Saltwater intrusion increases phosphorus abundance and alters availability in coastal soils with implications for future sea level rise.

Sea level rise (SLR) promotes saltwater intrusion (SWI) into coastal soils globally at an increasing rate, impacting phosphorus (P) dynamics and adjacent water quality. However, how SWI influences P molecular speciation and availability in coastal soils remains poorly understood. By using a space-for-time substitution strategy, we evaluated the SWI impacts on P transformation along a SWI gradient at the Rehoboth Inland Bay, which consists of five sampling locations along a transect representing different SWI degrees. Soils were analyzed at the macro- and micro-scale using X-ray absorption near edge spectroscopy (XANES) and the modified Hedley fractionation. With increasing distance from the Bay, soil salinity (29.3-0.07 mmhos cm-1), the proportion of Fe3+ to total Fe, and P concentrations decreased. The fractionation showed that recalcitrant P was dominant (86.9-89.5% of total P). With increasing SWI, labile P increased gradually, reached a plateau, and then decreased sharply. Bulk XANES spectroscopy showed that soil P was likely dominated by iron and aluminum-associated P (Fe/Al-P), regardless of the SWI degree. Hence, with increasing SWI, P increasingly accumulated in a recalcitrant pool, mainly as Fe/Al-P. µ-XANES spectroscopy revealed that calcium-associated P (Ca-P) existed in P-rich spots of the greatest SWI soil while Al-P occurred in P-rich spots of the low SWI soil, consistent with the greater HCl-P (presumably Ca-P) in the former soil. Overall, results demonstrate that SWI impacts P availability and environmental risk in coastal soils depending on the degree of SWI. These findings have important implications for understanding soil P cycling and availability in SLR-impacted coastal areas.

Subglacial precipitates record Antarctic ice sheet response to late Pleistocene millennial climate cycles.

Ice cores and offshore sedimentary records demonstrate enhanced ice loss along Antarctic coastal margins during millennial-scale warm intervals within the last glacial termination. However, the distal location and short temporal coverage of these records leads to uncertainty in both the spatial footprint of ice loss, and whether millennial-scale ice response occurs outside of glacial terminations. Here we present a >100kyr archive of periodic transitions in subglacial precipitate mineralogy that are synchronous with Late Pleistocene millennial-scale climate cycles. Geochemical and geochronologic data provide evidence for opal formation during cold periods via cryoconcentration of subglacial brine, and calcite formation during warm periods through the addition of subglacial meltwater originating from the ice sheet interior. These freeze-flush cycles represent cyclic changes in subglacial hydrologic-connectivity driven by ice sheet velocity fluctuations. Our findings imply that oscillating Southern Ocean temperatures drive a dynamic response in the Antarctic ice sheet on millennial timescales, regardless of the background climate state.

Elucidation of soil phosphorus speciation in mid-Atlantic soils using synchrotron-based microspectroscopic techniques.

Phosphorus deficiency and excess are concomitant problems in agricultural soils of the mid-Atlantic region. A fundamental understanding of soil P speciation is essential to assess P fate and transport in these soils. Current methods for soil P speciation often rely on sequential chemical extractions, which can introduce artifacts during analysis. To overcome limitations of current methods, this study evaluated synchrotron-based micro-focused X-ray fluorescence (µ-XRF) and X-ray absorption near-edge spectroscopy (µ-XANES) techniques to assess soil P speciation in agricultural soils collected from the mid-Atlantic region of the United States. Three soils with varying chemical and physical properties were analyzed with µ-XRF maps collected at high (12,000 eV) and tender (2240 eV) energies to evaluate colocation of P with Fe, Al, Ca, and Si in soil samples, and µ-XANES spectra were collected at the P K-edge for P hotspots. Combined µ-XRF and µ-XANES analysis was useful for identifying Ca phosphate, Fe phosphate, Al-sorbed P, and Fe-sorbed P species in heterogeneous soil samples. X-ray fluorescence maps were valuable to distinguish Al-oxide sorbed P from Fe-oxide sorbed P species. A low signal-to-noise ratio often limited µ-XANES data collection in regions with diffuse, low concentrations of P. Therefore, some P species may not have been detected during analysis. Even with varying degrees of self-absorption and signal-to-noise ratios in µ-XANES spectra, important inferences regarding P speciation in mid-Atlantic soils were made. This study highlights the potential of µ-XANES analysis for use in environmental and agricultural sciences to provide insights into P fate and transport in soils.

The TES beamline (8-BM) at NSLS-II: tender-energy spatially resolved X-ray absorption spectroscopy and X-ray fluorescence imaging.

The tender-energy X-ray spectroscopy (TES) beamline at the National Synchrotron Light Source II (NSLS-II) is now operational for general users. Its scientific mission includes static and in situ X-ray fluorescence imaging and spatially resolved X-ray absorption spectroscopy for characterization of complex heterogeneous, structured and dynamic natural or engineered materials and systems. TES is optimized for the tender-energy range, offering routine operations from 2.0 to 5.5 keV, with capabilities to reach down to 1.2 or up to 8 keV with configuration change. TES is designed as an extended X-ray absorption fine-structure microprobe (EXAFS microprobe) for applications of micrometre-scale EXAFS spectroscopy to heterogeneous samples. Beam size is user-tunable from ∼2 to 25 µm. Energy may be scanned on-the-fly or in traditional step scanning. Importantly, the position of the microbeam at the sample location does not move significantly during energy scanning or when changing energy across the entire routine energy range. This enables full EXAFS of a particle or domain the same size as the probe beam, and measurement of the same spot at different energies. In addition, there is no measureable drift in energy calibration (repeatability) scan-to-scan and over 24 h. This is critical where simultaneous calibration measurements are generally not feasible, and for speciation mapping where precise and stable control of incident energy is essential. The sample environment is helium atmosphere at room pressure with infrastructure for in situ electrochemistry and catalysis in small sample cells or microreactors. As the first bend-magnet beamline at NSLS-II, noteworthy commissioning aspects are described. Example measurements are presented to illustrate its capabilities.

Anionic redox reaction in layered NaCr2/3Ti1/3S2 through electron holes formation and dimerization of S-S.

The use of anion redox reactions is gaining interest for increasing rechargeable capacities in alkaline ion batteries. Although anion redox coupling of S2- and (S2)2- through dimerization of S-S in sulfides have been studied and reported, an anion redox process through electron hole formation has not been investigated to the best of our knowledge. Here, we report an O3-NaCr2/3Ti1/3S2 cathode that delivers a high reversible capacity of ~186 mAh g-1 (0.95 Na) based on the cation and anion redox process. Various charge compensation mechanisms of the sulfur anionic redox process in layered NaCr2/3Ti1/3S2, which occur through the formation of disulfide-like species, the precipitation of elemental sulfur, S-S dimerization, and especially through the formation of electron holes, are investigated. Direct structural evidence for formation of electron holes and (S2)n- species with shortened S-S distances is obtained. These results provide valuable information for the development of materials based on the anionic redox reaction.

Studying biomineralization pathways in a 3D culture model of breast cancer microcalcifications.

Microcalcifications serve as diagnostic markers for breast cancer, yet their formation pathway(s) and role in cancer progression are debated due in part to a lack of relevant 3D culture models that allow studying the extent of cellular regulation over mineralization. Previous studies have suggested processes ranging from dystrophic mineralization associated with cell death to bone-like mineral deposition. Here, we evaluated microcalcification formation in 3D multicellular spheroids, generated from non-malignant, pre-cancer, and invasive cell lines from the MCF10A human breast tumor progression series. The spheroids with greater malignancy potential developed necrotic cores, thus recapitulating spatially distinct viable and non-viable areas known to regulate cellular behavior in tumors in vivo. The spatial distribution of the microcalcifications, as well as their compositions, were characterized using nanoCT, electron-microscopy, and X-ray spectroscopy. Apatite microcalcifications were primarily detected within the viable cell regions and their number and size increased with malignancy potential of the spheroids. Levels of alkaline phosphatase decreased with malignancy potential, whereas levels of osteopontin increased. These findings support a mineralization pathway in which cancer cells induce mineralization in a manner that is linked to their malignancy potential, but that is distinct from physiological osteogenic mineralization.

Applications of "Tender" Energy (1-5 keV) X-ray Absorption Spectroscopy in Life Sciences.

The "tender" energy range of 1 to 5 keV, between the energy ranges of most "hard" (>5 keV) and "soft" (<1 keV) synchrotron X-ray facilities, offers some unique opportunities for synchrotron- based X-ray absorption fine structure spectroscopy in life sciences. In particular the K absorption edges of Na through Ca offer opportunities to study local structure, speciation, and chemistry of many important biological compounds, structures and processes. This is an area of largely untapped science, in part due to a scarcity of optimized facilities. Such measurements also entail unique experimental challenges. This brief review describes the technique, its experimental challenges, recent progress in development of microbeam measurement capabilities, and several highlights illustrating applications in life sciences.

Surface loading effects on orthophosphate surface complexation at the goethite/water interface as examined by extended X-ray Absorption Fine Structure (EXAFS) spectroscopy.

To investigate the effect of P surface loading on the structure of surface complexes formed at the goethite/water interface, goethite was reacted with orthophosphate at P concentrations of 0.1, 0.2, and 0.8 mmol L(-1) at pH 4.5 for 5 days. The P concentrations were chosen to ensure that P loadings at the surface would allow one to follow the transition between adsorption and surface precipitation. Extended X-ray Absorption Fine Structure (EXAFS) spectra were collected in fluorescence mode at the P K-edge at 2150 eV. The structural parameters were obtained through the fits of the sorption data to single and multiple scattering paths using Artemis. EXAFS analysis revealed a continuum among the different surface complexes, with bidentate mononuclear ((2)E), bidentate binuclear ((2)C) and monodentate mononuclear ((1)V) surface complexes forming at the goethite/water interface under the studied conditions. The distances for P-O (1.51-1.53Å) and P-Fe (3.2-3.3Å for bidentate binuclear and around 3.6Å for mononuclear surface complexes) shells observed in our study were consistent with distances obtained via other spectroscopic techniques. The shortest P-Fe distance of 2.83-2.87Å was indicative of a bidentate mononuclear bonding configuration. The coexistence of different surface complexes or the predominance of one sorption mechanism over others was directly related to surface loading.

Residence time and pH effects on the bonding configuration of orthophosphate surface complexes at the goethite/water interface as examined by Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy.

Identifying the mechanisms by which P is bound to soils and soil constituents is ultimately important as they provide information on the stability of bound species and their reactivity in the environment. EXAFS studies were carried out to provide information on how the local chemical environment of sorbed P changes as an effect of pH and time. Goethite was reacted with orthophosphate at a P concentration of 0.8mmolL(-1) P at pH 3.0, 4.5 and 6.0. The residence time effect on the mechanisms of P sorption on goethite was also evaluated for two different reaction times, 5 and 18days, on goethite suspensions reacted at pH 4.5. The objective of this study was to understand how P sorption mechanisms change over a wide pH range when subjected to P concentrations above the P saturation ratio of goethite. Phosphorus K-edge EXAFS spectra were collected at 2150eV in fluorescence mode and the structural parameters were obtained through the fits of sorption data using Artemis. The monodentate surface complex was shown to be the predominant mechanism by which P sorbs at the goethite surface under the experimental conditions. The lack of a discrete Fe-P shell and the presence of highly disordered structures, particularly, at R-space ⩾3.5 suggested the formation of P surface precipitates at the goethite/water interface.

Control of sulfidogenesis through bio-oxidation of H2S coupled to (per)chlorate reduction.

We investigated H2S attenuation by dissimilatory perchlorate-reducing bacteria (DPRB). All DPRB tested oxidized H2S coupled to (per)chlorate reduction without sustaining growth. H2S was preferentially utilized over organic electron donors resulting in an enriched (34S)-elemental sulfur product. Electron microscopy revealed elemental sulfur production in the cytoplasm and on the cell surface of the DPRB Azospira suillum. Based on our results, we propose a novel hybrid enzymatic-abiotic mechanism for H2S oxidation similar to that recently proposed for nitrate-dependent Fe(II) oxidation. The results of this study have implications for the control of biosouring and biocorrosion in a range of industrial environments.

Synchrotron radiation in life sciences.

Synchrotron Radiation (SR) presents itself as a "play-ground" with a large range of methods and techniques suitable to unveil the mysteries of life. Here we attempt to present a few of these methods that complement those employed in the home laboratory. SR diffraction, spectroscopy and imaging methods relevant to the atomic structure determination and characterization of the properties and function of chemical compounds and macromolecules of biological relevance, are introduced.

Products of SO2 adsorption on fuel cell electrocatalysts by combination of sulfur K-edge XANES and electrochemistry.

Electrochemical adsorption of SO(2) on platinum is complicated by the change in sulfur oxidation state with potential. Here, we attempt to identify SO(2) adsorption products on catalyst coated membranes (CCMs) at different electrode potentials using a combination of in situ sulfur K-edge XANES (X-ray absorption near-edge structure) spectroscopy and electrochemical techniques. CCMs employed platinum nanoparticles supported on Vulcan carbon (Pt/VC). SO(2) was adsorbed from a SO(2)/N(2) gas mixture while holding the Pt/VC-electrode potential at 0.1, 0.5, 0.7, and 0.9 V vs a reversible hydrogen electrode (RHE). Sulfur adatoms (S(0)) are identified as the SO(2) adsorption products at 0.1 V, while mixtures of S(0), SO(2), and sulfate/bisulfate ((bi)sulfate) ions are suggested as SO(2) adsorption products at 0.5 and 0.7 V. At 0.9 V, SO(2) is completely oxidized to (bi)sulfate ions. The identity of adsorbed SO(2) species on Pt/VC catalysts at different electrode potentials is confirmed by modeling of XANES spectra using FEFF8 and a linear combination of experimental spectra from sulfur standards. Results on SO(2) speciation gained from XANES are used to compare platinum-sulfur electronic interactions for Pt(3)Co/VC versus Pt/VC catalysts in order to understand the difference between the two catalysts in terms of SO(2) contamination.

Phosphorus K-edge XANES spectroscopy of mineral standards.

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.