate) and oxidized S species (ester sulfate, SO). These results support the concept of different S-retention processes for soils with different oxygen availability. Sulfur contents and speciation in two water-logged Histosols subject to permanently anoxic and temporarily oxic conditions, respectively, were very different. In the anoxic Histosol, reduced S accounted for 57% to 67% of total S; in the temporarily oxic Histosol, reduced S was only 43% to 54% of total S. Again, the extent of S accumulation and the contribution of reduced S forms to total S closely reflected the degree of O2 availability. Our study shows that XANES is a powerful tool to elucidate key patterns of the biogeochemical S cycling in oxic and anoxic soil environments. In contrast to traditional wet-chemical methods, it particularly allows to distinguish organic S compounds in much more detail. It can be used to elucidate microbial S-metabolism pathways in soils with different oxygen availability by combining soil inventories and repeated analyses of a sample in different stages of field or laboratory incubation experiments under controlled boundary conditions and also to study (sub)microspatial patterns of S speciation in aggregated soils.

The in situ or authigenic formation of calcium phosphate minerals in marine sediments is a major sink for the vital nutrient phosphorus. However, because typical sediment chemistry is not kinetically conducive to the precipitation of these minerals, the mechanism behind their formation has remained a fundamental mystery. Here, we present evidence from high-sensitivity x-ray and electrodialysis techniques to describe a mechanism by which abundant diatom-derived polyphosphates play a critical role in the formation of calcium phosphate minerals in marine sediments. This mechanism can explain the puzzlingly dispersed distribution of calcium phosphate minerals observed in marine sediments worldwide.

X-ray spectromicroscopy is a powerful tool for addressing key questions in the environmental sciences due to its high spectral and spatial resolution. It has been used successfully for material research, biology and environmental studies, e.g. in the form of μ-X-ray fluorescence and spectromicroscopy with a spatial resolution of

We show that the radiation from a helical undulator not only carries spin angular momentum (circular polarization) but also orbital angular momentum. This exotic property of the undulator radiation may be useful in coherent X-ray imaging and scattering experiments and to probe electronic transitions in matter by orbital dichroism spectroscopy. Also, we present that a new magnet configuration, similar to the structure of Figure-8 undulator or the PERA undulator, may generate right- and left-hand circularly polarized off-axis radiation simultaneously.

Fluctuation microscopy is a hybrid diffraction-imaging technique that detects medium range order in amorphous materials by examining spatial fluctuations in coherent scattering. These fluctuations appear as speckle in images and diffraction patterns. The volume of material contributing to the speckle is determined by the point-spread function (the resolution) of the imaging optics and the sample thickness. The spatial periodicities being probed are related to the diffraction vector. Statistical analysis of the speckle allows the random and non-random (ordered) contributions to be discriminated. The image resolution that gives the maximum speckle contrast, as determined by the normalized variance of the image intensity, is determined by the characteristic length scale of the ordering. Because medium range ordering length scales can extend out to about the tenth coordination shell, fluctuation microscopy tends to be a low image resolution technique.This review presents the kinematical scattering theory underpinning fluctuation microscopy and a description of fluctuation electron microscopy as it has been employed in the transmission electron microscope for studying amorphous materials. Recent results using soft x-rays for studying nanoscale materials are also presented. We summarize outstanding issues and point to possible future directions for fluctuation microscopy as a technique.

Fluctuation microscopy examines the spatial variations in coherent microdiffraction from an ensemble of small volumes in noncrystalline systems. The variance of scattered intensity into regions of reciprocal space can be used to give insight into three-body and four-body correlation functions, which are sensitive to medium-range order. The technique was originally developed for transmission electron microscopy and was successfully used to understand medium-range order in amorphous silicon and germanium. Applying this method to X-rays, we have developed a new approach: fluctuation X-ray microscopy (FXM). The approach offers quantitative insight into medium-range correlations in materials at nanometer and larger length scales. The FXM technique can be used to explore medium-range order and subtle structural changes in a wide range of disordered materials from soft matter to nanocomposites, nanowire and quantum dot arrays. We have demonstrated this new technique by studying films of polystyrene latex spheres.

We report a reconstruction of the phase space distribution of an X-ray beam after it has passed through a set of Young's slits. The resulting interference pattern has a quasi-probability distribution that has negative regions that do not have a classical interpretation. We experimentally reconstruct and observe these negative parts of the phase space distribution.

We used hard x-ray fluorescence and soft x-ray transmission microscopy to quantitatively measure “in situ” Cu/SiO2 interconnect dimensions down to 0.3 μm dimensions. We describe methods and analysis techniques for measuring submicron linewidths, lengths, and thicknesses with accuracies of 30–60 nm precision. The dimensions and shape of submicron Cu vias, W lines, and a 20 nm Ta liner and an electromigration defect (void) were determined by these methods. These nondestructive techniques promise to be useful for nanometer precision metrology studies of a variety of materials systems.

Tomographic X-ray phase reconstructions of an atomic force microscope tip with a spatial resolution of better than 900 nm are presented. The data was acquired using an X-ray energy of 1.83 keV using a zone plate based microscope at a third generation synchrotron, the Advanced Photon Source at the Argonne National Laboratory. The phase tomographic data is quantitatively accurate and we confirm that the deduced refractive index is in agreement with the known properties of the sample. Our results open the way for full 3D imaging of the complex refractive index with sub-micron spatial resolution.

The rational design of novel catalysts for CO2 reduction has attracted considerable attention, owing to the increasing global fuel demand and greenhouse gas emission. Cu2O has been suggested to be thermodynamically capable of photocatalytically reducing CO2 to methanol.1 However, due to the inertness of CO2 molecules, it is relatively hard for CO2 to draw electrons from the catalyst and become reactive. Earlier studies have shown that the CO2 conversion rate is quite limited on stoichiometric, defect-free oxide surfaces due to the low catalytic activity; on the other hand, defected surfaces generally have higher activity and may provide better catalytic performance.2 In this work, we performed density functional theory (DFT) calculations to investigate the catalytic activity of Cu2O(110) surface, with a primary focus on the surface affinity of CO2 molecules. The preferred CO2 adsorption sites and configurations on both pristine and defected Cu2O(110) surfaces are determined, and the surface stoichiometry that favors CO2 adsorption is thus identified. Scanning tunneling microscopy (STM) images and X-ray Absorption Near-Edge Structures (XANES) of various adsorption configurations are also simulated within the first-principles framework. The results from this study demonstrate the importance of rational surface engineering of catalysts for effective CO2 conversion, and provide important insight into experiment design. (1) Bendavid, L. I.; Carter, E. a. First-Principles Predictions of the Structure, Stability, and Photocatalytic Potential of Cu2O Surfaces. J. Phys. Chem. B 2013, 117 (49), 15750–15760. (2) Liu, L.; Zhao, H.; Andino, J. M.; Li, Y. Photocatalytic CO2 Reduction with H2O on TiO2Nanocrystals: Comparison of Anatase, Rutile, and Brookite Polymorphs and Exploration of Surface Chemistry. ACS Catal. 2012, 2 (8), 1817–1828.