The Largest Electron Differential Energy Flux Observed at Mars by the Mars Express Spacecraft, 2004-2016.

The goal of this paper is to understand the processes by which solar wind electrons are energized in the Martian magnetosphere and how this compares to processes at Venus and Earth. Each is unique in the source of its magnetic field topology and how this influences electron energization. To achieve this goal, 24 million spectra spanning 13 years have been examined using the electron spectrometer from the Mars Express spacecraft between about 12,000 km and about 250 km altitude, and from all latitudes and local times. The top 10 largest differential energy flux at energies above the differential energy flux peak have been found: seven spectra from the magnetosheath near noon, three from the dark tail (the largest two from the middle and ionospheric edge of the magnetosheath). Spectral comparisons show a decade range in the peak of the electron distributions; however, all distributions show a similar energy maximum dictated by solar wind/planet interaction. Similarly derived, the largest Venus spectrum occurred near the magnetosheath bow shock and had the same shape as the most intense Mars inner magnetosheath spectrum. The Mars and Venus dayside spectra compared to the Mars nightside spectrum that included an enhanced optical signal attributed to discrete "auroral" precipitation show a similar shape. These spectra are also compared to a selected auroral zone electron spectra from the Earth. The Mars and Venus results suggest that there is no more energy needed to generate electrons forming the nightside precipitation than is gained during the solar wind/planet interaction.

Quick scanning monochromator for millisecond in situ and in operando X-ray absorption spectroscopy.

The design and capabilities of a novel Quick scanning Extended X-ray Absorption Fine Structure (QEXAFS) monochromator are presented. The oscillatory movement of the crystal stage is realized by means of a unique open-loop driving scheme operating a direct drive torque motor. The entire drive mechanics are installed inside of a goniometer located on the atmospheric side of the vacuum chamber. This design allows remote adjustment of the oscillation frequency and spectral range, giving complete control of QEXAFS measurements. It also features a real step-scanning mode, which operates without a control loop to prevent induced vibrations. Equipped with Si(111) and Si(311) crystals on a single stage, it facilitates an energy range from 4.0 keV to 43 keV. Extended X-ray absorption fine structure spectra up to k = 14.4 Å(-1) have been acquired within 17 ms and X-ray absorption near edge structure spectra covering more than 200 eV within 10 ms. The achieved data quality is excellent as shown by the presented measurements.

Hard disk drive based microsecond X-ray chopper for characterization of ionization chambers and photodiodes.

A fast X-ray chopper capable of producing ms long X-ray pulses with a typical rise time of few µs was realized. It is ideally suited to investigate the temporal response of X-ray detectors with response times of the order of µs to ms, in particular, any kind of ionization chambers and large area photo diodes. The drive mechanism consists of a brushless DC motor and driver electronics from a common hard disk drive, keeping the cost at an absolute minimum. Due to its simple construction and small dimensions, this chopper operates at home lab based X-ray tubes and synchrotron radiation sources as well. The dynamics of the most important detectors used in time resolved X-ray absorption spectroscopy, namely, ionization chambers and Passivated Implanted Planar Silicon photodiodes, were investigated in detail. The results emphasize the applicability of this X-ray chopper.

New developments for the investigation of hard X-rays emitted by peeling adhesive tapes.

We realized an advanced apparatus for the investigation of emitted X-rays produced by peeling adhesive tape rolls under vacuum conditions. Two stepper motors can unwind and rewind a tape roll, and an additional roller with an optical encoder provides measurement and control of the tape speed. This way reproducible and consecutive experiments are feasible without having to change the tape or break the vacuum. The dependence of the X-ray emission on tape speed, gas pressure, type of adhesive tape, and detector angle has been investigated. The resulting spectra are continuous and span an X-ray energy range of typically 2-60 keV with high intensity. Furthermore, the new apparatus allows the in situ metalization of adhesive tape rolls by a gold sputter source. A significantly increased X-ray emission was observed for adhesive tapes with a metal coating. Thin metal foils have been placed between the tape and the detector, different K- and L-absorption edges could be measured. A considerable enhancement of the emission was achieved under the influence of the magnetic field of an NdFeB permanent magnet.

Structural properties of fluorozirconate-based glass ceramics doped with multivalent europium.

The structure/property relationships of fluorochlorozirconate glass ceramics as a function of divalent and trivalent europium (Eu) co-doping and thermal processing have been investigated; the influence of doping ratio on the formation of barium chloride (BaCl(2)) nanocrystals therein was elucidated. X-ray absorption near-edge structure spectroscopy shows that the post-thermal annealing changes the Eu valence of the as-poured glass slightly, but during the melting process Eu(3+) is more strongly reduced to Eu(2+), in particular, when doped as a chloride instead of fluoride compound. The Eu(2+)-to-Eu(3+) doping ratio also plays a significant role in chemical equilibrium in the melt. X-ray diffraction measurements indicate that a higher Eu(2+) fraction leads to a BaCl(2) phase transition from hexagonal to orthorhombic structure at a lower temperature.

A new flexible monochromator setup for quick scanning x-ray absorption spectroscopy.

A new monochromator setup for quick scanning x-ray absorption spectroscopy in the subsecond time regime is presented. Novel driving mechanics allow changing the energy range of the acquired spectra by remote control during data acquisition for the first time, thus dramatically increasing the flexibility and convenience of this method. Completely new experiments are feasible due to the fact that time resolution, edge energy, and energy range of the acquired spectra can be changed continuously within seconds without breaking the vacuum of the monochromator vessel and even without interrupting the measurements. The advanced mechanics are explained in detail and the performance is characterized with x-ray absorption spectra of pure metal foils. The energy scale was determined by a fast and accurate angular encoder system measuring the Bragg angle of the monochromator crystal with subarcsecond resolution. The Bragg angle range covered by the oscillating crystal can currently be changed from 0 degrees to 3.0 degrees within 20 s, while the mechanics are capable to move with frequencies of up to ca. 35 Hz, leading to ca. 14 ms/spectrum time resolution. A new software package allows performing programmed scan sequences, which enable the user to measure stepwise with alternating parameters in predefined time segments. Thus, e.g., switching between edges scanned with the same energy range is possible within one in situ experiment, while also the time resolution can be varied simultaneously. This progress makes the new system extremely user friendly and efficient to use for time resolved x-ray absorption spectroscopy at synchrotron radiation beamlines.

Novel angular encoder for a quick-extended x-ray absorption fine structure monochromator.

New concepts for time-resolved x-ray absorption spectroscopy using the quick-extended x-ray absorption fine structure (QEXAFS) method are presented. QEXAFS is a powerful tool to gain structural information about, e.g., fast chemical reactions or phase transitions on a subsecond scale. This can be achieved with a monochromator design that employs a channel-cut crystal on a cam driven tilt table for rapid angular oscillations of the Bragg angle. A new angular encoder system and a new data acquisition were described and characterized that were applied to a QEXAFS monochromator to get spectra with a directly measured accurate energy scale. New electronics were designed to allow a fast acquisition of the Bragg angle values and the absorption data during the measurements simultaneously.

The loss of ions from Venus through the plasma wake.

Venus, unlike Earth, is an extremely dry planet although both began with similar masses, distances from the Sun, and presumably water inventories. The high deuterium-to-hydrogen ratio in the venusian atmosphere relative to Earth's also indicates that the atmosphere has undergone significantly different evolution over the age of the Solar System. Present-day thermal escape is low for all atmospheric species. However, hydrogen can escape by means of collisions with hot atoms from ionospheric photochemistry, and although the bulk of O and O2 are gravitationally bound, heavy ions have been observed to escape through interaction with the solar wind. Nevertheless, their relative rates of escape, spatial distribution, and composition could not be determined from these previous measurements. Here we report Venus Express measurements showing that the dominant escaping ions are O+, He+ and H+. The escaping ions leave Venus through the plasma sheet (a central portion of the plasma wake) and in a boundary layer of the induced magnetosphere. The escape rate ratios are Q(H+)/Q(O+) = 1.9; Q(He+)/Q(O+) = 0.07. The first of these implies that the escape of H+ and O+, together with the estimated escape of neutral hydrogen and oxygen, currently takes place near the stoichometric ratio corresponding to water.

Combustion front dynamics in the combustion synthesis of refractory metal carbides and di-borides using time-resolved X-ray diffraction.

A compact diffraction-reaction chamber, using a 2-inch photodiode array detector, has been employed to investigate the chemical dynamics at the combustion front of a selected series of refractory metal carbides and di-borides from their constituent element reactants as well as binary products from B4C as a reactant. These systems are denoted as (i) M + C --> MC; (ii) M + 2B --> MB2; and (iii) 3M + B4C --> 2MB2 + MC, where M = Ti, Zr, Nb, Hf or Ta. Time-resolved X-ray diffraction using intense synchrotron radiation at frame rates up to 10 frames s(-1) (or 100 ms frame(-1)) was employed. The combustion reactions were found to complete within 200-400 ms. In contrast to the Ta + C --> TaC combustion system studied earlier, in which a discernible intermediate sub-carbide phase was first formed, reacted further and disappeared to yield the final TaC product, no intermediate sub-carbide or sub-boride was detected in the current systems. Combustion for the Ti, Zr and Hf systems involved a liquid phase, in which the adiabatic temperatures Tad are well above the melting points of the respective reactant metals and have a typical combustion front velocity of 5-6 mm s(-1). The Nb and Ta systems have lower Tad, involving no liquid phase. These are truly solid combustion systems and have a lower combustion front velocity of 1-2 mm s(-1). The current study opens up a new avenue to chemical dynamics and macrokinetic investigations of high-temperature solid-state reactions.

Plasma acceleration above martian magnetic anomalies.

Auroras are caused by accelerated charged particles precipitating along magnetic field lines into a planetary atmosphere, the auroral brightness being roughly proportional to the precipitating particle energy flux. The Analyzer of Space Plasma and Energetic Atoms experiment on the Mars Express spacecraft has made a detailed study of acceleration processes on the nightside of Mars. We observed accelerated electrons and ions in the deep nightside high-altitude region of Mars that map geographically to interface/cleft regions associated with martian crustal magnetization regions. By integrating electron and ion acceleration energy down to the upper atmosphere, we saw energy fluxes in the range of 1 to 50 milliwatts per square meter per second. These conditions are similar to those producing bright discrete auroras above Earth. Discrete auroras at Mars are therefore expected to be associated with plasma acceleration in diverging magnetic flux tubes above crustal magnetization regions, the auroras being distributed geographically in a complex pattern by the many multipole magnetic field lines extending into space.

A new cell for temperature-dependent X-ray absorption spectroscopy of liquid solutions: application to PbBr2 solutions in diethylene glycol.

An in situ cell has been constructed for temperature-dependent X-ray absorption experiments (EXAFS and XANES) of lead bromine (PbBr2) solutions in diethylene glycol in the temperature range from room temperature up to about 433 K. The solution is kept in a thermostated container made of carbon-reinforced teflon between two thin chemically inert quartz glass windows with a high transmission for hard X-rays. The construction of the cell ensures that these X-ray windows are thermalized so that any possible precipitation of solid products from the solution is inhibited. The cell consists mainly of two hermetically sealed teflon containers for the thermostating fluid (silicon oil) that were fitted together in such a way that a small and variable volume (approximately 2-4 cm3) for the liquid under investigation was achieved. A small thermocouple in a glass enclosure was placed in the solution to maintain temperature control and feedback to the thermostat. The cell design and its performance for temperature-dependent in situ investigations with X-rays are reported. Some preliminary results obtained for PbBr2 solutions in diethylene glycol are given.

Time-resolved study of the oxidation of ethanol by cerium(IV) using combined quick-XANES, UV-vis, and Raman spectroscopies.

Time-resolved X-ray absorption spectroscopy (Quick-XANES) has been combined with UV-vis and Raman spectroscopies to study the in situ reduction of Ce4+ to Ce3+ in ethanolic solution with a time resolution of ca. 4-5 s. For this purpose, a cam-driven oscillating double-crystal monochromator with a channel-cut crystal was combined with two spectrometers for UV-vis and Raman spectroscopies in a specialized cell which allows one to fit the optical pathways for all three spectroscopies individually. The results show that high-quality results can be obtained simultaneously, thus giving a detailed insight into the mechanisms of the investigated chemical reaction. The continuous release of nitrate and ethanol ligands from the initial Ce4+ into the solution finally leads to a trivalent cerium species which is only coordinated with water molecules after about 1800 s of reaction time.

Solar wind-induced atmospheric erosion at Mars: first results from ASPERA-3 on Mars Express.

The Analyzer of Space Plasma and Energetic Atoms (ASPERA) on board the Mars Express spacecraft found that solar wind plasma and accelerated ionospheric ions may be observed all the way down to the Mars Express pericenter of 270 kilometers above the dayside planetary surface. This is very deep in the ionosphere, implying direct exposure of the martian topside atmosphere to solar wind plasma forcing. The low-altitude penetration of solar wind plasma and the energization of ionospheric plasma may be due to solar wind irregularities or perturbations, to magnetic anomalies at Mars, or both.

[Imaging diagnostics of ulnar wrist pain]. / Bildgebende Diagnostik des ulnaren Handgelenkschmerzes.

An exact knowledge of the value of different pictorial diagnostic techniques allows a focussed and rapid diagnosis of ulnar wrist pain. A prerequisite for the choice of the best possible method of investigation is an exact clinical examination. The basic examination involves conventional recording at both the centralised at the symptomatic levels. If there is a suspicion of occult bone lesion, finely focused, magnified graphics, CT or bone scintigraphy should be used, depending on both the problem faced and availability. For tissue or ligament lesions, stress graphics, movement studies or MRT, also with contrast media, should be used. Bone scintigraphy is a suitable method to differentiate between inflammatory tissue and/or bone changes.

Piezo-QEXAFS with fluorescence detection: fast time-resolved investigations of dilute specimens.

First X-ray absorption spectroscopy experiments with a vibrating piezo-driven double-crystal monochromator (piezo-QEXAFS) and fluorescence detection are reported. It is shown that high-quality XANES spectra can be recorded on a time scale of about 50 ms per spectrum, even for very low concentrations of < 10 mmol l-1 using fluorescence detection. The quality of the spectra, possible applications, as well as present limits of the technique will be discussed.

Piezo-QEXAFS: advances in time-resolved X-ray absorption spectroscopy.

The Piezo-QEXAFS technique is a novel tool for time-resolved X-ray absorption spectroscopy in the hard X-ray range. Monochromator components consisting of specialized tilt stages to perform fast energy scans, lightweight crystal holders, bending mechanics, and control electronics are being installed and commissioned. It is planned to perform fast EXAFS scans with time resolution in the millisecond range. With Piezo-QEXAFS all typical X-ray absorption experiments will be possible as it retains the standard linear geometry. The achieved time resolution opens interesting insights into the dynamics of phase transitions and chemical reactions.

Reflection mode XAFS investigations of reactively sputtered thin films.

Amorphous Ta-oxide and Sn-nitride thin films were prepared by reactive sputter deposition on smooth float glass substrates and investigated ex situ using reflection mode XAFS. The absorption coefficient mu and its fine structure were extracted from the measured reflection mode XAFS spectra with a method based on the Kramers-Kronig transform. Bond distances, coordination numbers and Debye-Waller factors were determined by a detailed XAFS data analysis and compared to those of reference compounds. In addition, changes of the atomic short range order of the sputter deposited Ta2O5-films induced by a thermal heat treatment in ambient air were examined as a function of the annealing temperature.

XAFS investigations of tin nitrides.

Tin nitrides (Sn3N4) prepared by the reaction of Sn-halides with KNH2 in liquid ammonia and a subsequent vacuum annealing procedure were investigated with transmission mode XAFS experiments. While the near edge data suggest the presence of a univalent Sn-compound with a valency close to +4, the analysis of the extended X-ray absorption fine structure proves the presence of two different local Sn sites in this crystal structure: While Sn(1) is surrounded by 4 nitrogen in a distance of 2.06 A, each Sn(2) ion is coordinated with 6 nitrogen at about 2.17 A radial distance.