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A confocal set-up is presented that improves micro-XRF and XAFS experiment with high-pressure e 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
We present a new autoclave that enables in situ characterization of hydrothermal fluids at high pressures and high temperatures at synchrotron x-ray radiation sources. The autoclave has been specifically designed to enable x-ray absorption spectroscopy in fluids with applications to mineral solubility and element speciation analysis in hydrothermal fluids in complex compositions. However, other applications, such as Raman spectroscopy, in high-pressure fluids are also possible with the autoclave. First experiments were run at pressures between 100 and 600 bars and at temperatures between 25 degrees C and 550 degrees C, and preliminary results on scheelite dissolution in fluids of different compositions show that the autoclave is well suited to study the behavior of ore-forming metals at P-T conditions relevant to the Earth's crust.
Sulfur is an important component in volcanic gases at the Earth surface but also present in the deep Earth in hydrothermal or magmatic fluids. Little is known about the evolution of such fluids during ascent in the crust. A new optical cell was developed for in situ Raman spectroscopic investigations on fluids allowing abrupt or continuous changes of pressure up to 200 MPa at temperatures up to 750 degrees C. The concept is based on a flexible gold bellow, which separates the sample fluid from the pressure medium water. To avoid reactions between aggressive fluids and the pressure cell, steel components in contact with the fluid are shielded by gold foil. The cell was tested to study redox reactions in fluids using aqueous ammonium sulfate solutions as a model system. During heating at constant pressure of 130 MPa, sulfate ions transform first to HSO4- ions and then to molecular units such as H2SO4. Variation of pressure shows that the stability of sulfate species relies on fluid density, i.e., highly charged species are stable only in high-density fluids. Partial decomposition of ammonium was evident above 550 degrees C by the occurrence of a nitrogen peak in the Raman spectra. Reduced sulfur species were observed above 700 degrees C by Raman signals near 2590 cm(-1) assigned to HS- and H2S. No clear evidence for the formation of sulfur dioxide was found in contrary to previous studies on aqueous H2SO4, suggesting very reducing conditions in our experiments. Fluid-mineral interaction was studied by inserting into the cell a small, semi-open capsule filled with a mixture of pyrite and pyrrhotite. Oxidation of the sample assembly was evident by transformation of pyrite to pyrrhotite. As a consequence, sulfide species were observed in the fluid already at temperatures of similar to 600 degrees C.
In this study transmission X-ray microscopy (TXM) was tested as a method to investigate the chemistry and structure of corroded silicate glasses at the nanometer scale. Three different silicate glasses were altered in static corrosion experiments for 1-336 hours at temperatures between 60 degrees C and 85 degrees C using a 25% HCl solution. Thin lamellas were cut perpendicular to the surface of corroded glass monoliths and were analysed with conventional TEM as well as with TXM. By recording optical density profiles at photon energies around the Na and O K-edges, the shape of the corrosion rim/pristine glass interfaces and the thickness of the corrosion rims has been determined. Na and O near-edge X-ray absorption fine-structure spectra (NEXAFS) were obtained without inducing irradiation damage and have been used to detect chemical changes in the corrosion rims. Spatially resolved NEXAFS spectra at the O K-edge provided insight to structural changes in the corrosion layer on the atomic scale. By comparison to O K-edge spectra of silicate minerals and (hydrous) albite glass as well as to O K-edge NEXAFS of model structures simulated with ab initio calculations, evidence is provided that changes of the fine structure at the O K-edge are assigned to the formation of siloxane groups in the corrosion rim.
Amides as thermo-sensitive tracers for investigating the thermal state of geothermal reservoirs
(2016)
The application of thermo-sensitive tracers is a promising technique for evaluating the thermal state of geothermal reservoirs. To extend the compound spectrum for hydrolyzable compounds to reservoir temperatures between 100 and 200 degrees C carboxamides were studied. The kinetic parameters of 17 self-synthesized amides were determined in hydrothermal batch and autoclave experiments. The influence of the molecular structure and the role of pH/pOH on hydrolysis kinetics were studied. Additionally, the thermal stabilities of the hydrolysis products were evaluated. The results demonstrate the high potential of tracers based on amide hydrolysis for use in medium enthalpy reservoirs. (C) 2016 Elsevier Ltd. All rights reserved.
We present a study of the local atomic environment of the oxygen atoms in the aqueous solutions of NaOH and HCl under simultaneous high-temperature and high-pressure conditions. Experimental nonresonant X-ray Raman scattering core-level spectra at the oxygen K-edge show systematic changes as a function of temperature and pressure. These systematic changes are distinct for the two different solutes and are described well by calculations within the Bethe- Salpeter formalism for snapshots from ab initio molecular dynamics simulations. The agreement between experimental and simulation results allows us to use the computations for a detailed fingerprinting analysis in an effort to elucidate the local atomic structure and hydrogen-bonding topology in these relevant solutions. We observe that both electrolytes, especially NaOH, enhance hydrogen bonding and tetrahedrality in the water structure at supercritical conditions, in particular in the vicinity of the hydration shells. This effect is accompanied with the association of the HCl and NaOH molecules at elevated temperatures.
A confocal set-up for three-dimensional (3D) micro X-ray fluorescence (micro-XRF) was used at the mySpot beamline at BESSY II, which allows compositional depth profiling for various applications. We present results obtained with a confocal 3D micro-XRF set-up for chemical age dating using the U, Th and Pb concentrations of monazite within rock thin sections. The probing volume was determined to be approximately 21 x 21 x 24 mu m(3) for W-L alpha using an excitation energy of 19 keV. The relative detection limits particularly for Pb are below 10 ppm (for Counting times
X-ray emission and X-ray Raman scattering spectroscopy are powerful tools to investigate the local electronic and atomic structure of high and low Z elements in situ. Notably, these methods can be applied for in situ spectroscopy at high pressure and high temperature using resistively or laser-heated diamond anvil cells in order to achieve thermodynamic conditions which appear in the Earth's interior. We present a setup for combined X-ray emission and X-ray Raman scattering studies at beamline P01 of PETRA III using a portable wavelength-dispersive von Hamos spectrometer together with the permanently installed multiple-analyzer Johann-type spectrometer. The capabilities of this setup are exemplified by investigating the iron spin crossover of siderite FeCO3 up to 49.3 GPa by measuring the Fe M2,3-edge and the Fe Kβ1,3 emission line simultaneously. With this setup, the Fe valence-to-core emission can be detected together with the Kβ1,3 emission line providing complementary information on the sample's electronic structure. By implementing a laser-heating device, we demonstrate the strength of using a von Hamos type spectrometer for spin state mapping at extreme conditions. Finally, we give different examples of low Z elements' absorption edges relevant for application in geoscience that are accessible with the Johann-type XRS spectrometer. With this setup new insights into the spin transition and compression mechanisms of Earth's mantle materials can be obtained of importance for comprehension of the macroscopic physical and chemical properties of the Earth's interior.
Kim et al. recently measured the structure factor of deeply supercooled water droplets (Reports, 22 December 2017, p. 1589). We raise several concerns about their data analysis and interpretation. In our opinion, the reported data do not lead to clear conclusions about the origins of water’s anomalies.