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The separation of bromine (Br) to the surface of moist air is analyzed by using Rutherford backscattering spectrometry (RBS) in the measurement of Br concentration in the near surface region of bromine-doped sodium chloride single crystals. The natural aerosol particles show a higher Br/Cl molar ratio compared to seawater.

JUNGFRAU (adJUstiNg Gain detector FoR the Aramis User station) is a two-dimensional hybrid pixel detector for photon science applications at free-electron lasers and synchrotron light sources. The JUNGFRAU 0.4 prototype presented here is specifically geared towards low-noise performance and hence soft X-ray detection. The design, geometry and readout architecture of JUNGFRAU 0.4 correspond to those of other JUNGFRAU pixel detectors, which are charge-integrating detectors with 75 µm × 75 µm pixels. Main characteristics of JUNGFRAU 0.4 are its fixed gain and r.m.s. noise of as low as 27 e− electronic noise charge (<100 eV) with no active cooling. The 48 × 48 pixels JUNGFRAU 0.4 prototype can be combined with a charge-sharing suppression mask directly placed on the sensor, which keeps photons from hitting the charge-sharing regions of the pixels. The mask consists of a 150 µm tungsten sheet, in which 28 µm-diameter holes are laser-drilled. The mask is aligned with the pixels. The noise and gain characterization, and single-photon detection as low as 1.2 keV are shown. The performance of JUNGFRAU 0.4 without the mask and also in the charge-sharing suppression configuration (with the mask, with a `software mask' or a `cluster finding' algorithm) is tested, compared and evaluated, in particular with respect to the removal of the charge-sharing contribution in the spectra, the detection efficiency and the photon rate capability. Energy-dispersive and imaging experiments with fluorescence X-ray irradiation from an X-ray tube and a synchrotron light source are successfully demonstrated with an r.m.s. energy resolution of 20% (no mask) and 14% (with the mask) at 1.2 keV and of 5% at 13.3 keV. The performance evaluation of the JUNGFRAU 0.4 prototype suggests that this detection system could be the starting point for a future detector development effort for either applications in the soft X-ray energy regime or for an energy-dispersive detection system. [ABSTRACT FROM AUTHOR]

Phosphine metal–organic frameworks (P-MOFs) are crystalline porous coordination polymers that contain phosphorus functional groups within their pores. We present the use of X-ray absorption spectroscopy (XAS) at the P K-edge to determine the phosphine to phosphine oxide ratio in two P-MOFs with MIL-101 topology. The phosphorus oxidation state is of particular interest as it strongly influences the coordination affinity of these materials for transition metals. This method can determine the oxidation state of phosphorus even when the material contains paramagnetic nuclei, differently from NMR spectroscopy. We observed that phosphine in LSK-15 accounts for 72 ± 4% of the total phosphorus groups and that LSK-12 contains only phosphine oxide. [ABSTRACT FROM AUTHOR]

Sulphur poisoning of nickel–based solid oxide fuel cell (SOFC) anode catalysts is a well-documented shortcoming, but not yet fully understood. Here, a novel experiment is demonstrated to obtain spectroscopic information at operando conditions, in particular the molecular structure of sulphur species in the sulphur K-shell X-ray absorption near edge structure (XANES) region for a SOFC anode under realistic operando conditions, thus, with the flux of O2− from cathode to anode. Cooling from T = 550 °C stepwise down to 250 °C, 5 ppm H2S/H2 reacting with Ni-gadolinium doped ceria (GDC) anode resulted in several sulphur species in different oxidation states (6+, 4+, 0, −2) and in amounts being at a minimum at high temperature. According to sulphur speciation analysis, the species could either relate to –SO4 2− or SO3 (g), –SO3 2− or SO2 (g), S2 (g) or surface-adsorbed S atoms, and, Ni or Ce sulphides, respectively. The coexistence of different sulphur oxidation states as a function of temperature was analysed in the context of thermodynamic equilibrium calculations. Deviations between experimental results and calculations are most likely due to limitations in the speed of some intermediate oxidation steps as well as due to differences between stoichiometric CeO2 used in calculations and partially reduced Ce0.9Gd0.1O2−δ . [ABSTRACT FROM AUTHOR]

Sulfur K-edge X-ray absorption spectroscopy(XAS) has been usedto distinguish between aqueous and solid sulfates and to investigatechanges in their speciation. Data have been collected for tetrahedrallycoordinated S in K2SO4and KHSO4solidsand aqueous solutions. With a first qualitative analysis of the X-rayabsorption near-edge structure (XANES) spectra, it has been observedthat those for solids are much more structured and distinguishablefrom those of aqueous solutions. The protonation state has a strongeffect on the white line of sulfates and has been assigned to thedifferent charge delocalization in the samples, the effect of thesolvating water molecules and multiple scattering effects. In theextended X-ray absorption fine structure (EXAFS) spectra, the backscatteringfrom the first O shell dominated the EXAFS fine structure function,χ(k), but the nonlinear multiple scatteringcontributions occurring in the first coordination shell are significantand must be considered in the EXAFS analysis. The intensity of thesecontributions strongly depend on the symmetry of the system. For adistorted tetrahedron, the intensity of the multiple scattering contributionsis less than that found in a regular tetrahedron. The FEFF code hasbeen used to model the contributions of the multiple-scattering processes.The observed experimental evidence in the XAS data can be used todistinguish between sulfates in solids and liquids. This is applicableto many chemical, geochemical, and biological systems. [ABSTRACT FROM AUTHOR]

Soot particles can significantly influence the Earth's climate by absorbing and scattering solar radiation as well as by acting as cloud condensation nuclei. However, despite their environmental (as well as economic and political) importance, the way these properties are affected by atmospheric processing of the combustion exhaust gases is still a subject of discussion. In this work, individual soot particles emitted from two different vehicles, a EURO 2 transporter, a EURO 3 passenger car, and a wood stove were investigated on a single-particle basis. The emitted exhaust, including the particulate and the gas phase, was processed in a smog chamber with artificial solar radiation. Single particle specimens of both unprocessed and aged soot were characterized using near edge X-ray absorption fine structure spectroscopy (NEXAFS) and scanning electron microscopy. Comparison of NEXAFS spectra from the unprocessed particles and those resulting from exhaust photooxidation in the chamber revealed changes in the carbon functional group content. For the wood stove emissions, these changes were minor, related to the relatively mild oxidation conditions. For the EURO 2 transporter emissions, the most apparent change was that of carboxylic carbon from oxidized organic compounds condensing on the primary soot particles. For the EURO 3 car emissions oxidation of primary soot particles upon photochemical aging has likely contributed as well. Overall, the changes in the NEXAFS fingerprints were in qualitative agreement with data from an aerosol mass spectrometer. Furthermore, by taking full advantage of our in situ microreactor concept, we show that the soot particles from all three combustion sources changed their ability to take up water under humid conditions upon photochemical aging of the exhaust. Due to the selectivity and sensitivity of the NEXAFS technique for the water mass, also small amounts of water taken up into the internal voids of agglomerated particles could be detected. Because such small amounts of water uptake do not lead to measurable changes in particle diameter, it may remain beyond the limits of volume growth measurements, especially for larger agglomerated particles. [ABSTRACT FROM AUTHOR]

The article focuses on the microtomography and its usefulness in hailstones and graupel porosity quantification and 3-D imaging. The tomographic method along with the Swiss Light Source's (SLS) beamline. It cites its effectiveness along with 3-D imaging technology in determining the features, morphology, and properties of both graupel and hailstones through infrared wavelength resolution.

Soot particles can significantly influence the Earth's climate by absorbing and scattering solar radiation as well as by acting as cloud condensation nuclei. However, despite their environmental (as well as economic and political) importance, the way these properties are affected by atmospheric processing is still a subject of discussion. In this work, soot particles emitted from two different cars, a EURO 2 transporter, a EURO 3 passenger vehicle, and a wood stove were investigated on a single-particle basis. The emitted exhaust, including the particulate and the gas phase, was processed in a smog chamber with artificial solar radiation. Single particle specimens of both unprocessed and aged soot were characterized using x-ray absorption spectroscopy and scanning electron microscopy. Comparison of the spectra from the unprocessed and aged soot particles revealed changes in the carbon functional group content, such as that of carboxylic carbon, which can be ascribed to both the condensation of secondary organic compounds on the soot particles and oxidation of primary soot particles upon photochemical aging. Changes in the morphology and size of the single soot particles were also observed upon aging. Furthermore, we show that the soot particles take up water in humid environments and that their water uptake capacity increases with photochemical aging. [ABSTRACT FROM AUTHOR]

A new in situ cell to study phase transitions and chemical processes on individual aerosol particles in the x-ray transmission microscope at the PolLux beamline of the Swiss light source has been built. The cell is machined from stainless steel and aluminum components and is designed to be used in the standard mount of the microscope without need of complicated rearrangements of the microscope. The cell consists of two parts, a back part which contains connections for the gas supply, heating, cooling devices, and temperature measurement. The second part is a removable clip, which hosts the sample. This clip can be easily exchanged and brought into a sampling unit for aerosol particles. Currently, the cell can be operated at temperatures ranging from -40 to +50 °C. The function of the cell is demonstrated using two systems of submicron size: inorganic sodium bromide aerosols and soot originating from a diesel passenger car. For the sodium bromide we demonstrate how phase transitions can be studied in these systems and that O1s spectra from aqueous sodium bromide solution can be taken from submicron sized particles. For the case of soot, we demonstrate that the uptake of water onto individual soot particles can be studied. [ABSTRACT FROM AUTHOR]

The article presents a study on the development of a cryo-stage to adapt to the standard setup of the SLS X04SA tomography beamline at the Swiss Light Source synchrotron facility to the requirements of ice particle micro-tomography. The study states that the cryo-stage gives three-dimensional data on the individual inner pore shape delineation. Also, quantitative information on the in situ pore structure statistics in individual samples can be derived through the synchroton tomography approach.

The heterogeneous reaction of HNO3with mineral dust aerosol (Arizona Test Dust) was studied in an aerosol flow tube at atmospherically relevant conditions (298 K, ∼1 atm, 6–60% RH) and using radioactively labelled HNO3. The uptake of nitric acid was found to depend on HNO3and H2O concentrations in the gas phase. A reaction mechanism is suggested to describe the heterogeneous interaction, involving Langmuir type adsorption and surface reaction. This mechanism is incorporated in a flux based aerosol kinetic model framework that is able to reproduce the observations within the range of experimental conditions. The experiments show that the reactive surface sites of the relatively calcium poor, but silicate rich dust surface are efficiently depleted at higher HNO3concentrations in the gas phase or longer exposure times. A set of kinetic parameters is extracted from the data, which can be used to calculate uptake coefficients as function of time, concentration and humidity for use in atmospheric chemistry models to improve especially the representation of the effects of relative humidity on dust aging and to allow following dust aging with time. [ABSTRACT FROM AUTHOR]

We report on the successful installation and operation of a scanning transmission x-ray microspectroscope (STXM) at the PolLux facility at the Swiss Light Source. This integration of an advanced STXM with improved sample handling capabilities and a novel beamline provides unique capabilities. PolLux uses linearly or circularly polarized x-rays from a bending magnet with an extended photon energy range (200–1400 eV). It is therefore well suited to determine a sample’s quantitative chemical composition, molecular orientation, or thickness of organic as well as condensed matter materials. The local magnetic state of magnetic thin films is accessible through fast helicity switching by steering the electron beam off axis through the bending magnet. Ex vacuo girder movers allow fast and highly reproducible (<1 μm) alignment of the instrument with respect to the photon beam. The present spatial resolution is ∼20 nm, limited by the zone plates utilized. The instrument has the stability and positional resolution to operate with much higher resolution optics as it becomes available. In addition to characterization experiments, we present several typical examples from materials research and environmental science to exemplify the capabilities. [ABSTRACT FROM AUTHOR]

Chemical and physical processes, such as heterogeneous chemical reactions, light scattering, and metamorphism occur in the natural snowpack. To model these processes in the snowpack, the specific surface area (SSA) is a key parameter. In this study, two methods, computed tomography and methane adsorption, which have intrinsically different effective resolutions - molecular and 30μm, respectively-were used to determine the SSA of similar natural snow samples. Except for very fresh snow, the two methods give identical results, with an uncertainty of 3%. This implies that the surface of aged natural snow is smooth up to a scale of about 30μm and that if smaller structures are present they do not contribute significantly to the overall SSA. It furthermore implies that for optical methods a voxel size of 10μm is sufficient to capture all structural features of this type of snow; however, fresh precipitation appears to contain small features that cause an under-estimation of SSA with tomography at this resolution. The methane adsorption method is therefore superior to computed tomography for very fresh snow having high SSA. Nonetheless, in addition to SSA determination, tomography provides full geometric information about the ice matrix. It can also be advantageously used to investigate layered snow packs, as it allows measuring SSA in layers of less than 1 mm. [ABSTRACT FROM AUTHOR]

Snow on the ground is a complex multiphase photochemical reactor that dramatically modifies the chemical composition of the overlying atmosphere. A quantitative description of the emissions of reactive gases by snow requires knowledge of snow physical properties. This overview details our current understanding of how those physical properties relevant to snow photochemistry vary during snow metamorphism. Properties discussed are density, specific surface area, thermal conductivity, permeability, gas diffusivity and optical properties. Inasmuch as possible, equations to parameterize these properties as functions of climatic variables are proposed, based on field measurements, laboratory experiments and theory. The potential of remote sensing methods to obtain information on some snow physical variables such as grain size, liquid water content and snow depth are discussed. The possibilities for and difficulties of building a snow photochemistry model by adapting current snow physics models are explored. Elaborate snow physics models already exist, and including variables of particular interest to snow photochemistry such as light fluxes and specific surface area appears possible. On the other hand, understanding the nature and location of reactive molecules in snow seems to be the greatest difficulty modelers will have to face for lack of experimental data, and progress on this aspect will require the detailed study of natural snow samples. [ABSTRACT FROM AUTHOR]

Chemical and physical processes, such as heterogeneous chemical reactions, light scattering, and metamorphism occur in the natural snowpack. To model these processes in the snowpack, the specific surface area (SSA) is a key parameter. In this study, two methods, computed tomography and methane adsorption, which have intrinsically different spatial resolutions --molecular and 30 µm, respectively -- were used to determine the SSA of identical natural snow samples. The two methods give identical results, with an uncertainty of 3%. This implies that the surface of natural snow is smooth up to a scale of about 30 µm and that for optical methods a voxel size of 10 µm is sufficient to capture all structural features of natural snow. This smoothness can be physically explained by calculating sublimation and surface diffusion on the snow particles. The methane adsorption method is superior to computed tomography for very fresh snow, but thin layers typical for natural snowpacks can not be resolved. Computed tomography can measure SSA in layers of less than 1mm thickness, and is therefore advantageous in layered snowpacks. [ABSTRACT FROM AUTHOR]

A Knudsen cell flow reactor was coupled to an online gas phase source of the short-lived radioactive tracer 13N to study the adsorption of nitrogen oxides on ice at temperatures relevant for the upper troposphere. This novel approach has several benefits over the conventional coupling of a Knudsen cell with a mass spectrometer. Experiments at lower partial pressures close to atmospheric conditions are possible. The uptake to the substrate is a direct observable of the experiment. Operation of the experiment in continuous or pulse mode allows to retrieve steady state uptake kinetics and more details of adsorption and desorption kinetics. [ABSTRACT FROM AUTHOR]

Dehydration of antigorite in subduction zones releases a large amount of aqueous fluid and volatile elements, which can potentially oxidize the mantle wedge. The redox capacity of three synthetic serpentinites with variable Fe total , Fe 3+ and S − contents is investigated using XANES spectroscopy at both, Fe and S K -edges. Experiments are performed between 450 and 900 °C, at 2 GPa and f O 2 ∼ QFM-2 ; conditions similar to those encountered in subduction zones. Redox reactions in the synthetic serpentinites, which involve Fe and S can be summarized as follows: 1) the reduction of (S − )-pyrite into (S 2− )-pyrrhotite (∼450 °C), with ∼4.4 mg/g of the sulfur degassed most likely as H 2 S, 2) the consumption of magnetite that reacts with antigorite to form Fe-rich olivine (<500 °C), 3) the reduction of (Fe 3+ )-antigorite into (Fe 2+ )-antigorite (∼580 °C), occurring about 100 °C below the temperature of antigorite breakdown, 4) the main (Fe 2+ )-antigorite breakdown that forms olivine and enstatite (∼675 °C), and 5) the decomposition of minor amounts of (Fe 2+/3+ )-clinochlore (∼800 °C). The bulk Fe 3+ /Fe total ratio is found to decrease with run temperature from ∼0.82–0.97 depending on the hydrous starting material, down to 0.1–0.2 in the high-temperature anhydrous assemblages. The evolution of mineral modes and Fe 3+ /Fe total with temperature in our synthetic samples shows similar trends to what has been reported in serpentinite rocks collected, for example, along a metamorphic transect in the western Alps. We show that a large amount of O 2 -equivalent – up to 10 mol/kg of rock – can be generated at temperature around 450 °C due to the presence of oxides and sulfides such as magnetite and pyrite. Owing to the poor capacity of aqueous fluid to transfer redox conditions, we surmise that this O 2 -equivalent is “consumed” at the scale of the lithospheric-mantle top which is partially serpentinized and therefore bear strong redox gradients. [ABSTRACT FROM AUTHOR]