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Light Isotopes and Trace Organics Analysis of Mars Samples with Mass Spectrometry

Precision measurement of light isotopes in Mars surface minerals and comparison of this isotopic composition with atmospheric gas and other, well-mixed reservoirs such as surface dust are necessary to understand the history of atmospheric evolution from a possibly warmer and wetter Martian surface to the present state. Atmospheric sources and sinks that set these ratios are volcanism, solar wind sputtering, photochemical processes, and weathering. Measurement of a range of trace organic species with a particular focus on species such as amino acids that are the building blocks of terrestrial life are likewise important to address the questions of prebiotic and present or past biological activity on Mars. The workshop topics "isotopic mineralogy" and "biology and pre-biotic chemistry" will be addressed from the point of view of the capabilities and limitations of insitu mass spectrometry (MS) techniques such as thermally evolved gas analysis (TEGA) and gas chromatography (GC) surface experiments using MS, in both cases, as a final chemical and isotopic composition detector. Insitu experiments using straightforward adaptations of existing space proven hardware can provide a substantial improvement in the precision and accuracy of our present knowledge of isotopic composition both in molecular and atomic species in the atmosphere and those chemically bound in rocks and soils. Likewise, detection of trace organic species with greatly improved sensitivity from the Viking GCMS experiment is possible using gas enrichment techniques. The limits to precision and accuracy of presently feasible insitu techniques compared to laboratory analysis of returned samples will be explored. The insitu techniques are sufficiently powerful that they can provide a high fidelity method of screening samples obtained from a diverse set of surface locations such as the subsurface or the interior of rocks for selection of those that are the most interesting for return to Earth.

Mahaffy, P.↗

The Impact of the Assimilation of Aquarius Sea Surface Salinity Data in the GEOS Ocean Data Assimilation System

Ocean salinity and temperature differences drive thermohaline circulations. These properties also play a key role in the ocean-atmosphere coupling. With the availability of L-band space-borne observations, it becomes possible to provide global scale sea surface salinity (SSS) distribution. This study analyzes globally the along-track (Level 2) Aquarius SSS retrievals obtained using both passive and active L-band observations. Aquarius alongtrack retrieved SSS are assimilated into the ocean data assimilation component of Version 5 of the Goddard Earth Observing System (GEOS-5) assimilation and forecast model. We present a methodology to correct the large biases and errors apparent in Version 2.0 of the Aquarius SSS retrieval algorithm and map the observed Aquarius SSS retrieval into the ocean models bulk salinity in the topmost layer. The impact of the assimilation of the corrected SSS on the salinity analysis is evaluated by comparisons with insitu salinity observations from Argo. The results show a significant reduction of the global biases and RMS of observations-minus-forecast differences at in-situ locations. The most striking results are found in the tropics and southern latitudes. Our results highlight the complementary role and problems that arise during the assimilation of salinity information from in-situ (Argo) and space-borne surface (SSS) observations

Salinty↗

Status of Thermal NDT of Space Shuttle Materials at NASA

Since the Space Shuttle Columbia accident, NASA has focused on improving advanced NDE techniques for the Reinforced Carbon-Carbon (RCC) panels that comprise the orbiter's wing leading edge and nose cap. Various nondestructive inspection techniques have been used in the examination of the RCC, but thermography has emerged as an effective inspection alternative to more traditional methods. Thermography is a non-contact inspection method as compared to ultrasonic techniques which typically require the use of a coupling medium between the transducer and material. Like radiographic techniques, thermography can inspect large areas, but has the advantage of minimal safety concerns and the ability for single-sided measurements. Details of the analysis technique that has been developed to allow insitu inspection of a majority of shuttle RCC components is discussed. Additionally, validation testing, performed to quantify the performance of the system, will be discussed. Finally, the results of applying this technology to the Space Shuttle Discovery after its return from the STS-114 mission in July 2005 are discussed.

Cramer, K. Elliott↗

Status of Thermal NDT of Space Shuttle Materials at NASA

Since the Space Shuttle Columbia accident, NASA has focused on improving advanced NDE techniques for the Reinforced Carbon-Carbon (RCC) panels that comprise the orbiter s wing leading edge and nose cap. Various nondestructive inspection techniques have been used in the examination of the RCC, but thermography has emerged as an effective inspection alternative to more traditional methods. Thermography is a non-contact inspection method as compared to ultrasonic techniques which typically require the use of a coupling medium between the transducer and material. Like radiographic techniques, thermography can inspect large areas, but has the advantage of minimal safety concerns and the ability for single-sided measurements. Details of the analysis technique that has been developed to allow insitu inspection of a majority of shuttle RCC components is discussed. Additionally, validation testing, performed to quantify the performance of the system, will be discussed. Finally, the results of applying this technology to the Space Shuttle Discovery after its return from the STS-114 mission in July 2005 are discussed.

Cramer, K. Elliott↗

Status of Thermal NDT of Space Shuttle Materials at NASA

Since the Space Shuttle Columbia accident, NASA has focused on improving advanced nondestructive evaluation (NDE) techniques for the Reinforced Carbon-Carbon (RCC) panels that comprise the orbiter's wing leading edge and nose cap. Various nondestructive inspection techniques have been used in the examination of the RCC, but thermography has emerged as an effective inspection alternative to more traditional methods. Thermography is a non-contact inspection method as compared to ultrasonic techniques which typically require the use of a coupling medium between the transducer and material. Like radiographic techniques, thermography can inspect large areas, but has the advantage of minimal safety concerns and the ability for single-sided measurements. Details of the analysis technique that has been developed to allow insitu inspection of a majority of shuttle RCC components is discussed. Additionally, validation testing, performed to quantify the performance of the system, will be discussed. Finally, the results of applying this technology to the Space Shuttle Discovery after its return from the STS-114 mission in July 2005 are discussed.

Cramer, K. Elliott↗

Mineralogy of the Martian Surface: Crustal Composition to Surface Processes

Over the course of this award we have: 1) Completed and published the results of a study of the effects of hyperfine particles on reflectance spectra of olivine and quartz, which included the development of scattering codes. Research has also progressed in the analysis of the effects of fine particle sizes on clay spectra. 2) Completed the analysis of the mineralogy of dark regions, showed the insitu compositions are highly correlated to the SNC meteorites, and determined that the martian mantle was depleted in aluminum prior to 2-3 GA ago; Studies of the mineralogic heterogeneity of surficial materials on Mars have also been conducted. and 3) Performed initial work on the study of the physical and chemical processes likely to form and modify duricrust. This includes assessments of erosion rates, solubility and transport of iron in soil environments, and models of pedogenic crust formation.

Mustard, John F.↗

Measurement Protocols for In situ Analysis of Organic Compounds at Mars and Comets

The determination of the abundance and chemical and isotopic composition of organic molecules in comets and those that might be found in protected environments at Mars is a first step toward understanding prebiotic chemistries on these solar system bodies. While future sample return missions from Mars and comets will enable detailed chemical and isotopic analysis with a wide range of analytical techniques, precursor insitu investigations can complement these missions and facilitate the identification of optimal sites for sample return. Robust automated experiments that make efficient use of limited spacecraft power, mass, and data volume resources are required for use by insitu missions. Within these constraints we continue to explore a range of instrument techniques and measurement protocols that can maximize the return from such insitu investigations.

Mahaffy, P. R.↗

Measurement Protocols for In Situ Analysis of Organic Compounds at Mars and Comets

The determination of the abundance and chemical and isotopic composition of organic molecules in comets and those that might be found in protected environments at Mars is a first step toward understanding prebiotic chemistries on these solar system bodies. While future sample return missions from Mars and comets will enable detailed chemical and isotopic analysis with a wide range of analytical techniques, precursor insitu investigations can complement these missions and facilitate the identification of optimal sites for sample return. Robust automated experiments that make efficient use of limited spacecraft power, mass, and data volume resources are required for use by insitu missions. Within these constraints we continue to explore a range of instrument techniques and measurement protocols that can maximize the return from such insitu investigations.

Mahaffy, P. R.↗

Micro-measurements of mechanical properties for adhesives and composites using digital imaging technology

The need for a constituent based durability or accelerated life prediction procedure to be used for the engineering design of polymer matrix composites is discussed in the light of current plans for the High Speed Civil Transport (HSCT) concerns about the U.S. infrastructure (bridges, pipelines, etc.) and other technological considerations of national concern. It is pointed out that good measurement procedures for insitu resin properties are needed for both adhesives and composites. A double cantilever beam (DCB) specimen which shows promise for the easy determination of adhesive shear properties is presented and compared with measurements of strains within the bondline using a new optical digital imaging micro-measurement system (DIMMS). The DCB specimen is also used to assess damage in a bonded joint using a dynamic mechanical thermal analysis system (DMTA). The possible utilization of the same DIMMS and DMTA procedures to determine the insitu properties of the resin in a composite specimen are discussed as well as the use of the procedures to evaluate long term mechanical and physical aging. Finally, a discussion on the state-of-the art of the measurement of strains in micron and sub-micron domains is given.

Brinson, Hal F.↗

An investigation of theories of failure for ceramic matrix composites

This final report is comprised of the abstract of a masters thesis research grant. The abstract of the thesis, 'An Investigation of Acoustic Emission Techniques for the Discrimination of Damage Mechanisms in Ceramic Matrix Composites', is as follows: In order to further advance the understanding of the mechanical behavior of ceramic matrix composites (CMS's), acoustic emission (AE) techniques were implemented to monitor and identify damage mechanisms in CMC's under tensile loading. In addition to real-time AE monitoring techniques, a data acquisition system was developed and implemented in order to capture AE waveforms resulting from stress-induced damage. Waveforms were inspected for multiple events, separated in distinct events, and then analyzed to determine waveform characteristics in the time and frequency domains. Waveform characteristics included peak amplitude, event duration, MARSE, energy, and dominant and centroidal frequency. In addition to conventional methods for determining a damage discrimination criteria, a study of the distribution and correlation of the waveform characteristics criteria and a study of the distribution and correlation of the waveform characteristics were performed to aid in the determination of a damage discrimination criteria. The damage discrimination criteria was tested for 'uniqueness', i.e., the effectiveness of the criteria to identify and monitor damage independent of the stress-strain relationship. Insitu radiography was used to substantiate the damage accumulation. A simulation test was also performed over the loading history to study the changes in the waveform characteristics of the system response from a constant excitation. This thesis demonstrates the use of waveform analysis to study the AE activity resulting from stress-induced damage in CMC's in conjunction with other nondestructive evaluation techniques to investigate the mechanical behavior of CMC's.

Hemann, John H.↗

The Vertical Structure of Relative Humidity and Ozone in the Tropical Upper Troposphere: Intercomparisons Among In Situ Observations, A-Train Measurements and Large-Scale Models

In situ measurements in the tropics have shown that in regions of active convection, relative humidity with respect to ice in the upper troposphere is typically close to saturation on average, and supersaturations greater than 20% are not uncommon. Balloon soundings with the cryogenic frost point hygrometer (CFH) at Costa Rica during northern summer, for example, show this tendency to be strongest between 11 and 15.5 km (345-360 K potential temperature, or approximately 250-120 hPa). this is the altitude range of deep convective detrainment. Additionally, simultaneous ozonesonde measurements show that stratospheric air (O3 greater than 150 ppbv) can be found as low as approximately 14 km (350 K/150 hPa). In contrast, results from northern winter show a much drier upper troposphere and little penetration of stratospheric air below the tropopause at 17.5 km (approximately 383 K). We show that these results are consistent with in situ measurements from the Measurement of Ozone and water vapor by Airbus In-service airCraft (MOZAIC) program which samples a wider, though still limited, range of tropical locations. To generalize to the tropics as a whole, we compare our insitu results to data from two A-Train satellite instruments, the Atmospheric Infrared Sounder (AIRS) and the Microwave Limb Sounder (MLS) on the Aqua and Aura satellites respectively. Finally, we examine the vertical structure of water vapor, relative humidity and ozone in the NASA Goddard MERRA analysis, an assimilation dataset, and a new version of the GEOS CCM, a free-running chemistry-climate model. We demonstrate that conditional probability distributions of relative humidity and ozone are a sensitive diagnostic for assessing the representation of deep convection and upper troposphere/lower stratosphere mixing processes in large-scale analyses and climate models.

Selkirk, Henry B.↗

Managing Large Datasets for Atmospheric Research

Since the mid-1980s, airborne and ground measurements have been widely used to provide comprehensive characterization of atmospheric composition and processes. Field campaigns have generated a wealth of insitu data and have grown considerably over the years in terms of both the number of measured parameters and the data volume. This can largely be attributed to the rapid advances in instrument development and computing power. The users of field data may face a number of challenges spanning data access, understanding, and proper use in scientific analysis. This tutorial is designed to provide an introduction to using data sets, with a focus on airborne measurements, for atmospheric research. The first part of the tutorial provides an overview of airborne measurements and data discovery. This will be followed by a discussion on the understanding of airborne data files. An actual data file will be used to illustrate how data are reported, including the use of data flags to indicate missing data and limits of detection. Retrieving information from the file header will be discussed, which is essential to properly interpreting the data. Field measurements are typically reported as a function of sampling time, but different instruments often have different sampling intervals. To create a combined data set, the data merge process (interpolation of all data to a common time base) will be discussed in terms of the algorithm, data merge products available from airborne studies, and their application in research. Statistical treatment of missing data and data flagged for limit of detection will also be covered in this section. These basic data processing techniques are applicable to both airborne and ground-based observational data sets. Finally, the recently developed Toolsets for Airborne Data (TAD) will be introduced. TAD (tad.larc.nasa.gov) is an airborne data portal offering tools to create user defined merged data products with the capability to provide descriptive statistics and the option to treat measurement uncertainty.

Chen, Gao↗

A study of Minnesota land and water resources using remote sensing

The author has identified the following significant results. Both LANDSAT imagery and digital data were studied for usefulness in surveying water conditions of Minnesota lakes. Initial consideration was given to analysis of LANDSAT image densities because of the low technologic and cost requirements. The techniques employed, however, yield inconsistent and unreliable results. A set of criteria are given for using LANDSAT data in identification of three categories of particulate contaminants in Lake Superior. A linear transformation giving the relationship between the residual LANDSAT intensities and concentrations of three contaminants was obtained from correlation of remote sensing data with insitu measurements. LANDSAT imagery was found useful in placing peat bogs and fens in their respective geologic settings. Artificial disturbances and drainageways in peatlands could be recognized and classified.

Shepherd, W. G.↗

Mars Solar Balloon Landed Gas Chromatograph Mass Spectrometer

A Mars surface lander Gas Chromatograph Mass Spectrometer (GCMS) is described to measure the chemical composition of abundant and trace volatile species and isotope ratios for noble gases and other elements. These measurements are relevant to the study of atmospheric evolution and past climatic conditions. A Micromission plan is under study where a surface package including a miniaturized GCMS would be delivered to the surface by a solar heated hot air balloon based system. The balloon system would be deployed about 8 km above the surface of Mars, wherein it would rapidly fill with Martian atmosphere and be heated quickly by the sun. The combined buoyancy and parachuting effects of the solar balloon result in a surface package impact of about 5 m/sec. After delivery of the package to the surface, the balloon would ascend to about 4 km altitude, with imaging and magnetometry data being taken for the remainder of the daylight hours as the balloon is blown with the Martian winds. Total atmospheric entry mass of this mission is estimated to be approximately 50 kg, and it can fit as an Ariane 5 piggyback payload. The GCMS would obtain samples directly from the atmosphere at the surface and also from gases evolved from solid phase material collected from well below the surface with a Sample Acquisition and Transport Mechanism (SATM). The experiment envisioned in the Mars Micromission described would obtain samples from a much greater depth of up to one meter below the surface, and would search for organic molecules trapped in ancient stratified layers well below the oxidized surface. Insitu instruments on upcoming NASA missions working in concert with remote sensing measurement techniques have the potential to provide a more detailed investigation of mineralogy and the extent of simple volatiles such as CO2 and H2O in surface and subsurface solid phase materials. Within the context of subsequent mission opportunities such as those provided by the Ariane 5 piggyback payload based Micromissions, it is essential to implement an even broader chemical analysis and to enable a significant extension of previous isotope measurements. Such a development would enhance the presently very active study of questions of atmospheric evolution and loss and past climatic conditions. The method selected to implement this program can be based on well-established mass spectrometry techniques. Sampled gas is chemically and physically processed to separate the gas mixture into components using gas chromatograph and related enrichment techniques. This allows trace species to be identified and reveals isotopic distributions in many cases with improved precision. Samples of interest, such as organic molecules, may lie deep below the highly oxidized surface layer and the suggested program includes enhanced sampling techniques to measure volatiles preserved in solid phase material deep below the surface as well as gas from the well mixed atmosphere.

Mahaffy, P.↗

InSitu SEM Investigation of Microstructural Damage Evolution and Strain Relaxation in a Melt Infiltrated SiC/SiC Composite

With CMC components poised to complete flight certification in turbine engines on commercial aircraft within the near future, there are many efforts within the aerospace community to model the mechanical and environmental degradation of CMCs. Direct observations of damage evolution are needed to support these modeling efforts and provide quantitative measures of damage parameters used in the various models. This study was performed to characterize the damage evolution during tensile loading of a melt infiltrated (MI) silicon carbide reinforced silicon carbide (SiC/SiC) composite. A SiC/SiC tensile coupon was loaded to a maximum global stress of 30 ksi in a tensile fixture within an SEM while observations were made at 5 ksi increments. Both traditional image analysis and DIC (digital image correlation) were used to quantify damage evolution. With the DIC analysis, microscale damage was observed at the fiber-matrix interfaces at stresses as low as 5 ksi. First matrix cracking took place between 20 and 25 ksi, accompanied by an observable relaxation in strain near matrix cracks. Matrix crack opening measurements at the maximum load ranged from 200 nm to 1.5 m. Crack opening along the fiber-matrix interface was also characterized as a function of load and angular position relative to the loading axis. This characterization was funded by NASA GRC and was performed to support NASA GRC modeling of SiC/SiC environmental degradation

testing↗

Plasma Processing of Lunar Regolith Simulant for Diverse Applications

Versatile manufacturing technologies for extracting resources from the moon are needed to support future space missions. Of particular interest is the production of gases and metals from lunar resources for life support, propulsion, and in-space fabrication. Deposits made from lunar regolith could yield highly emissive coatings and near-net shaped parts for replacement or repair of critical components. Equally important is development of high fidelity lunar simulants for ground based validation of potential lunar surface operations. Described herein is an innovative plasma processing technique for insitu production of gases, metals, coatings, and deposits from lunar regolith, and synthesis of high fidelity lunar simulant from NASA issued lunar simulant JSC-1. Initial plasma reduction trials of JSC-1 lunar simulant have indicated production of metallic iron and magnesium. Evolution of carbon monoxide has been detected subsequent to reduction of the simulant using the plasma process. Plasma processing of the simulant has also resulted in glassy phases resembling the volcanic glass and agglutinates found in lunar regolith. Complete and partial glassy phase deposits have been obtained by varying the plasma process variables. Experimental techniques, product characterization, and process gas analysis will be discussed.

Schofield, Elizabeth C.↗

Temporal Stability of Surface Roughness Effects on Radar Based Soil Moisture Retrieval During the Corn Growth Cycle

A representative soil surface roughness parameterization needed for the retrieval of soil moisture from active microwave satellite observation is difficult to obtain through either in-situ measurements or remote sensing-based inversion techniques. Typically, for the retrieval of soil moisture, temporal variations in surface roughness are assumed to be negligible. Although previous investigations have suggested that this assumption might be reasonable for natural vegetation covers (Moran et al. 2002, Thoma et al. 2006), insitu measurements over plowed agricultural fields (Callens et al. 2006) have shown that the soil surface roughness can change considerably over time. This paper reports on the temporal stability of surface roughness effects on radar observations and soil moisture retrieved from these radar observations collected once a week during a corn growth cycle (May 10th - October 2002). The data set employed was collected during the Optimizing Production Inputs for Economic and Environmental Enhancement (OPE3) field campaign covering this 2002 corn growth cycle and consists of dual-polarized (HH and VV) L-band (1.6 GHz) acquired at view angles of 15, 35, and 55 degrees. Cross-polarized L baud radar data were also collected as part of this experiment, but are not used in the analysis reported on here. After accounting for vegetation effects on radar observations, time-invariant optimum roughness parameters were determined using the Integral Equation Method (IEM) and radar observations acquired over bare soil and cropped conditions (the complete radar data set includes entire corn growth cycle). The optimum roughness parameters, soil moisture retrieval uncertainty, temporal distribution of retrieval errors and its relationship with the weather conditions (e.g. rainfall and wind speed) have been analyzed. It is shown that over the corn growth cycle, temporal roughness variations due to weathering by rain are responsible for almost 50% of soil moisture retrieval uncertainty depending on the sensing configuration. The effects of surface roughness variations are found to be smallest for observations acquired at a view angle of 55 degrees and HH polarization. A possible explanation for this result is that at 55 degrees and HH polarization the effect of vertical surface height changes on the observed radar response are limited because the microwaves travel parallel to the incident plane and as a result will not interact directly with vertically oriented soil structures.

Joseph, A.T.↗

The Application of Principal Component Analysis Using Fixed Eigenvectors to the Infrared Thermographic Inspection of the Space Shuttle Thermal Protection System

The Nondestructive Evaluation Sciences Branch at NASA s Langley Research Center has been actively involved in the development of thermographic inspection techniques for more than 15 years. Since the Space Shuttle Columbia accident, NASA has focused on the improvement of advanced NDE techniques for the Reinforced Carbon-Carbon (RCC) panels that comprise the orbiter s wing leading edge. Various nondestructive inspection techniques have been used in the examination of the RCC, but thermography has emerged as an effective inspection alternative to more traditional methods. Thermography is a non-contact inspection method as compared to ultrasonic techniques which typically require the use of a coupling medium between the transducer and material. Like radiographic techniques, thermography can be used to inspect large areas, but has the advantage of minimal safety concerns and the ability for single-sided measurements. Principal Component Analysis (PCA) has been shown effective for reducing thermographic NDE data. A typical implementation of PCA is when the eigenvectors are generated from the data set being analyzed. Although it is a powerful tool for enhancing the visibility of defects in thermal data, PCA can be computationally intense and time consuming when applied to the large data sets typical in thermography. Additionally, PCA can experience problems when very large defects are present (defects that dominate the field-of-view), since the calculation of the eigenvectors is now governed by the presence of the defect, not the good material. To increase the processing speed and to minimize the negative effects of large defects, an alternative method of PCA is being pursued when a fixed set of eigenvectors is used to process the thermal data from the RCC materials. These eigen vectors can be generated either from an analytic model of the thermal response of the material under examination, or from a large cross section of experimental data. This paper will provide the details of the analytic model; an overview of the PCA process; as well as a quantitative signal-to-noise comparison of the results of performing both embodiments of PCA on thermographic data from various RCC specimens. Details of a system that has been developed to allow insitu inspection of a majority of shuttle RCC components will be presented along with the acceptance test results for this system. Additionally, the results of applying this technology to the Space Shuttle Discovery after its return from flight will be presented.

Cramer, K. Elliott↗