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At least 19 records

Investigating Surface Mineralogy, Alteration Processes, and Biomarkers on Mars Using Laser Raman Spectroscopy

Despite a wealth of information from past and ongoing missions to Mars, the capability to determine the mineralogy of surface materials and to connect mineralogy with lithologic characteristics that are diagnostic of the environment in which those materials formed remains inadequate. The 2003 Mars Exploration Rovers (MER) will carry a Mini-TES and a Mossbauer spectrometer, which will provide some detailed mineralogy information. For general characterization of minerals and/or biogenic phases (reduced carbon, PAHs, etc) on the surface of Mars, we have been developing a miniaturized laser Raman spectrometer for in situ analyses -- the Mars Microbeam Raman Spectrometer, MMRS. We are also developing strategies to use Raman spectroscopy as a stand-alone technique and to be used synergistically with other in situ analysis methods in future planetary missions. Through studies of Martian meteorites and terrestrial analogs, we are gaining experience of what compositional and structural information can be obtained on key mineral groups using in-situ Raman measurements. We are developing methods for determining mineral proportions in rocks or soils and identifying rock types from sets of closely spaced, rapidly acquired spectra. We are studying how weathering and alteration affect the Raman and luminescence features of minerals and rocks, and we are investigating the Raman characteristics of biogenic organisms and their remains. These studies form the scientific basis for in-situ planetary Raman spectroscopy, and they are being done in parallel with instrument development towards a flight version of the MMRS.

Alian Wang↗

Destabilization of yttria-stabilized zirconia induced by molten sodium vanadate-sodium sulfate melts

The extent of surface destabilization of ZrO2 - 8 wt percent Y2O3 ceramic disks was determined after exposure to molten salt mixtures of sodium sulfate containing up to 15 mole percent sodium metavanadate (NaVO3) at 1173 K. The ceramic surface was observed to transform from the cubic/tetragonal to monoclinic phase, concurrent with chemical changes in the molten salt layer in contact with the ceramic. Significant attack rates were observed in both pure sulfate and metavanadate sulfate melts. The rate of attack was found to be quite sensitive to the mole fraction of vanadate in the molten salt solution and the partial pressure of sulfur trioxide in equilibrium with the salt melt. The observed parabolic rate of attack is interpreted to be caused by a reaction controlled by diffusion in the salt that penetrates into the porous layer formed by the destabilization. The parabolic rate constant in mixed sodium metavanadate - sodium sulfate melts was found to be proportional to the SO3 partial pressure and the square of the metavanadate concentration. In-situ Raman spectroscopic measurements allowed simultaneous observations of the ceramic phases and salt chemistry during the attack process.

Nagelberg, A. S.↗

Low Temperature Growth of Nanostructured Diamond Films on Metals

The field of nanocrystalline diamond and tetrahedral amorphous carbon films has been the focus of intense experimental activity in the last few years for applications in field emission display devices, optical windows, and tribological coatings, The choice of substrate used in most studies has typically been silicon. For metals, however, the thermal expansion mismatch between the diamond film and substrate gives rise to thermal stress that often results in delamination of the film. To avoid this problem in conventional CVD deposition low substrate temperatures (less than 700 C) have been used, often with the incorporation of oxygen or carbon monoxide to the feedgas mixture. Conventionally grown CVD diamond films are also rough and would require post-deposition polishing for most applications. Therefore, there is an obvious need to develop techniques for deposition of well-adhered, smooth nano-structured diamond films on metals for various tribological applications. In our work, nanostructured diamond films are grown on a titanium alloy substrate using a two-step deposition process. The first step is performed at elevated temperature (820 C) for 30 minutes using a H2/CH4/N2 gas mixture in order to grow a thin (approx. 600 nm) nanostructured diamond layer and improve film adhesion. The remainder of the deposition involves growth at low temperature (less than 600 C) in a H2/CH4/O2 gas mixture. Laser reflectance Interferometry (LRI) pattern during growth of a nanostructured diamond film on Ti-6Al-4V alloy. The first 30 minutes are at a high temperature of 820 C and the rest of the film is grown at a low temperature of 580 T. The fringe pattern is observed till the very end due to extremely low surface roughness of 40 nm. The continuation of the smooth nanostructured diamond film growth during low temperature deposition is confirmed by in-situ laser reflectance interferometry and by post-deposition micro-Raman spectroscopy and surface profilometry. Similar experiments performed without the starting nanostructured diamond layer resulted in poorly adhered films with a more crystalline appearance and a higher surface roughness. This low temperature deposition of nanostructured diamond films on metals offers advantages in cases where high residual thermal stress leads to delamination at high temperatures.

Baker, Paul A.↗

Raman Gas Species Measurements in Hydrocarbon-Fueled Rocket Engine Injector Flows

Rocket engine propellent injector development at NASA-Marshall includes experimental analysis using optical techniques, such as Raman, fluorescence, or Mie scattering. For the application of spontaneous Raman scattering to hydrocarbon-fueled flows a technique needs to be developed to remove the interfering polycyclic aromatic hydrocarbon fluorescence from the relatively weak Raman signals. A current application of such a technique is to the analysis of the mixing and combustion performance of multijet, impinging-jet candidate fuel injectors for the baseline Mars ascent engine, which will burn methane and liquid oxygen produced in-situ on Mars to reduce the propellent mass transported to Mars for future manned Mars missions. The Raman technique takes advantage of the strongly polarized nature of Raman scattering. It is shown to be discernable from unpolarized fluorescence interference by subtracting one polarized image from another. Both of these polarized images are obtained from a single laser pulse by using a polarization-separating calcite rhomb mounted in the imaging spectrograph. A demonstration in a propane-air flame is presented, as well as a high pressure demonstration in the NASA-Marshall Modular Combustion Test Artice, using the liquid methane-liquid oxygen propellant system

Wehrmeyer, Joseph↗

NASA/GSFC Scanning Raman Lidar Measurements of Water Vapor and Cirrus Clouds during WVIOP2000 and AFWEX

The NASA/GSFC Scanning Raman Lidar (SRL) was deployed to the Southern Great Plains CART site from September - December, 2000 and participated in two field campaigns devoted to comparisons of various water vapor measurement technologies and calibrations. These campaigns were the Water Vapor Intensive Operations Period 2000 (WVIOP2000) and the ARM FIRE Water Vapor Experiment (AFWEX). WVIOP2000 was devoted to validating water vapor measurements in the lower atmosphere while AFWEX had similar goals but for measurements in the upper troposphere. The SRL was significantly upgraded both optically and electronically prior to these field campaigns. These upgrades enabled the SRL to demonstrate the highest resolution lidar measurements of water vapor ever acquired during the nighttime and the highest S/N Raman lidar measurements of water vapor in the daytime; more than a factor of 2 increase in S/N versus the DOE CARL Raman Lidar. Examples of these new measurement capabilities along with comparisons of SRL and CARL, LASE, MPI-DIAL, in-situ sensors, radiosonde, and others will be presented. The profile comparisons of the SRL and CARL have revealed what appears to be an overlap correction or countrate correction problem in CARL. This may be involved in an overall dry bias in the precipitable water calibration of CARL with respect to the MWR of approx. 4%. Preliminary analysis indicates that the application of a temperature dependent correction to the narrowband Raman lidar measurements of water vapor improves the lidar/Vaisala radiosonde comparisons of upper tropospheric water vapor. Other results including the comparison of the first-ever simultaneous measurements from four water vapor lidar systems, a bore-wave event captured at high resolution by the SRL and cirrus cloud optical depth studies using the SRL and CARL will be presented at the meeting.

Whiteman, D. N.↗

Raman Gas Species Measurements in Hydrocarbon-Fueled Rocket Engine Injector Flows

Propellent injector development at MSFC (Marshall Space Flight Center) includes experimental analysis using optical techniques, such as Raman, fluorescence, or Mie scattering. For the application of spontaneous Raman scattering to hydrocarbon-fueled flows a technique needs to be developed to remove the interfering polycyclic aromatic hydrocarbon fluorescence from the relatively weak Raman signals. A current application of such a technique is to the analysis of the mixing and combustion performance of multijet, impinging-jet candidate fuel injectors for the baseline Mars ascent engine, which will burn methane and liquid oxygen produced in-situ on Mars to reduce the propellent mass transported to Mars for future manned Mars missions. The present technique takes advantage of the strongly polarized nature of Raman scattering. It is shown to be discernable from unpolarized fluorescence interference by subtracting one polarized image from another. Both of these polarized images are obtained from a single laser pulse by using a polarization-separating calcite rhomb mounted in the imaging spectrograph. A demonstration in a propane-air flame is presented.

Wehrmeyer, Joseph A.↗

Raman Spectroscopy for Instantaneous Multipoint, Multispecies Gas Concentration and Temperature Measurements in Rocket Engine Propellant Injector Flows

Propellent injector development at MSFC includes experimental analysis using optical techniques, such as Raman, fluorescence, or Mie scattering. For the application of spontaneous Raman scattering to hydrocarbon-fueled flows a technique needs to be developed to remove the interfering polycyclic aromatic hydrocarbon fluorescence from the relatively weak Raman signals. A current application of such a technique is to the analysis of the mixing and combustion performance of multijet, impinging-jet candidate fuel injectors for the baseline Mars ascent engine, which will bum methane and liquid oxygen produced in-situ on Mars to reduce the propellent mass transported to Mars for future manned Mars missions. The present technique takes advantage of the strongly polarized nature of Raman scattering. It is shown to be discernable from unpolarized fluorescence interference by subtracting one polarized image from another. Both of these polarized images are obtained from a single laser pulse by using a polarization-separating calcite rhomb mounted in the imaging spectrograph. A demonstration in a propane-air flame is presented.

Wehrmeyer, Joseph A.↗

Raman Spectroscopy for Instantaneous Multipoint, Multispecies Gas Concentration and Temperature Measurements in Rocket Engine Propellant Injector Flows

Propellant injector development at MSFC includes experimental analysis using optical techniques, such as Raman, fluorescence, or Mie scattering. For the application of spontaneous Raman scattering to hydrocarbon-fueled flows a technique needs to be developed to remove the interfering polycyclic aromatic hydrocarbon fluorescence from the relatively weak Raman signals. A current application of such a technique is to the analysis of the mixing and combustion performance of multijet, impinging-jet candidate fuel injectors for the baseline Mars ascent engine, which will burn methane and liquid oxygen produced in-situ on Mars to reduce the propellant mass transported to Mars for future manned Mars missions. The present technique takes advantage of the strongly polarized nature of Raman scattering. It is shown to be discernable from unpolarized fluorescence interference by subtracting one polarized image from another. Both of these polarized images are obtained from a single laser pulse by using a polarization-separating calcite rhomb mounted in the imaging spectrograph. A demonstration in a propane-air flame is presented.

Wehrmeyer, Joseph A.↗

In-Situ Cure Monitoring of the Immidization Reaction of PMR-15

Glass fiber reinforced polymer composites are becoming widely used in industry. With this increase in production, an in-situ method of quality control for the curing of the polymer is desirable. This would allow for the production of high-quality parts having more uniform properties.' Recently, in-situ fiber optic monitoring of polymer curing has primarily focused on epoxy resins and has been performed by Raman or fluorescence methods. In addition, some infrared (IR) investigations have been performed using transmission or ATR cells. An alternate IR approach involves using optical fibers as a sensor by utilizing evanescent wave spectroscopy.

Cossins, Sheryl↗

MEAD In-situ Sampling and Testing at Haughton Crater

The Mars Exploration through Analog-site Drilling (MEAD) project is designed to demonstrate the feasibility and scientific value of robotic drilling missions to Mars in the search for evidence of past or extant life. MEAD conducts high-fidelity field simulations integrating drilling, autonomous operations, and in-situ life-detection and mineralogical instruments. The project tests the Signs of Life Detector (SOLID), proposed for the 2019 Discovery Mars Icebreaker mission, and ARIA (Astronaut Raman Instrument for ISRU and Astrobiology), which provides mineral identification and detects trace organics and volatiles, including indicators of organic thermal maturity. Because current and planned Mars drilling missions operate largely “blind,” MEAD also evaluates the use of drill-induced vibrations recorded by deployed geophones to enable local subsurface mapping for improved targeting of drilling and sampling. In August 2025, MEAD completed its first-year field deployment to Haughton Crater in the Canadian High Arctic, an established Mars impact-crater terrestrial analog site, bringing a Honeybee Robotics TRIDENT drill with applied automation, alongside ARIA, SOLID, and FleetSpace geophones.

Haughton Crater↗

First results from the aerosol lidar and backscatter sonde intercomparison campaign STRAIT'1997 at table mountain facility during February-March 1997

First results of an intercomparison measurement campaign between three aerosol lidar instruments and in-situ backscatter sondes performed at Table Mountain Facility (34.4 deg N, 117.7 deg E, 2280 m asl) in February-March 1997 are presented. During the campaign a total of 414 hours of lidar data were acquired by the Aerosol-Temperature-Lidar (ATL, Goddard Space Flight Center) the Mobile-aerosol-Raman-Lidar (MARL, Alfred Wegener Institute), and the TMF-Aerosol-Lidar (TAL, Jet Propulsion Laboratory), and four backscatter sondes were launched. From the data set altitude profiles of backscatter ratio and volume depolarization of stratospheric background aerosols at altitudes between 15 and 25 km and optically thin high-altitude cirrus clouds at altitudes below 13 km are derived. On the basis of a sulfuric acid aerosol model color ratio profiles obtained from two wavelength lidar data are compared to the corresponding profiles derived from the sonde observations. We find an excellent agreement between the in-situ and ATL lidar data with respect to backscatter and color ratio. Cirrus clouds were present on 16 of 26 nights during the campaign. Lidar observations with 17 minute temporal and 120-300 m spatial resolution indicate high spatial and temporal variability of the cirrus layers. Qualitative agreement is found between concurrent lidar measurements of backscatter ratio and volume depolarization.

Beyerle, G.↗

Lidar Observations of Raman Scattering from S02 in a Power Plant Stack Plume

LIDAR techniques have been successfully applied to the detection of the Raman backscatter from S02 in the plume of a 200 megawatt coal-burning electrical- generating plant from a distance of 210 meters. The LIDAR system used consists of a 61-centimeter-diameter, f /4 Newtonian telescope and a 1.0-1.5-joules per pulse, 1-pulse-per-second ruby laser. Narrow band interference filters are used to select the 7546-angstrom v (sub 1) vibrational line of S02. The signal from a photomultiplier tube was sequentially applied to each 254-nanosecond-wide channel of a 15-cihannel photon counting system, resulting in a direct correlation between channel number and range increment. Photon counts were accumulated from the backscatter of a number of laser pulses (typically 50 or 100), and the accumulated counts per channel printed on paper tape. One sequence of measurements was made during a two-hour period while the plant electrical output was being reduced by approximately 50 percent. Although the Raman system had not been quantitatively calibrated, the LIDAR data correlated well with the varying plant electrical output. N2 scattering observations were also made and an approximate quantitative S02 concentration obtained by ratioing the S02 data to N2 data. This ratio compared well to the in-situ measurements made during the same period by Environmental Protection Agency sampling instruments.

Brumfield, M. L.↗

Applications of excimer lasers for atmospheric species measurements

Excimer lasers are proven sources of high pulse energy and high average power coherent radiation at several wavelength regions throughout the ultraviolet spectrum. If designed properly, excimer lasers can be operated with both low divergence and narrow spectral bandwidth, and using an oscillator - injection-locked amplifier configuration they can be tuned over a 10 to 20 A bandwidth without appreciable loss in energy. Additional wavelength coverage from excimer lasers can be obtained by stimulated Raman scattering. With the development of magnetic switching for the high voltage, high power switches, the electric discharge excimer laser can also be operated reliably for extended periods of time at high pulse rates. All these features make excimer lasers ideal sources of ultraviolet radiation for a variety of remote and in-situ atmospheric species measurements.

Laudenslager, J. B.↗

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.↗

Scanning Raman Lidar Measurements During the WVIOP2000 and AFWEX Field Experiments

The NASA/Goddard Space Flight Center Scanning Raman Lidar (SRL) participated in the Water Vapor IOP 2000 (WVIOP2000) and ARM FIRE Water Vapor Experiment (AFWEX) at the DOE SGP CART site in northern Oklahoma. These experiments occurred during the period of September and December, 2000. The goals of both the WVIOP2000 and AFWEX were to better characterize the water vapor measurement capability of numerous sensors in the lower atmosphere and upper troposphere, respectively. The SRL received several hardware upgrades in anticipation of these experiments that permitted improved measurements of water vapor during the daytime and in the upper troposphere (UT). The daytime SRL water vapor error statistics were demonstrated a factor of 2-3 improvement compared to the permanently stationed CART Raman lidar (CARL). The performance of the SRL in the UT showed improvements as well. The technological upgrades that permitted these improved SRL measurements could also be implemented in the CARL system. Data examples demonstrating the new daytime and upper tropospheric measurement capability of the SRL will be shown at the meeting. In addition, preliminary analysis will be presented on several topics: 1) inter comparison of the water vapor measurements for several water vapor sensors including SRL, CARL, the NASA/Langley Lidar Atmospheric Sensing Experiment (LASE) flown onboard the NASA DC-8, in-situ sensors flown on the DC-8, and the Max Planck Institute Differential Absorption Lidar 2) comparison of cirrus cloud measurements using SRL and CARL and 3) case studies of meteorological events that occurred during the IOPs such as a cold frontal passage on the night of September 23.

Whiteman, David N.↗

A Study of Olivine Alteration to Iddingsite Using Raman Spectroscopy

A crucial task of Mars surface science is to determine past environmental conditions, especially aqueous environments and their nature. Identification of mineral alteration by water is one way to do this. Recent work interprets TES spectra as indicating altered basalt on Mars. Olivine, a primary basaltic mineral, is easily altered by aqueous solutions. Alteration assemblages of olivine may be specific to deuteric, hydrothermal, surface water, or metamorphic environments. Raman spectra are produced by molecular vibrations and provide direct means for studying and identifying alteration products. Here, we present a combined study of changes in the chemical composition and Raman spectra of an olivine as it alters to iddingsite. Iddingsite is found in some SNC meteorites and is presumably present on Mars. The term 'iddingsite' has been used as a catch-all term to describe reddish alteration products of olivine, although some authors ascribe a narrower definition: an angstrom-scale intergrowth of goethite and smectite (presumably saponite) formed in an oxidizing and fluid-rich environment. Alteration conserves Fe (albeit oxidized) but requires addition of Al and H2O and removal of Mg and Si. The smectite that forms may be removed by continued alteration. Dehydration of the goethite forms hematite. Our purpose is to study the mineral assemblage, determine the structural and chemical variability of the components with respect to the degree of alteration, and to find spectral indicators of alteration that will be useful during in-situ analyses on Mars.

Kuebler, K. E.↗

LASE validation experiment: preliminary processing of relative humidity from LASE derived water vapor in the middle to upper troposphere

Lidar Atmospheric Sensing Experiment (LASE) is the first fully engineered, autonomous airborne DIAL (Differentials Absorption Lidar) system to measure water vapor, aerosols, and clouds throughout the troposphere. This system uses a double-pulsed Ti:sapphire laser, which is pumped by a frequency-doubled flashlamp-pumped Nd: YAG laser, to transmit light in the 815 mn absorption band of water vapor. LASE operates by locking to a strong water vapor line and electronically tuning to any spectral position on the absorption line to choose the suitable absorption cross-section for optimum measurements over a range of concentrations in the atmosphere. During the LASE Validation Experiment, which was conducted over Wallops Island during September, 1995, LASE operated on either the strong water line for measurements in middle to upper troposphere, or on the weak water line for measurements made in the middle to lower troposphere including the boundary layer. Comparisons with water vapor measurements made by airborne dew point and frost point hygrometers, NASA/GSFC (Goddard Space Flight Center) Raman Lidar, and radiosondes showed the LASE water vapor mixing ratio measurements to have an accuracy of better than 6% or 0.01 g/kg, whichever is larger, throughout the troposphere. In addition to measuring water vapor mixing ratio profiles, LASE simultaneously measures aerosol backscattering profiles at the off-line wavelength near 815 nm from which atmospheric scattering ratio (ASR) profiles are calculated. ASR is defined as the ratio of total (aerosol + molecular) atmospheric scattering to molecular scattering. Assuming a region with very low aerosol loading can be identified, such as that typically found just below the tropopause, then the ASR can be determined. The ASR profiles are calculated by normalizing the scattering in the region containing enhanced aerosols to the expected scattering by the "clean" atmosphere at that altitude. Images of the total ASR clearly depict cloud regions, including multiple cloud layers, thin upper level cirrus, etc., throughout the troposphere. New data products that are being derived from the LASE aerosol and water measurements include: 1) aerosol extinction coefficient, 2) aerosol optical thickness, 3) precipitable water vapor, and 4) relative humidity (RH). These products can be compared with airborne in-situ, and ground and satellite remote sensing measurements,. This paper presents a preliminary examination of RH profiles in the middle to upper troposphere that are generated from LASE measured water vapor mixing ratio profiles coupled with rawinsonde profiles of temperature and pressure.

Brackett, Vincent G.↗