Karen Appel

Combined bromine and chlorine release from large explosive volcanic eruptions: A threat to stratospheric ozone?

Large explosive volcanic eruptions inject gases, aerosols, and fi ne ashes into the stratosphere, potentially infl uencing climate. Emissions of chlorine (Cl) and bromine (Br) from such large eruptions play an important role for catalytic destruction of ozone in the stratosphere, but hitherto the global effects of simultaneous catastrophic release of volcanic Br and Cl into the stratosphere have not been investigated. The Br release from 14 large explosive eruptions throughout Nicaragua covering an entire subduction zone segment in the past 70 ka was determined with petrologic methods. Melt inclusions in volcanic phenocrysts were analyzed using a new optimized synchrotron‐X-ray fl uorescence microprobe set-up. Single eruptions produced Br outputs of 4‐600 kt, giving an average Br emission of 27 kt per eruption. Using the assumption that 10% of the emitted halogens reach the stratosphere, the average Br and Cl loading to the stratosphere would be 3 ppt and 1500 ppt, respectively, which together would account for 185% of the preindustrial equivalent effective stratospheric Cl loading. We thus conclude that many large tropical volcanic eruptions had and have the potential to substantially deplete ozone on a global scale, eventually forming future ozone holes.

A confocal set-up for micro-XRF and XAFS experiments using diamond-anvil cells

A confocal set-up is presented that improves micro-XRF and XAFS experiments with high-pressure diamond-anvil cells (DACs). In this experiment a probing volume is defined by the focus of the incoming synchrotron radiation beam and that of a polycapillary X-ray half-lens with a very long working distance, which is placed in front of the fluorescence detector. This set-up enhances the quality of the fluorescence and XAFS spectra, and thus the sensitivity for detecting elements at low concentrations. It efficiently suppresses signal from outside the sample chamber, which stems from elastic and inelastic scattering of the incoming beam by the diamond anvils as well as from excitation of fluorescence from the body of the DAC.

The combined effect of dissolved organic carbon and salinity on the bioaccumulation of copper in marine mussel larvae.

Larvae of Mytilus spp. are among the most Cu sensitive marine species. In this study we assessed the combined effect of salinity and dissolved organic carbon (DOC) on Cu accumulation on mussel larvae. Larvae were exposed for 48 h to three Cu concentrations in each of nine salinity/DOC treatments. Synchrotron radiation X-ray fluorescence was used to determine the Cu concentration in 36 individual larvae with a spatial resolution of 10 × 10 μm. Cu body burden concentrations varied between 1.1 and 27.6 μg/g DW larvae across all treatments and Cu was homogeneously distributed at this spatial resolution level. Our results indicate decreasing Cu accumulation with increasing DOC concentrations which can be explained by an increase in Cu complexation. In contrast, salinity had a nonlinear effect on Cu. This cannot be explained by copper speciation or competition processes and suggests a salinity-induced alteration in physiology.

Distribution of selected elements in calcific human aortic valves studied by microscopy combined with SR-μXRF: influence of lipids on progression of calcification.

Calcified heart valves display a significant imbalance in tissue content of trace and essential elements. The valvular calcification is an age-related process and there are data suggesting involvement of lipids. We studied elemental composition and lipid distribution in three distinct regions of calcified human aortic valves, representing successive stages of the calcific degeneration: normal, thickened (early lesion) and calcified (late lesion), using SR-μXRF (Synchrotron Radiation Micro X-Ray Fluorescence) for elemental composition and Oil Red O (ORO) staining for demonstration of lipids. Two-dimensional SR-μXRF maps and precise point spectra were compared with histological stainings on consecutive valve sections to prove topographical localization and colocalization of the examined elements and lipids. In calcified valve areas, accumulation of calcium and phosphorus was accompanied by enhanced concentrations of strontium and zinc. Calcifications preferentially developed in lipid-rich areas of the valves. Calcium concentration ratio between lipid-rich and lipid-free areas was not age-dependent in early lesions, but showed a significant increase with age in late lesions, indicating age-dependent intensification of lipid involvement in calcification process. The results suggest that mechanisms of calcification change with progression of valve degeneration and with age.

Reactions of strontium anorthite with H2O+CaCl2 fluids at 500 °C and high pressure: Kinetic information from in situ synchrotron-radiation XRF analyses of the fluid

Abstract The assemblage strontium anorthite, quartz, and kyanite was reacted with H2O+CaCl2 solutions at 500 °C and pressures between 460 and ~1300 MPa using a hydrothermal diamond-anvil cell. Information on the kinetics was obtained in situ based on time-resolved synchrotron-radiation X-ray fluorescence analyses of the Sr concentration in the fluid. The reaction products (anorthite or zoisite) were studied using transmission electron microscopy to obtain information on the reaction mechanism and mineral-fluid partitioning of strontium. The time required for equilibration was primarily controlled by the reaction mechanism, but not discernibly affected by pressure or chloride concentration. Nucleation and growth of zoisite at the expense of strontium anorthite was much faster than the Sr-Ca exchange reaction of strontium anorthite to anorthite, and resulted in chemically homogeneous crystals. The anorthite had developed a high nanoporosity during the reaction, which is indicative of coupled dissolution-precipitation. A zoisite-fluid exchange coefficient was obtained for the Sr-Ca fractionation at 500 °C and ~1300 MPa. At low bulk Sr/Ca, this value is in very good agreement with literature data, which are based on zoisite syntheses from oxide and hydroxide mixtures in chloridic fluids at 600 °C, 2 GPa and analyses after quench. This suggests that the Ca-Sr ratios in fluid and zoisite were not affected by back reactions during quenching. The constrained anorthite-fluid Sr partition coefficient for 500 °C, 460 MPa is, likewise, consistent with literature data, but determination of mineral-fluid partition and exchange coefficients can be hampered by quench phases in nanopores if coupled dissolution-precipitation acted as reaction mechanism.

A hard x-ray split-and-delay unit for the HED experiment at the European XFEL

For the High Energy Density (HED) experiment [1] at the European XFEL [2] an x-ray split- and delay-unit (SDU) is built covering photon energies from 5 keV up to 20 keV [3]. This SDU will enable time-resolved x-ray pump / x-ray probe experiments [4,5] as well as sequential diffractive imaging [6] on a femtosecond to picosecond time scale. Further, direct measurements of the temporal coherence properties will be possible by making use of a linear autocorrelation [7,8]. The set-up is based on geometric wavefront beam splitting, which has successfully been implemented at an autocorrelator at FLASH [9]. The x-ray FEL pulses are split by a sharp edge of a silicon mirror coated with multilayers. Both partial beams will then pass variable delay lines. For different photon energies the angle of incidence onto the multilayer mirrors will be adjusted in order to match the Bragg condition. For a photon energy of hν = 20 keV a grazing angle of θ = 0.57° has to be set, which results in a footprint of the beam (6σ) on the mirror of l = 98 mm. At this photon energy the reflectance of a Mo/B4C multi layer coating with a multilayer period of d = 3.2 nm and N = 200 layers amounts to R = 0.92. In order to enhance the maximum transmission for photon energies of hν = 8 keV and below, a Ni/B4C multilayer coating can be applied beside the Mo/B4C coating for this spectral region. Because of the different incidence angles, the path lengths of the beams will differ as a function of wavelength. Hence, maximum delays between +/- 2.5 ps at hν = 20 keV and up to +/- 23 ps at hν = 5 keV will be possible.

Integrating high-repetition rate high-energy/high-intensity laser to FEL experiments (Conference Presentation)

The combination of powerful optical lasers and an x-ray free-electron laser (XFEL) provides unique capabilities to study the transient behavior of matter in extreme conditions. The high energy density science instrument (HED instrument) at the European XFEL will provide the experimental platform on which an unique x-ray source can be combined with various types of high-power optical lasers. In this paper, we highlight selected scientific examples together with the associated x-ray techniques, with particular emphasis on femtosecond (fs)-timescale pump–probe experiments. Subsequently, we present the current design status of the HED instrument, outlining how the experiments could be performed. First user experiments will start at the beginning of 2018, after which various optical lasers will be commissioned and made available to the international scientific community.

Simulations of ultrafast x–ray laser experiments

Simulations of experiments at modern light sources, such as optical laser laboratories, synchrotrons, and free electron lasers, become increasingly important for the successful preparation, execution, and analysis of these experiments investigating ever more complex physical systems, e.g. biomolecules, complex materials, and ultra–short lived states of matter at extreme conditions. We have implemented a platform for complete start–to–end simulations of various types of photon science experiments, tracking the radiation from the source through the beam transport optics to the sample or target under investigation, its interaction with and scattering from the sample, and registration in a photon detector. This tool allows researchers and facility operators to simulate their experiments and instruments under real life conditions, identify promising and unattainable regions of the parameter space and ultimately make better use of valuable beamtime. In this paper, we present an overview about status and future development of the simulation platform and discuss three applications: 1.) Single–particle imaging of biomolecules using x–ray free electron lasers and optimization of x–ray pulse properties, 2.) x–ray scattering diagnostics of hot dense plasmas in high power laser–matter interaction and identification of plasma instabilities, and 3.) x–ray absorption spectroscopy in warm dense matter created by high energy laser–matter interaction and pulse shape optimization for low–isentrope dynamic compression.

In situ stability of carbonates in presence of mantle phases

Understanding the processes within the Earth’s lower mantle and transition zone and their physical properties as well as compositional variations is one of the grand challenges in modern geoscience. One of the large gaps concerning the Earth’s lower mantle is the role of carbonates. The structure and stability of mantle carbonates has been studied intensively in the past years [1–3] and it has been shown that magnesite can be stable along the geotherm down to lower mantle conditions [3]. However, the stability of carbonates in presence of mantle silicates at relevant temperatures is far from being well understood. Related to this, very little is known about distribution processes of trace elements between carbonates and silicates.

Novel platform for high-pressure static and dynamic X-ray diffraction experiments

Recent developments in experimental techniques have significantly enlarged the possibilities of high-pressure crystallography: with the development of double-stage Diamond Anvil Cells (DACs), the structure of matter can now be studied statically at pressures beyond 1 TPa [1]. Ultrafast probes such as X-ray diffraction or X-ray absorption at modern light sources enable to study snapshots of states at a time resolution down to 100 ps at the synchrotron [2] or down to the few fs at Free-Electron-Lasers [3]. Nowadays, these probes can be combined with fast drivers such as dynamically driven DACs, laser shocks or pulsed-laser heated DACs. While the first two drivers enable measurements of pressure-induced phase transformations at different strain rates, the latter allows to study the properties of matter at extreme PT conditions.