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At least 595 records · Page 33

Wellbore cement alteration and roles of CO 2 and shale during underground hydrogen storage

To mitigate climate change and adopt renewable energy, energy storage is crucial and can be done in the form of hydrogen gas (H 2 ). Subsurface geologic reservoirs are positioned to store H 2 on the largest scales for the longest terms of all potential options. However, H 2 injection may boost reactions that consume hydrogen, generate undesired gases, and alter pore structures of geomedia. To explore the extent of H 2 -associated biotic reactions at a near wellbore location, four experiments were conducted under underground storage conditions with wellbore cement cores and, in most instances, shale samples submerged in synthetic formation brine. Post-reaction gas, aqueous, and solid phase samples were analyzed using olfactory screening and, later, gas chromatography (GC-MS), inductively coupled plasma optical emission spectroscopy (ICP-OES), scanning electron microscopy (SEM), and synchrotron micro-scale x-ray fluorescence (μ-XRF). Within a period of 16 weeks, hydrogen sulfide (H 2 S) was generated in systems containing both H 2 and shale. XRF mapping identified a zone enriched in iron(II) and reduced sulfur along the rim of cement cross sections that was largely associated with CO 2 -induced cement carbonation. Shale did not show noticeable alteration, but there is evidence it contributed to the initial inoculation of the system and provided nutrients for microbes via water-rock interactions. Here, this study considers both rock formations and wellbore cement not previously evaluated concurrently. Findings support understanding and modeling of H 2 -associated biogeochemical reactions during underground hydrogen storage.

36 MATERIALS SCIENCE↗

New reflections on hard X-ray photon-in/photon-out spectroscopy

Analysis of the electronic structure and local coordination of an element is an important aspect in the study of the chemical and physical properties of materials. This is particularly relevant at the nanoscale where new phases of matter may emerge below a critical size. X-ray emission spectroscopy (XES) at synchrotron radiation sources and free electron lasers has enriched the field of X-ray spectroscopy. Additionally, the spectroscopic techniques derived from the combination of X-ray absorption and emission spectroscopy (XAS–XES), such as resonant inelastic X-ray scattering (RIXS) and high energy resolution fluorescence detected (HERFD) XAS, are an ideal tool for the study of nanomaterials. New installations and beamline upgrades now often include wavelength dispersive instruments for the analysis of the emitted X-rays. With the growing use of XAS–XES, scientists are learning about the possibilities and pitfalls. We discuss some experimental aspects, assess the feasibility of measuring weak fluorescence lines in dilute, radiation sensitive samples, and present new experimental approaches for studying magnetic properties of colloidal nanoparticles directly in the liquid phase.

47 OTHER INSTRUMENTATION↗

Diagnostics of plasma–liquids systems: Challenges and their mitigation

This article will review two popular methods of laser diagnostics in a plasma–liquid system and generally in low-temperature plasmas. These are Thomson scattering and laser-induced fluorescence. Setting up the plasma–liquid interaction experiment will be described while stressing the important points for laser diagnostics and maintaining conditions for correct and repeatable measurements. In this work, I will discuss the caveats that are encountered when measuring an inherently unstable and collisional system, such as plasma interacting with the liquid and how these challenges impact that data analysis and calibration efforts for these two-diagnostic approaches.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Optical and Probe Diagnostics Applied to Reacting Flows

We plan to explore three major threads during the fellowship period. The first interrogates the flame synthesis of carbon nanotubes using aerosol catalysts. Laser light scattering will reveal changes in particle size at various heights above the burner. Analysis of the flame gas by mass spectroscopy will reveal the chemical composition of the mixture. Finally, absorption measurements will map the nanotube concentration within the flow. The second thread explores soot oxidation kinetics. Cavity ring-down absorption measurements of the carbonaceous aerosol can provide a measure of the mass concentration with time and, hence, an oxidation rate. Spectroscopic and direct probe measurements will provide the temperature of the system needed for subsequent modeling. The third thread will explore the details of turbulent flame dynamics. Laser induced incandescence will be applied to measurements of soot volume fraction in a 2-d configuration. Analysis of seed tracer particles by planar laser light MIE scattering will reveal the elemental fuel mixture fraction in the flames. Cavity ring-down spectroscopy, a pulsed transient absorption method, will determine the instantaneous mass loading and its fluctuation. Finally, fluorescence measurements will investigate the formation of PAH's in these flames.

Ticich, Thomas M.↗

4U 1909+07: A Hidden Pearl

We present a detailed spectral and timing analysis of the High Mass X-ray Binary (HMXB) 4U 1909+07 with INTEGRAL and RXTE. 4U 1909+07 is a persistent accreting X-ray pulsar with a period of approximately 605 s. The period changes erratically consistent with a random walk expected for a wind accreting system. INTEGRAL detects the source with an average of 2.4 cps (corresponding to 15 mCrab), but sometimes exhibits flaring activity up to 50 cps (i.e. 300 mCrab). The strongly energy dependent pulse profile shows a double peaked structure at low energies and only a single narrow peak at energies above 20 keV. The phase averaged spectrum is well described by a powerlaw modified at higher energies by an exponential cutoff and photoelectric absorption at low energies. In addition at 6.4 keV a strong iron fluorescence line and at lower energies a black body component are present. We performed phase resolved spectroscopy to study the pulse phase dependence of the spectral parameters: while most spectral parameters are constant within uncertainties, the blackbody normalization and the cutoff folding energy vary strongly with phase.

Kreykenbohm, Ingo↗

NASA Tech Briefs, May 2005

Topics covered include: Fastener Starter; Multifunctional Deployment Hinges Rigidified by Ultraviolet; Temperature-Controlled Clamping and Releasing Mechanism; Long-Range Emergency Preemption of Traffic Lights; High-Efficiency Microwave Power Amplifier; Improvements of ModalMax High-Fidelity Piezoelectric Audio Device; Alumina or Semiconductor Ribbon Waveguides at 30 to 1,000 GHz; HEMT Frequency Doubler with Output at 300 GHz; Single-Chip FPGA Azimuth Pre-Filter for SAR; Autonomous Navigation by a Mobile Robot; Software Would Largely Automate Design of Kalman Filter; Predicting Flows of Rarefied Gases; Centralized Planning for Multiple Exploratory Robots; Electronic Router; Piezo-Operated Shutter Mechanism Moves 1.5 cm; Two SMA-Actuated Miniature Mechanisms; Vortobots; Ultrasonic/Sonic Jackhammer; Removing Pathogens Using Nano-Ceramic-Fiber Filters; Satellite-Derived Management Zones; Digital Equivalent Data System for XRF Labeling of Objects; Identifying Objects via Encased X-Ray-Fluorescent Materials - the Bar Code Inside; Vacuum Attachment for XRF Scanner; Simultaneous Conoscopic Holography and Raman Spectroscopy; Adding GaAs Monolayers to InAs Quantum-Dot Lasers on (001) InP; Vibrating Optical Fibers to Make Laser Speckle Disappear; Adaptive Filtering Using Recurrent Neural Networks; and Applying Standard Interfaces to a Process-Control Language.

Source record↗

In-Field Diffuse Ultraviolet Spectroscopy and Imaging of the Stardust Sample Return Capsule

In-field diffuse Ultraviolet (UV) spectroscopy and imaging systems were developed for the purposes of evaluating the surface chemical composition of spacecraft thermal control coatings and materials. The investigation of these systems and the compilation of an associated UV reflectance and luminescence database were conducted using the Stardust Sample Return Capsule (SRC), located at the Johnson Space Center. Spectral responses of the surfaces of the Stardust forebody and aftbody in both reflectance and fluorescence modes were examined post-flight. In this paper, we report on two primary findings of in-field diffuse UV spectroscopy and imaging: (1) deduction of the thermal history of thermal control coatings of the forebody and (2) bond line variations in the aftbody. In the forebody, the thermal history of thermal control coatings may be deduced from the presence of particular semiconducting defect states associated with ZnO, a common emissivity constituent in thermal control coatings. A spatial dependence of this history was mapped for these regions. In the aftbody, luminescing defect states, associated with Si and SiO2 color centers were found along regions of bond variability.

Pugel, D. Elizabeth↗

High Resolution Emission Spectroscopy of the Alpha Pi-1 - Chi Sigma-1(+) Fourth Positive Band System of CO from Electron Impact

We report electron-impact induced fluorescence spectra [300 mA full width at half maximum (FWHM)] of CO for 20 and 100 eV impact energies of the spectral region of 1300 to 2050 A and high resolution spectra (FWHM) of the v'=5 to v"=l and the v'=3 to v"=O bands showing that the rotational structure of the band system are modeled accurately. The excitation function of the (0,1) band (1597 A) was measured from electron impact in the energy range from threshold to 750 eV and placed on an absolute scale from modem calibration standards.

Beegle, Luther W.↗

A Compact, Tunable Near-UV Source for Quantitative Microgravity Combustion Diagnostics

There is a need for improved optical diagnostic methods for use in microgravity combustion research. Spectroscopic methods with fast time response that can provide absolute concentrations and concentration profiles of important chemical species in flames are needed to facilitate the understanding of combustion kinetics in microgravity. Although a variety of sophisticated laser-based diagnostics (such as planar laser induced fluorescence, degenerate four wave mixing and coherent Raman methods) have been applied to the study of combustion in laboratory flames, the instrumentation associated with these methods is not well suited to microgravity drop tower or space station platforms. Important attributes of diagnostic systems for such applications include compact size, low power consumption, ruggedness, and reliability. We describe a diode laser-based near-UV source designed with the constraints of microgravity research in mind. Coherent light near 420 nm is generated by frequency doubling in a nonlinear crystal. This light source is single mode with a very narrow bandwidth suitable for gas phase diagnostics, can be tuned over several 1/cm and can be wavelength modulated at up to MHz frequencies. We demonstrate the usefulness of this source for combustion diagnostics by measuring CH radical concentration profiles in an atmospheric pressure laboratory flame. The radical concentrations are measured using wavelength modulation spectroscopy (WMS) to obtain the line-of-sight integrated absorption for different paths through the flame. Laser induced fluorescence (LIF) measurements are also demonstrated with this instrument, showing the feasibility of simultaneous WMS absorption and LIF measurements with the same light source. LIF detection perpendicular to the laser beam can be used to map relative species densities along the line-of-sight while the integrated absorption available through WMS provides a mathematical constraint on the extraction of quantitative information from the LIF data. Combining absorption with LIF - especially if the measurements are made simultaneously with the same excitation beam - may allow elimination of geometrical factors and effects of intensity fluctuations (common difficulties with the analysis of LIF data) from the analysis.

Peterson, K. A.↗

Photoionization of seeded combustion products as a method of enhancing the efficiency of magnetohydrodynamic power generators

Here, in this study, we performed an experimental and computational investigation into the feasibility of utilizing photoionization to enhance the electrical conductivity of seeded oxy-fuel combustion products and improve the performance of magnetohydrodynamic (MHD) power generators. We applied a variety of optical and microwave diagnostics to study the ionization and recombination processes of potassium excited by an excimer laser in a high-velocity oxy-fuel free jet. Computational fluid dynamic (CFD) simulations were performed to model the thermophysical properties and species densities of the free jet. The CFD results were validated with position-dependent potassium concentration measurements. Electron recombination exponential lifetimes were measured through time-resolved microwave transmission. The experimental electron lifetimes were compared with lifetimes calculated from CFD-predicted species densities and literature recombination rates. It was determined that K + or O 2 are the most likely recombination partners for photoionized electrons. Time-resolved fluorescence measurements provided evidence of an ionization pathway involving a two-photon ionization of KOH . Finally, a zero-dimensional chemical kinetic model was developed to assess the fundamental viability of inducing a non-equilibrium electron population to provide a net energy return in combustion-driven MHD power generators. We determined that a high energy return is feasible for targeting electrode boundary layers with ultraviolet photoionization. We also found that photoionization could potentially lower the required temperature of the bulk gas flow.

20 FOSSIL-FUELED POWER PLANTS↗

Probing the Mechanism of Selective Phosphate Adsorption from Wastewater Using Aqueous and Synchrotron X-ray Characterization

Ion exchange shows promise for recovering phosphate from wastewater as value-added products, but requires high phosphate selectivity to compete with conventional treatment. Hybrid anion exchange (HAIX) resins, which contain non-selective basic functional groups and selective iron oxide nanoparticles (FeOnp), can effectively remove phosphate from wastewater. However, knowledge gaps remain regarding the mechanisms of phosphate selectivity and influence of competing ions, hindering needed efforts to model adsorption dynamics and design scalable adsorption processes for varying wastewaters. To address these gaps, we integrated aqueous-phase adsorption analysis with solid-phase, synchrotron-based X-ray characterization; this integration facilitated elucidation of the distribution and speciation of iron, phosphate, and competing anions on HAIX resins. We compared a quaternary ammonium-functionalized HAIX resin (SBA) to a tertiary amine version (WBA) to determine the role of functional groups. X-ray radiography revealed differences in FeOnp speciation (goethite vs. ferrihydrite) and distribution (peripheral vs. homogeneous) between the resins, resulting in varied phosphate affinity and intraparticle diffusion resistance. Using micro-X-ray fluorescence (μ-XRF) and micro-X-ray absorption near-edge structure (μ-XANES) spectroscopy, we identified differences in where and how phosphate binds across resin types and wastewaters. Across wastewater compositions, FeOnp sites in WBA contribute more to phosphate adsorption than in SBA, possibly due to variations in Fe distribution and speciation. Phosphate adsorption densities calculated from quantitative μ-XRF maps matched those from aqueous analysis, demonstrating the effectiveness of this integrated approach. Altogether, results demonstrate the use of synchrotron-based X-ray characterization for investigating adsorption mechanisms and advance HAIX as a phosphate recovery technology from complex wastewaters.

Nutrient recovery↗

Synthesis and composition control of epitaxial FeWO4 thin films using pulsed laser deposition

We report the growth of epitaxial FeWO4 thin films on c-plane sapphire via pulsed laser deposition using a Fe 2 O 3 /WO 3 target ablated in an O 2 atmosphere. At a constant O 2 pressure of 1 mTorr, x-ray diffraction (XRD) confirms FeWO 4 as the major crystalline phase for substrate temperatures from 500 to 800 °C. As temperature increases, x-ray fluorescence (XRF) shows the Fe/W ratio remains nearly constant at 0.90 ± 0.02, while x-ray photoelectron spectroscopy (XPS) shows Fe 3+ to Fe 2+ conversion increases from 20% to 35%. Morphological analysis reveals phase separation, likely of amorphous Fe 3+ oxide from crystalline FeWO 4 , increasing with Fe 3+ conversion. This is attributed to an O-rich laser ablated flux, where conversion is driven by the Arrhenius temperature dependence of Fe 3+ → Fe 2+ reduction on the film surface. At a constant substrate temperature of 750 °C, XRD confirms FeWO 4 formation for O 2 pressures from 0.5 to 10 mTorr. As pressure increases, XRF shows the Fe/W ratio decreases from 0.98 to 0.70, while XPS shows Fe 3+ conversion rises from 15% to 70%. Morphology shows phase separation decreasing with increasing Fe 3+ conversion. This is attributed to scattering, where higher O 2 pressure makes the laser ablated flux O-deficient relative to Fe and W, facilitating Fe 2+ formation. Films with Fe 3+ conversion above ∼30% and Fe/W ratios from 0.86 to 0.96 exhibit FeWO 4 optical and electronic properties suitable for photoanode applications.

36 MATERIALS SCIENCE↗

Seeded stimulated X-ray emission at 5.9 keV

X-ray free-electron lasers (XFELs) provide intense pulses that can generate stimulated X-ray emission, a phenomenon that has been observed and studied in materials ranging from neon to copper. Two schemes have been employed: amplified spontaneous emission (ASE) and seeded stimulated emission (SSE), where a second color XFEL pulse provides the seed. Both phenomena are currently explored for coherent X-ray laser sources and spectroscopy. Here, we report measurements of ASE and SSE of the 5.9 keV Mn K α 1 fluorescence line from a 3.9 molar NaMnO 4 solution, pumped with 7 femtosecond FWHM XFEL pulses at 6.6 keV. We observed ASE at a pump pulse intensity of 1.7×10 19 W/cm 2 , consistent with earlier findings. We observed SSE at dramatically reduced pump pulse intensities down to 1.1×10 17 W/cm 2 . These intensities are well within the range of many existing XFEL instruments, which supports the experimental feasibility of SSE as a tool to generate coherent X-ray pulses, spectroscopic studies of transition metal complexes, and other applications.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

EUVE survey observations of the moon

Preliminary survey images of the moon obtained by the Extreme Ultraviolet Explorer and results of data analysis are presented. The preliminary results indicate that the brightness of the moon varies little from observation to observation. Early results also show that the lunar albedo closely matches the relative reflectivity of mineral found on the moon's surface. Further studies are conducted during the spectroscopy phase of the EUVE mission to confirm current results regarding the presence of X-ray fluorescence in the data.

Mcdonald, J. S.↗

Measuring the Chemical Potential of the Martian Regolith to Generate and Sustain Life

A critical component for identifying chemical biosignatures is the ability to assess in-situ the potential of an aqueous geochemical environment to generate and sustain life. On Mars or other solar bodies, in-situ chemical characterization could provide evidence as to whether the chemical composition of the regolith or evaporites in suspected ancient water bodies have been biologically influenced or possess the chemical parameters within which life may have existed, or may still exist. A variety of analytical techniques have been proposed for use in detecting and identify signatures of past or present life. These techniques fall into two groups; visual observation with instruments such as cameras or optical/atomic-force microscopes; or elemental chemical analysis with such instruments as X-ray fluorescence (XRF) and diffraction (XRD), a-proton backscatter (APX), y-ray, Mossbauer, Raman, IR, UV/VIS spectroscopies, gas chromatography (GC), or mass spectrometry (MS). Direct observation of an identifiable lifeform by the first set of instruments in a single sample is highly unlikely, especially for extinct organisms or on the surface. The later instruments can provide vital data as to the elemental mineralogy and geological history of the planet, but are highly inadequate for understanding the chemistry of the planet in terms of indigenous life or interactions with human explorers. Techniques such as XRD, XRF, and APX, provide elemental composition at high limits of detection. Some of this data can be extrapolated or interpolated to provide chemical parameters such as oxidation state or composition. Gas chromatography (GC) without standards and non-specific detectors, has little chance of identifying a mixture of unknown components. Combined with GC or by itself, mass spectrometry (MS) can provide identification of compounds, but in both cases the sample must be appropriately prepared for accurate and reliable analysis. Life as we know it, and probably identify it as such, requires an aqueous environment. Deciphering die chemical speciation of this aqueous environment is the key to recognizing therein the biosignatures of any extinct or present life forms. Identifying the soluble (ionic and nonionic) components by reacting a currently dormant environment can provide a "picture" of the thermodynamics and chemical components of a possibly bioactive environment. The only devices which can provide such information are electrochemical sensors based on the potentiometric ion selective electrodes (ISEs) and on dynamic techniques such as cyclic voltammetry (CV) and stripping voltammetry (SV). Such an array of devices can provide not only the chemical composition of a water-soluble Martian soil sample, but also several other vital chemical parameters such as pH, conductivity, redox potential, and dissolved gases. To address these issues we have been investigating the possible use of an electrochemically-based ion sensor array as a new integrated approach to quantitative analytical and chemometric electrochemical measurements. The sensor array will consist of specific and semispecific ion selective and amperometric transducers, which can simultaneously and continuously identify and semiquantitatively determine over 50 organic and inorganic analytes in water-based environments. Several individual sensors, based on the same principle, have been flight-tested and have been installed as part of the MECA instrumentation on the Mars 2001 Lander for in-situ analyses. However, the microfabrication, integration and multiplexing of such a large number of these sensors on a single substrate have not been previously attempted.

Kounaves, S. P.↗

Experimental Alteration of Basalt to Support Interpretation of Remote Sensing and In Situ Meausrements from Mars

Major occurrences of hydrous alteration minerals on Mars have been found in Noachian impact craters formed in basaltic targets and detected using visible/near infrared (VNIR) spectroscopy. Until recently phyllosilicates were detected only in craters in the southern hemisphere [1, 2]. However, it has been reported that at least nine craters in the northern plains apparently excavated thick layers of lava and sediment to expose phyllosilicates [3] as well. The MER (Mars Exploration Rovers) rovers previously reported results of in situ measurement indicating the presence of alteration minerals on Mars [4,5] and it was recently reported that the Mars Curiosity rover has detected alteration phases in situ at Yellowknife Bay in Gale crater as well [6,7]. An important discovery for Mars geochronology is that the Chemistry and Mineralogy (CheMin) x-ray diffraction (XRD) instrument on Curiosity detected phyllosilicates indicating that phyllosilicate formation on Mars extended beyond the Noachian Epoch [8]. These discoveries indicate that Mars was globally altered by water in the past but does not constrain formation conditions for alteration phase occurrences, which have important implications for the evolution of the surface and the biological potential on Mars. Understanding the alteration assemblages produced by a range of conditions is vital for the interpretation of phyllosilicate spectral signatures as well as in situ measurements and to decipher the environment and evolution of early Mars. The martian surface has been intensely altered by meteorite impacts whose effects include brecciation and melting of target materials as well as the initiation of hydrothermal circulation in a hydrous target [9,10,11,12]. Impact effects may facilitate aqueous alteration of a basaltic target because the rate of silicate dissolution is a function of the degree of crystallinity, surface area, and temperature. The resultant alteration mineralogies from shocked basaltic target material are a function of the original mineral assemblage in the parent rocks, the chemistry of fluids that interacted with the rocks, and physico-chemical conditions (pH, temperatures, and pressure) during the time of mineral formation. Understanding the alteration assemblages produced by a range of conditions is vital for the interpretation of phyllosilicate spectral signatures and to decipher the environment and evolution of early Mars, and especially for identifying habitable niches in which life could be initiated and sustained. No experimentally controlled and well characterized analog materials that simulate martian shock metamorphism and alteration conditions currently exist for calibrating either remote sensing or in situ measurements of Mars. A series of experiments was initiated to assess the effects of systematic changes in the physico-chemical conditions on Mars analog materials thereby providing samples to ground-truth Mars remote sensing observations from CRISM (Compact Reconnaissance Imaging Spectrometer for Mars) and in situ measurements from Opportunity's Mössbauer and Curiosity's CHEMIN (Chemistry and Mineralogy X-Ray Diffraction/XRay Fluorescence) instruments. Results of initial experimental runs as analysed by SEM-EDS (Secondary Electron Microscopy -Energy Dispersive Spectroscopy) and X-ray Diffraction (XRD) analysis are reported here and lay the foundation for comparison with shocked and altered samples that will be characterized in the next phase of this work.

Bell, M. S.↗