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144 records · Page 8

Image Guider Subsystem Analysis for the GHAPS Project

The Gondola for High-Altitude Planetary Science (GHAPS) project is a balloon-borne astronomical observatory designed operate in the UV, Visible, and near-mid IR spectral region. The GHAPS Optical Telescope Assembly (OTA) is designed around a one meter aperture narrow field-of-view telescope with near-diffraction-limited performance. GHAPS will utilize Wallops Arc-Second Pointing System (WASP) for pointing the OTA with an accuracy of 1 arc second or better. WASP relies heavily on a self-contained star tracker assembly to determine the OTA line of sight. Preliminary structural analysis indicates that potential misalignments could be present between the OTA line of sight and the star tracker FOV center during the expected flight conditions that could compromise GHAPS pointing accuracy. In response the GHAPS project undertook a trade study to resolve the following issues: (1) estimate the worst case long-term (or bias) pointing misalignments for the GHAPS opto-mechanical configuration, (2) examine the need for additional hardware to correct pointing errors, and (3) determine the best hardware and software implementation to do so. Quantitative comparisons of performance and qualitative estimates of other factors such as mass, volume, power consumption, and cost are combined into an overall assessment of potential solutions. Results are discussed and a recommended implementation is given that is optimized to best achieve pointing performance goals, while minimizing impact to the design, cost, and resources of the GHAPS project.

Star Tracker↗

10 Boron-film-based gas detectors at ESS

The development of detectors for the European Spallation Source is an important parallel element to the effort put into the design and construction of the neutron source and instruments. The 10Boron-film-based detector developments that started over a decade ago as basic detector concepts have now reached technical maturity after intense prototyping work and numerous testing campaigns. Several of the ESS beamlines that will soon enter the commissioning phase started welcoming the detector systems built with the 10 B-film converter technology. The real-size demonstrators evolved in the last 2–3 years into a diverse suite of gas proportional counters for use in diffraction, reflectometry and small-angle scattering studies in spite of the operational complexity posed by the requirements for large-area coverage, low material budget and robustness for operation in the high-flux and high-radiation environment of ESS. The detectors are now being shipped to ESS or undergoing the last performance and calibration tests before being handed over to the instrument teams for installation in the host beamlines. A common feature of these detector systems is the very large number of readout channels that they are instrumented with in order to fulfill the demanding requirements for sensitivity, spatial resolution and count-rate capability. Across all of the detector types that will operate at ESS, the integration, testing and commissioning of the read-out technologies and software tools for data reduction, calibration and analysis are the focus of the detector and integration teams. These will yield a wealth of knowledge about their operation as well as initial results on the in-situ performance, a very important asset to ensure rapid commissioning of the detectors when neutrons from the ESS source become available. In this paper we will give an overview of the 10 B-film-based detector technologies included in the ESS detector suite that are currently facing the transition from the production phase to installation and integration with the other beamline components, which comes with its own specific challenges of both organizational and technical nature.

47 OTHER INSTRUMENTATION↗

TIA: A forward model and analyzer for Talbot interferometry experiments of dense plasmas

Interferometry is one of the most sensitive and successful diagnostic methods for plasmas. However, owing to the design of most common interferometric systems, the wavelengths of operation and, therefore, the range of densities and temperatures that can be probed are severely limited. Talbot–Lau interferometry offers the possibility of extending interferometry measurements to x-ray wavelengths by means of the Talbot effect. While there have been several proof-of-concept experiments showing the efficacy of this method, it is only recently that experiments to probe High Energy Density (HED) plasmas using Talbot–Lau interferometry are starting to take place. To improve these experimental designs, we present here the Talbot-Interferometry Analyzer (TIA) tool, a forward model for generating and postprocessing synthetic x-ray interferometry images from a Talbot–Lau interferometer. Although TIA can work with any two-dimensional hydrodynamic code to study plasma conditions as close to reality as possible, this software has been designed to work by default with output files from the hydrodynamic code FLASH, making the tool user-friendly and accessible to the general plasma physics community. Here, the model has been built into a standalone app, which can be installed by anyone with access to the MATLAB runtime installer and is available upon request to the authors.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Broadband Interferometer for Measuring Transmitted Wavefronts of Optical Bandpass Filters for HST (ACS)

The transmitted wavefronts of optical filters for the Hubble Space Telescope (HST) Advanced Camera for Surveys (ACS) are characterized using the Wildly and Openly Modified Broadband Achromatic Twyman Green (WOMBAT) Interferometer developed in the NASA/GSFC Optics Branch's Diffraction Grating Evaluation Facility (DGEF). Because only four of thirty-three of ACS's optical bandpass filters transmit the 633 nm light of most commercial interferometers, a broadband interferometer is required to verify specified transmitted wavefront of ACS filters. WOMBAT's design is a hybrid of the BAT interferometer developed by JPL used for HST Wide Field and Planetary Camera 2 (WFPC-2) filters and a WYKO 400 phase shifting interferometer. It includes a broadband light source, monochromator, off-axis, parabolic collimating and camera mirrors, an aluminum-coated fused silica beam splitter, flat retroreflecting mirrors for the test and reference arms, and a LTV-sensitive CCD camera. An outboarded, piezo-electric phase shifter holds the flat mirror in the interferometer's reference arm. The interferometer is calibrated through interaction between the WYKO system's software and WONMAT hardware for the test wavelength of light entering the beam splitter. Phase-shifted interferograms of the filter mounted in the test arm are analyzed using WYKO's Vision' software. Filters as large as 90 mm in diameter have been measured over a wavelength range from 200 to 1100 nm with a sensitivity of lambda/200 rms at lambda = 633 nm. Results of transmitted wavefront measurements are shown for ACS fixed band pass and spatially-variable bandpass filters for a variety of wavelengths.

Boucarut, R. A.↗

Analysis of AIS Data of the Recluse Oil Field, Recluse, Wyoming

Airborne Imaging Spectrometer (AIS) data were flown over the Recluse, Wyoming oil field on September 9, 1984. Processing software was developed at Earth Satellite Corporation (EarthSat) for interactive analysis of the AIS data. EarthSat's AIS processing capabilities include destriping, solar irradiance corrections, residual calculations, geometric resampling, equal energy normalization, interactive spectral classifications and a variety of compressive algorithms to reduce the data to 8-bit format with a minimum of information loss. The in-house photolab facilities of EarthSat can routinely produce high-quality color renditions of the enhanced AIS data. A total of 80 lithologic samples were collected under the AIS flight lines. Correlation (within the atmospheric windows) between the laboratory and the AIS spectra of sample sites was generally poor. Reasonable correlation was only possible in large, freshly plowed fields. Mixed pixels and contrast between the natural and sample's surfaces were believed responsible for the poor correlation. Finally, a drift of approximately three channels was observed in the diffraction grating position within the 1.8 to 2.1 micron quadrant.

Dykstra, J. D.↗

NASA Tech Briefs, December 2006

Topic include: Inferring Gear Damage from Oil-Debris and Vibration Data; Forecasting of Storm-Surge Floods Using ADCIRC and Optimized DEMs; User Interactive Software for Analysis of Human Physiological Data; Representation of Serendipitous Scientific Data; Automatic Locking of Laser Frequency to an Absorption Peak; Self-Passivating Lithium/Solid Electrolyte/Iodine Cells; Four-Quadrant Analog Multipliers Using G4-FETs; Noise Source for Calibrating a Microwave Polarimeter; Hybrid Deployable Foam Antennas and Reflectors; Coating MCPs with AlN and GaN; Domed, 40-cm-Diameter Ion Optics for an Ion Thruster; Gesture-Controlled Interfaces for Self-Service Machines; Dynamically Alterable Arrays of Polymorphic Data Types; Identifying Trends in Deep Space Network Monitor Data; Predicting Lifetime of a Thermomechanically Loaded Component; Partial Automation of Requirements Tracing; Automated Synthesis of Architecture of Avionic Systems; SSRL Emergency Response Shore Tool; Wholly Aromatic Ether-Imides as n-Type Semiconductors; Carbon-Nanotube-Carpet Heat-Transfer Pads; Pulse-Flow Microencapsulation System; Automated Low-Gravitation Facility Would Make Optical Fibers; Alignment Cube with One Diffractive Face; Graphite Composite Booms with Integral Hinges; Tool for Sampling Permafrost on a Remote Planet; and Special Semaphore Scheme for UHF Spacecraft Communications.

Source record↗

Propagation model for the Land Mobile Satellite channel in urban environments

This paper presents the major characteristics of a simulation package capable of performing a complete narrow and wideband analysis of the mobile satellite communication channel in urban environments for any given orbital configuration. The wavelength-to-average urban geometrical dimension ratio has required the use of the Geometrical Theory of Diffraction (GTD). For the RF frequency range, the model has been designed to be (1 up to 60 GHz) extended to include effects of non-perfect conductivity and surface roughness. Taking advantage of the inherent capabilities of such a high frequency method, we are able to provide a complete description of the electromagnetic field at the mobile terminal. Using the information made available at the ray-tracer and GTD solver outputs, the Land Mobile Satellite (LMS) urban model can also give a detailed description of the communication channel in terms of power delay profiles, Doppler spectra, channel scattering functions, and so forth. Statistical data, e.g. cumulative distribution functions, level crossing rates or distributions of fades are also provided. The user can access the simulation tool through a Design-CAD user-friendly interface by means of which she can effectively design her own urban layout and run consequently all the envisaged routines. The software is optimized in its execution time so that numerous runs can be achieved in a considerably short time.

Sforza, M.↗

Efficient structure-factor modeling for crystals with multiple components

Diffraction intensities from a crystallographic experiment include contributions from the entire unit cell of the crystal: the macromolecule, the solvent around it and eventually other compounds. These contributions cannot typically be well described by an atomic model alone, i.e . using point scatterers. Indeed, entities such as disordered (bulk) solvent, semi-ordered solvent ( e.g. lipid belts in membrane proteins, ligands, ion channels) and disordered polymer loops require other types of modeling than a collection of individual atoms. This results in the model structure factors containing multiple contributions. Most macromolecular applications assume two-component structure factors: one component arising from the atomic model and the second one describing the bulk solvent. A more accurate and detailed modeling of the disordered regions of the crystal will naturally require more than two components in the structure factors, which presents algorithmic and computational challenges. Here an efficient solution of this problem is proposed. All algorithms described in this work have been implemented in the computational crystallography toolbox ( CCTBX ) and are also available within Phenix software. These algorithms are rather general and do not use any assumptions about molecule type or size nor about those of its components.

59 BASIC BIOLOGICAL SCIENCES↗

Design and Characterization of a Lens-Coupled System for Dynamic X-Ray Diffraction

X-ray diffraction (XRD) is a necessary technique for understanding states of materials under static and dynamic loading conditions. The higher-pressure Equation of State (EOS) of many materials can only be explored via shock or ramp compression at temperatures and pressures of interest. While static XRD work has yielded EOS measurements in the 100 - 200 GPa regime, dynamic X-ray diffraction (DXRD) can explore EOS phases in the TPa regime, which closely resembles inner-core planetary conditions. DXRD hinges on the ability to measure the exact phase or phase change of a material while under dynamic loading conditions. Macroscopic diagnostic systems (e.g. velocimetry and pyrometry) can infer a phase change but not identify the specific phase entered by a material. While microscopic (atomic-level) diagnostic systems (e.g. DXRD) have been designed and implemented in Department of Energy’s (DOE) National Laboratories complex, the unique nature of Sandia National Laboratories’ Pulsed Power Facility (Z Machine) prohibits the use of such devices. The destructive nature of Z experiments presents a challenge to data capture and retrieval. Furthermore there are electromagnetic interference, X-ray background, and mechanical constraints to consider. Thus, a multi-part X-ray diagnostic for use on the Z Machine and Z-Beamlet Laser system has been designed and analyzed. Portions of this new DYnamic SCintillator Optic (DYSCO) have been built, tested and fielded. A data analysis software has been written. Finally, the radiance profile of the DYSCO’s scintillator has been characterized through experiments performed at the University of Arizona.

36 MATERIALS SCIENCE↗

Blinking statistics and molecular counting in direct stochastic reconstruction microscopy (dSTORM)

Abstract Motivation Many recent advancements in single-molecule localization microscopy exploit the stochastic photoswitching of fluorophores to reveal complex cellular structures beyond the classical diffraction limit. However, this same stochasticity makes counting the number of molecules to high precision extremely challenging, preventing key insight into the cellular structures and processes under observation. Results Modelling the photoswitching behaviour of a fluorophore as an unobserved continuous time Markov process transitioning between a single fluorescent and multiple dark states, and fully mitigating for missed blinks and false positives, we present a method for computing the exact probability distribution for the number of observed localizations from a single photoswitching fluorophore. This is then extended to provide the probability distribution for the number of localizations in a direct stochastic optical reconstruction microscopy experiment involving an arbitrary number of molecules. We demonstrate that when training data are available to estimate photoswitching rates, the unknown number of molecules can be accurately recovered from the posterior mode of the number of molecules given the number of localizations. Finally, we demonstrate the method on experimental data by quantifying the number of adapter protein linker for activation of T cells on the cell surface of the T-cell immunological synapse. Availability and implementation Software and data available at https://github.com/lp1611/mol_count_dstorm. Supplementary information Supplementary data are available at Bioinformatics online.

Patel, Lekha↗

Raytracing the long trace profiler

The optical design of the Long Trace Profiler optical system is explored with a commercial raytrace program, Zemax OpticStudio™ (ZOS)1, with the intent of finding and correcting sources of systematic error. ZOS provides both geometric raytracing tools and physical optics Gaussian beam propagation and diffraction image calculation tools, and two design modes, sequential component (SC) and non-sequential component (NSC) that are optimized for different aspects of the design process. The original LTP-II system employs a singlet lens with a 1250 mm focal length. It is optimized to provide minimum distortion over a surface slope angle range of ±5 mrad. Using the ZOS tools, we are able to simulate ghost rays that produce distortion in the beam spot image and can minimize the distortion by deliberate misalignment of the beamsplitter (BS) components. Unfortunately, the reference beam is compromised because of the component tilts. The most recent LTP500 system design simplifies the optical system and makes the reference beam usable again, even with misalignment of the polarizing beamsplitter (PBS). Two lenses are designed for the LTP500 - a cemented doublet that has been fabricated, and a singlet with one aspheric surface. Both have focal distances of 500 mm with an expanded angular measurement range of ±10 mrad. The aspheric singlet provides superior performance. ZOS allows the import of wavefront measurement data produced by commercial interferometer software. We apply the wavefront error measurement from the cemented doublet to the model to show that the 19nm RMS wavefront error needs to be improved by at least a factor of ten in order to reduce the systematic error to a level that will allow the LTP to approach its design limit of a few tens of nanoradians.

Takacs, Peter Z.↗

Fabricating Radial Groove Gratings Using Projection Photolithography

Projection photolithography has been used as a fabrication method for radial grove gratings. Use of photolithographic method for diffraction grating fabrication represents the most significant breakthrough in grating technology in the last 60 years, since the introduction of holographic written gratings. Unlike traditional methods utilized for grating fabrication, this method has the advantage of producing complex diffractive groove contours that can be designed at pixel-by-pixel level, with pixel size currently at the level of 45 45 nm. Typical placement accuracy of the grating pixels is 10 nm over 30 nm. It is far superior to holographic, mechanically ruled or direct e-beam written gratings and results in high spatial coherence and low spectral cross-talk. Due to the smooth surface produced by reactive ion etch, such gratings have a low level of randomly scattered light. Also, due to high fidelity and good surface roughness, this method is ideally suited for fabrication of radial groove gratings. The projection mask is created using a laser writer. A single crystal silicon wafer is coated with photoresist, and then the projection mask, with its layer of photoresist, is exposed for patterning in a stepper or scanner. To develop the photoresist, the fabricator either removes the exposed areas (positive resist) of the unexposed areas (negative resist). Next, the patterned and developed photoresist silicon substrate is subjected to reactive ion etching. After this step, the substrate is cleaned. The projection mask is fabricated according to electronic design files that may be generated in GDS file format using any suitable CAD (computer-aided design) or other software program. Radial groove gratings in off-axis grazing angle of incidence mount are of special interest for x-ray spectroscopy, as they allow achieving higher spectral resolution for the same grating area and have lower alignment tolerances than traditional in-plane grating scheme. This is especially critical for NASA Constellation- X project that will utilize hundreds of gratings all of which need to be precisely aligned for x-ray observation of space.

Iazikov, Dmitri↗

Reaching the Diffraction Limit - Differential Speckle and Wide-Field Imaging for the WIYN Telescope

Speckle imaging allows telescopes to achieve diffraction limited imaging performance. The technique requires cameras capable of reading out frames at a very fast rate, effectively 'freezing out' atmospheric seeing. The resulting speckles can be correlated and images reconstructed that are at the diffraction limit of the telescope. These new instruments are based on the successful performance and design of the Differential Speckle Survey Instrument (DSSI).The instruments are being built for the Gemini-N and WIYN telescopes and will be made available to the community via the peer review proposal process. We envision their primary use to be validation and characterization of exoplanet targets from the NASA, K2 and TESS missions and RV discovered exoplanets. Such targets will provide excellent follow-up candidates for both the WIYN and Gemini telescopes. We expect similar data quality in speckle imaging mode with the new instruments. Additionally, both cameras will have a wide-field mode and standard SDSS filters. They will be highly versatile instruments and it is that likely many other science programs will request time on the cameras. The limiting magnitude for speckle observations will remain around 13-14th at WIYN and 16-17th at Gemini, while wide-field, normal CCD imaging operation should be able to go to much fainter, providing usual CCD imaging and photometric capabilities. The instruments will also have high utility as scoring cameras for telescope engineering purposes, or other applications where high time resolution is needed. Instrument support will be provided, including a software pipeline that takes raw speckle data to fully reconstructed images.

detector↗

Mapping structural heterogeneity at the nanoscale with scanning nano-structure electron microscopy (SNEM)

Here, in this work, we explore the use of scanning electron diffraction (also known as 4D-STEM) coupled with electron atomic pair distribution function analysis (ePDF) to understand the local order (structure and chemistry) as a function of position in a complex multicomponent system, a hot rolled, Ni-encapsulated, Zr 65 Cu 17.5 Ni 10 Al 7.5 bulk metallic glass (BMG), with a spatial resolution of 3 nm. We show that it is possible to gain insight into the chemistry and chemical clustering/ordering tendency in different regions of the sample, including in the vicinity of nano-scale crystallites that are identified from virtual dark field images and in heavily deformed regions at the edge of the BMG. In addition to simpler analysis, unsupervised machine learning was used to extract partial PDFs from the material, modeled as a quasi-binary alloy, and map them in space. These maps allowed key insights not only into the local average composition, as validated by EELS, but also a unique insight into chemical short-range ordering tendencies in different regions of the sample during formation. The experiments are straightforward and rapid and, unlike spectroscopic measurements, don’t require energy filters on the instrument. We spatially map different quantities of interest (QoI’s), defined as scalars that can be computed directly from positions and widths of ePDF peaks or parameters refined from fits to the patterns. We developed a flexible and rapid data reduction and analysis software framework that allows experimenters to rapidly explore images of the sample on the basis of different QoI’s. The power and flexibility of this approach are explored and described in detail. Because of the fact that we are getting spatially resolved images of the nanoscale structure obtained from ePDFs we call this approach scanning nano-structure electron microscopy (SNEM), and we believe that it will be powerful and useful extension of current 4D-STEM methods.

36 MATERIALS SCIENCE↗

Evolving Design Criteria for Very Large Aperture Space Based Telescopes and Their Influence on the Need for Integrated Tools in the Optimization Process

NASA's Advanced Mirror Technology Development (AMTD) program has been developing the means to design and build the future generations of space based telescopes. With the nearing completion of the James Webb Space Telescope (JWST), the astrophysics community is already starting to define the requirements for follow-on observatories. The restrictions of available launch vehicles and the possibilities of planned future vehicles have fueled the competition between monolithic primaries (with better optical quality) and segmented primaries (with larger apertures, but with diffraction, costs and figure control issues). Regardless of the current shroud sizes and lift capacities, these competing architectures share the need for rapid design tools. As part of the AMTD program a number of tools have been developed and tested to speed up the design process. Starting with the Arnold Mirror Modeler (which creates Finite Element Models (FEM) for structural analysis) and now also feeds these models into thermal stability analyses. They share common file formats and interchangeable results. During the development of the program, numerous trade studies were created for 4-meter and 8-meter monolithic primaries, complete with support systems. Evaluation of these results has led to a better understanding of how the specification drives the results. This paper will show some of the early trade studies for typical specification requirements such as lowest mirror bending frequency and suspension system lowest frequency. The results use representative allowable stress values for each mirror substrate material and construction method and generic material properties. These studies lead to some interesting relationships between feasible designs and the realities of actually trying to build these mirrors. Much of the traditional specifications were developed for much smaller systems, where the mass and volume of the primary where a small portion of the overall satellite. JWST shows us that as the aperture grows, the primary takes up the majority of the mass and volume and the established rules need to be adjusted. For example, a small change in lowest frequency requirement can change the cost by millions of dollars. The paper uses numerous trade studies created during the software development phase of the Arnold Mirror Modeler to illustrate the influences of system specifications on the design space. The future telescopes will require better performance, stability and documented feasibility to meet the hurdles of today's budget and schedules realities. AMTD is developing the tools, but the basic system planning mentality also has to adopt to the requirements of these very large and complex physical structures.

Arnold, William R., Sr.↗

Further Development Of Aperture: A Precise Extremely Large Reflective Telescope Using Re-Configurable Elements: NASA Innovative Advanced Concepts (NIAC) - Phase II

One of the pressing needs for space ultraviolet-visible astronomy is a design to allow larger mirrors than the James Webb Space Telescope primary. The diameter of the rocket fairing limits the mirror diameter such that all future missions calling for mirrors up to 16 meters in diameter or larger will require a mirror that is deployed post-launch. In response to the deployment requirement, we address the issues of this concept called "A Precise Extremely Large Reflective Telescope Using Reconfigurable Elements (APERTURE) with both hardware experiments and software simulations... We designed and built several fixtures with O-rings to hold a membrane. We established a coating process to make a membrane that was coated on one side with Cr and the other side with Cr-Terfenol-D-NiCo. The Terfenol-D (T-D hereafter) is the MSM (Magnetic Smart Memory) we use. We bought and established a procedure for measuring a deformation over time and purchased a Shack Hartmann system from Imagine Optic (https://www.imagine-optic.com). The first substrate we used was DuPont (TM) Kapton® polyimide film. Due to material creep, we found the stability over a 48-hour period with a Kapton substrate was not as good as desired (greater than 1 micron). We then switched to CP1 Polyimide. We found the CP1 much more stable to creep, being stable from about 3 hours to 48 hours to within a measurement error to below approximately 0.1 micron. We produced a 13 micron maximum deviation on a 50-millimeter-diameter piece of CP1 (25 microns thick). The T-D coating was about 2 microns, and the other layers, about 10 nanometers. The magnetic field at the base was about 0.1 teslas. We can make the T-D film at least 5 times thicker and the magnetic field at least 5 times stronger, and hence make deformations as much as 25 times larger. We have a formed a collaboration produced at the NIAC (NASA Innovative Advanced Concepts) mid-term review with Dr. Ron Shiri of Goddard Space Flight Center (GSFC) to explore making controlled deviations on lambda/14-lambda/20 scales which are required to bring a surface to the diffraction limit. We carried out only preliminary work on Si using a Coordinate Measuring Machine (CMM), which produced deviations on the 1 micron level. We are still working on a program to bring to GSFC a flat enough (radius of curvature greater than 10 microns) -coated a Si piece with Cr, T-D, NiCo. Then we plan to carry out tests with an interferometer. Further, we formed a new collaboration with Prof. Rajan Vaidyanathan of the University of Central Florida to replace the CP1 with a shape memory alloy (SMA). With his collaboration, we acquired new Federal funding outside of NASA to explore the use of SMAs (we use NiTi). Our preliminary results indicate that we can produce deformations greater than 1 micron on approximately 100 microns thick. Furthermore we have shown that the NiTi can deploy to better than 1 micron of its set original and then trained shape.

Re-Configurable Elements↗

Synchrotron-based techniques for characterizing STCH water-splitting materials

Understanding the role of oxygen vacancy–induced atomic and electronic structural changes to complex metal oxides during water-splitting processes is paramount to advancing the field of solar thermochemical hydrogen production (STCH). The formulation and confirmation of a mechanism for these types of chemical reactions necessitate a multifaceted experimental approach, featuring advanced structural characterization methods. Synchrotron X-ray techniques are essential to the rapidly advancing field of STCH in part due to properties such as high brilliance, high coherence, and variable energy that provide sensitivity, resolution, and rapid data acquisition times required for the characterization of complex metal oxides during water-splitting cycles. X-ray diffraction (XRD) is commonly used for determining the structures and phase purity of new materials synthesized by solid-state techniques and monitoring the structural integrity of oxides during water-splitting processes (e.g., oxygen vacancy–induced lattice expansion). X-ray absorption spectroscopy (XAS) is an element-specific technique and is sensitive to local atomic and electronic changes encountered around metal coordination centers during redox. While in operando measurements are desirable, the experimental conditions required for such measurements (high temperatures, controlled oxygen partial pressures, and H 2 O) practically necessitate in situ measurements that do not meet all operating conditions or ex situ measurements. Here, we highlight the application of synchrotron X-ray scattering and spectroscopic techniques using both in situ and ex situ measurements, emphasizing the advantages and limitations of each method as they relate to water-splitting processes. The best practices are discussed for preparing quenched states of reduction and performing synchrotron measurements, which focus on XRD and XAS at soft (e.g., oxygen K-edge, transition metal L-edges, and lanthanide M-edges) and hard (e.g., transition metal K-edges and lanthanide L-edges) X-ray energies. The X-ray absorption spectra of these complex oxides are a convolution of multiple contributions with accurate interpretation being contingent on computational methods. The state-of-the-art methods are discussed that enable peak positions and intensities to be related to material electronic and structural properties. Through careful experimental design, these studies can elucidate complex structure–property relationships as they pertain to nonstoichiometric water splitting. A survey of modern approaches for the evaluation of water-splitting materials at synchrotron sources under various experimental conditions is provided, and available software for data analysis is discussed.

08 HYDROGEN↗

Investigation of Magmatic Activities on Early Mars Using Igneous Mineral Chemistry in Gale Crater, Mars

One objective of rover missions is exploring the geological context of the surroundings. Over the years, igneous petrology and sedimentology have been disconnected, the first investigating magmatic processes and volcanic activities, and the second seeking environmental conditions in the past and assessing the habitability of the planet. Although different, one is related to the other: igneous rocks are altered and broken down, leading to the formation of sedimentary rocks, which can in turn be used to back out the nature of their magmatic source. The Curiosity rover that landed in the 3.7 Gyr old impact crater Gale is traveling through sedimentary rocks. About fifty float rocks have been observed, and several of them with ambiguous texture and composition have been classified as igneous or sedimentary depending on studies such as Jake_M. The composition of several unambiguous igneous rocks has been analyzed [4- 6] but their heterogeneity at a larger instrumental (measurement size < 2 cm) scale prevents the measurement of a bulk composition as performed on Earth. An original approach avoiding these two last issues is to consider igneous mineral chemistry analyzed within igneous and sedimentary rocks to assess magmatic processes that could have formed them. Most Curiosity data are used to explore ancient environmental conditions, and a significant number of compositional analyses are under-explored for constraining magmatic activities. We will present how we can make use of sedimentary data for investigating igneous processes in the vicinity of Gale crater. Geological Context: We focus on the first 750 martian days, corresponding to measurements in a coherent lacustrine sedimentary unit called Bradbury, because all sedimentary rocks were sourced from the same watershed and appear to have a consistent source with minimal alteration [2-3]. Igneous detrital minerals including feldspar and pyroxene, are observed in sedimentary rocks. Monte Carlo models showed that minimal cation loss is observed based on the composition of all Bradbury rocks, implying negligible weathering [3]. Although clay minerals are detected in few rocks [7], chemical compositions of rocks can be explained by a mixture of primary igneous minerals [3]. Variation of composition within Bradbury rocks can be explained by mineral sorting and one distinct source component. While a common magmatic source is suggested, Bradbury sediments likely come from several volcanic eruptions from a single magmatic chamber [9- 10]. The occurrence of alkali minerals like sanidine and K-rich rocks throughout Bradbury supports the presence of a potassic component, likely trachytic, while plagioclase and a mafic composition suggest a basaltic component [8-9]. Instruments: Mineral chemistry can be estimated by three instruments onboard Curiosity. The CheMin instrument enables detection of mineral assemblages using X-ray diffraction (XRD). Using Rietveld refinement, each mineral is identified according to their 1D XRD pattern [11]. Note that distinction between pyroxene minerals is challenging with the CheMin instrument due to overlapping peaks on XRD patterns and low angular resolution of the instrument [12]. Then, using least square regression and optimization algorithms based on unit-cell parameters, mineral chemistry has been estimated by [11]. Plagioclase composition has been estimated using the NaAlSi3O8- CaAl2Si2O8 system and alkali feldspar is based on the NaAlSi3O8-KAlSi3O8 system (stars in Fig.1). Two mudstone samples (John Klein and Cumberland) and one sandstone sample (Windjana) were analyzed by CheMin at Yellowknife Bay and Kimberley, respectively. Figure 1. Ternary diagrams of feldspars (top) and pyroxene (bottom) quadrilateral. Stars correspond to CheMin composition and the gray patches to ChemCam composition. The colored dots are the composition of feldspar and pyroxene that crystallized during fractional crystallization at FMQ+1 of a melt extracted at distinct melting degree during the adiabatic ascent of a primitive mantle composition, without any water (left panels) and with 0.5 wt.% of water (right panels) at distinct pressure. The ChemCam instrument enables the analysis of the chemical compositions of rocks at hundreds of micrometer scale (350-550 μm) using laser induced breakdown spectroscopy (LIBS), which may provide the composition of minerals when they are larger than the beam spot (>550 μm) [13]. Within >5000 LIBS points, we performed a typical stoichiometric filtering allowing us to distinguish 56 feldspar and 10 pyroxene mineral compositions (grey patches in Fig. 1). Finally, the Alpha Particle X-ray Spectrometer (APXS) analyzes the composition of rocks with a 1.6 cm diameter spot size. Monte Carlo mass balance modeling allowed [3] to decipher a feldspar range varying between An30 and An40 (Fig. 1). Discussion: Although there could be a more complex history and other ways to form the whole compositional range of igneous minerals analyzed within the Bradbury formation, we are presenting here simple magmatic pathways commonly occurring on Earth using the thermodynamical softwares pMELTS and rhyoliteMELTS [14]. The objective is to find reasonable igneous processes that produce minerals that parallel the compositions of feldspar and pyroxene analyzed by the Curiosity rover. As commonly observed for mid-ocean ridge basalts, the adiabatic ascent of a primitive mantle composition [15] partially melting at 2 GPa has been modeled, followed by the extraction of a liquid at distinct degrees of partial melting, which undergoes fractional crystallization at an oxygen fugacity +1 log unit above the fayalite-magnetite-quartz (FMQ) buffer within the crust (0.02-0.4 GPa) with H2O = 0- 0.5 wt. %. These latter conditions correspond to those recorded within igneous clasts from the Noachian martian breccia NWA 7034 and paired and within Gale igneous rocks (colored dots in Fig. 1) [16-17]. To check the reliability of these 2-step models, we also tested fractional crystallization at similar conditions (FMQ+1; P=0.02-0.4 GPa; H2O = 0-0.5 wt. %) of starting compositions corresponding to that of magmas with distinct melting degrees obtained from isobaric experiments at 2 GPa [18]. Mineral compositions obtained from both models are similar. As shown on Fig. 1, the whole range of observed feldspar compositions cannot be reproduced by fractionation of one magma only. Indeed, while alkali feldspar and Na-plagioclase likely crystallized from fractional crystallization of a low-degree melt (here <15%), plagioclase and pyroxene can only be formed by fractional crystallization of a higher degree melt (here >19%). The corresponding liquid descent lines are broadly in agreement with compositions estimated by ChemCam corresponding to float igneous rocks (Fig. 2) [4-6]. Figure 2. Silica versus alkali content. Lines show the liquid lines of descent from magmas with distinct degrees of melting. Gray patches represents the composition of Gale igneous rocks [4-6]. Trachytic to rhyolitic magmas crystallize alkali feldspar, and andesite to dacite magmas likely form plagioclase. Therefore, at least two starting magmas at distinct melting degrees, which could easily come from a single mantle source, are necessary to explain the whole compositional range of feldspar and pyroxene analyzed within Bradbury rocks. Conclusion: Because rocks from the Bradbury formation are likely originating from the same magmatic source with minimal weathering as supported by several studies using different approaches, igneous mineral chemistry analyzed by CheMin and ChemCam allows us to back out reasonable magmatic pathways that could have crystallized them. Fractional crystallization of at least two starting magmas originating from distinct melting degrees of a single mantle source can explain the whole range of feldspar and pyroxene composition. Both alkaline and sub-alkaline liquids can be produced, with compositions corresponding to those of the igneous rocks analyzed by ChemCam within the Bradbury formation, highlighting the complexity of Mars magmatism.

Payre, V.↗