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Reducing Organic Contamination in NASA JSC Astromaterial Curation Facility

Future robotic and human spaceflight missions to the Moon, Mars, asteroids and comets will require handling and storing astromaterial samples with minimal inorganic and organic contamination to preserve the scientific integrity of each sample. Much was learned from the rigorous attempts to minimize and monitor organic contamination during Apollo, but it was not adequate for current analytical requirements; thus [1]. OSIRIS-REx, Hayabusa-2, and future Mars sample return will require better protocols for reducing organic contamination. Future isolation con-tainment systems for astromaterials, possibly nitrogen enriched gloveboxes, must be able to reduce organic and inorganic cross-contamination. In 2012, a baseline study established the current state of organic cleanliness in gloveboxes used by NASA JSC astromaterials curation labs that could be used as a benchmark for future mission designs [2, 3]. After standard ultra-pure water (UPW) cleaning, the majority of organic contaminates found were hydrocarbons, plasticizers, silicones, and solvents. Hydro-carbons loads (> C7) ranged from 1.9 to 11.8 ng/cm2 for TD-GC-MS wafer exposure analyses and 5.0 to 19.5 ng/L for TD-GC-MS adsorbent tube exposure. Plasticizers included < 0.6 ng/cm2 of DBP, DEP, TXIB, and DIBP. Silicones included < 0.5 ng/cm2 of cyclo(Me2SiO)x (x = 6, 8, 9, 10) and siloxane. Solvents included < 1.0 ng/cm2 of 2-cyclohexen-1-one, 3,5,5-trimethyl- (Isopho-rone), N-formylpiperidine, and 2-(2-butoxyethoxy) ethanol. In addition, DBF, rubber/polymer additive was found at < 0.2 ng/cm2 and caprolactam, nylon-6 at < 0.6 ng/cm2. Reducing Organics: The Apollo program was the last sam-ple return mission to place high-level organic requirements and biological containment protocols on a curation facility. The high vacuum complex F-201 glovebox in the Lunar Receiving Labora-tory used ethyl alcohol (190 proof), 3:1 benzene/methanol (nano grade solution), and heat sterilization at 130degC for 48 hours to reduce organic contamination. In addition, both heat sterilization and peracetic acid sterilization were used in the atmospheric de-contamination (R) cabinets. Later, Lunar curation gloveboxes were degreased with a pressurized Freon 113 wash. Today, UPW has replaced Freon as the standard cleaning procedure, but does not have the degreasing solvency power of Freon. Future Cleaning Studies: Cleaning experiments are cur-rently being orchestrated to study how to degrease and reduce organics in a JSC curation glovebox lower than the established baseline. Several new chemicals in the industry have replaced traditional degreasing solvents such as Freon and others that are now federally restricted. However, these new suites of chemicals remain untested for lowering organics in curation gloveboxes. 3M's HFE-7100DL and DuPont's Vertrel XF are currently being tested as a replacement for Freon 113 as a degreaser at JSC cura-tion facilities. In addition, the use of UPW as a final rinse is be-ing tested, which presumably can maintain a lower total organic carbon load than the filtered purity of chemical solutions. References: [1] Allton J.H. et al. (2012) LPS XLIII, 2439; [2] Calaway M.

Calaway, M. J.↗

Advances in X-ray Instruments to Support Mars Sample Return

The Mars 2020 Perseverance rover is currently collecting drill cores of ancient igneous and sedimentary rock in and around Jezero crater for potential transport to Earth. These samples from the martian surface will enable detailed mineralogical, geochemical, and petrological measurements to characterize ancient depositional and diagenetic environments, quantitatively age-date the samples, and identify the building blocks for life or evidence for life itself. Furthermore, these drill cores are especially precious because they may represent the most pristine samples from the martian surface and our best chance at identifying martian life, as future sample return missions may be conducted by humans that can introduce biological contaminants to the samples. Because of the importance of these samples, we must take great care in their handling, curation, and preliminary analyses so that they are preserved for scientific measurements for decades to come. In-situ measurements by Perseverance have identified minerals that further warrant special treatment of the returned samples. Hydrated sulfate carbonate, swelling clay minerals, and oxychlorine salts are extremely sensitive to changes in temperature and relative humidity. The structures of hydrated sulfates and oxychlorine minerals, in particular, readily change when exposed to different conditions, meaning the mineral assemblage of the as-returned samples may be lost if the samples aren’t handled properly. Characterizing the as-returned mineral assemblage, particularly of the salts, is essential for reconstructing past aqueous conditions and habitability. To characterize the as-returned mineral assemblage, the samples must be analyzed rapidly before phase changes occur and/or under controlled conditions (e.g., within a glove box). Significant recent advances in X-ray instrumentation for robotic exploration of the solar system have resulted in high-resolution miniaturized instruments that would provide mineralogical, geochemical, and petrological information on the returned martian samples without degradation of the mineral assemblage. Here, we describe a combined X-ray diffractometer/X-ray fluorescence spectrometer (XRD/XRF), an X-ray computed tomographic (XCT) instrument, and a scanned beam XRF mapping instrument that could be used in a glove box so that the martian samples remain under controlled conditions.

E. B. Rampe↗

From Apollo to the Future, the NASA Curation Model for Engaging the Sample Science Community Maximizes Science on Extraterrestrial Samples

The Astromaterials Acquisition and Curation Office at Johnson Space Center (JSC) has enjoyed a long-term partnership (50 years!) with a broad community of planetary sample scientists. This partnership has enabled the curators of planetary samples to plan for and enact evolving requirements for preservation of sample scientific integrity and for handling and long-term storage. The basis for this relationship is a standing peer review advisory committee composed of leading scientists who are recognized for achievements in sample analysis. The committee and its descendants have brought familiarity with the most relevant scientific investigations and the associated analytical and contamination challenges. Beginning with Apollo, the review committee was charged with oversight of curatorial operations and with ensuring fair access to samples. As additional samples from other planetary bodies were acquired, the committee evolved, taking on new responsibilities, reflected in committee name changes. However, oversight of curatorial operations and fair allocation of samples remain basic responsibilities. Committee recommendations are sent to the NASA Headquarters Discipline Scientist for approval. To minimize conflict of interest and maximize fair access, the rules governing the make-up of the committee is structured. Systematic rotation of leadership and staggered terms of membership allow the committee to retain expertise while bringing in fresh ideas. The first peer review committee was called the Lunar Sample Analysis and Planning Team (LSAPT) and was formalized in early 1968 with about 15 members. Their function was to review a) the equipment and procedures used in the new Lunar Receiving Laboratory (LRL); b) the proficiency and capability of the LRL staff; c) the sequence of sample analysis and allocation after quarantine release; and d) the findings of the Preliminary Examination Team (PET). According to LSAPT member Gerald Wasserburg, one of the first issues they faced was deciding whether to have most of the sample analyses performed in house at the LRL or to distribute samples to members of the scientific community. LSAPT concluded that the major scientific investigations should be carried out externally to the LRL by scientists chosen for their expertise in specific disciplines. Further they recommended that the PET's basic characterization of samples be circulated to the broad scientific community. LSAPT set its own agenda, paid attention to facility details, closely monitored the move of samples from the LRL to the interim curatorial facility in 1973, and was active in inspecting curation facilities. Between 1975 and 1979, a Facility Subcommittee of LSAPT oversaw the design and construction of a permanent facility for preservation of lunar samples. The result was an outstanding facility still in use today. In 1977, a separate peer review committee, the Meteorite Working Group (MWG), was formed to evaluate requests for new meteorites then being collected in Antarctica under what would in 1980 become a 3-agency agreement (National Science Foundation, NASA, Smithsonian Institution). By 1979, after lunar samples were moved into the new permanent facility, the vacated gloveboxes and laboratory were prepared for meteorite curation. Recognizing that LSAPT had been helpful in setting up the JSC curatorial facility for Antarctic meteorites, JSC recommended the review committee be given expanded duties, including advice on curation and analysis of materials from other planetary bodies and the name be changed to Lunar and Planetary Sample Team (LAPST). In 1993, LAPST was renamed the Curation and Analysis Planning Team for Extraterrestrial Materials (CAPTEM) to reflect additional functions. CAPTEM is chartered to be (1) a community-based, interdisciplinary forum for discussion and analysis of matters concerning the collection and curation of extraterrestrial samples, including planning future sample return missions and (2) a standing review panel, charged with evaluating proposals requesting allocation of all extraterrestrial samples contained in NASA collections. Efficiency and flexibility are gained through use of subcommittees, both ad hoc and standing. Transition of the MWG to a subcommittee of CAPTEM was completed in 2017. Today subcommittees review allocation requests for lunar samples, Antarctic meteorites, cosmic dust, Stardust cometary samples, Genesis solar wind samples, and samples returned from asteroids. Other subcommittees address facilities, informatics, and micro-cratered substrates. Planetary samples have been sent to research teams in over 30 countries world-wide. The expertise in the care and fair distribution of astromaterials by NASA using this model spans generations of planetary sample scientists and is a valuable resource to be tapped for future sample returns - OSIRIS-REx, Hayabusa 2, and Mars 2020.

Allton, Judith↗

Pieces of Other Worlds - Extraterrestrial Samples for Education and Public Outreach

During the Year of the Solar System spacecraft from NASA and our international partners will encounter two comets; orbit the asteroid Vesta, continue to explore Mars with rovers, and launch robotic explorers to the Moon and Mars. We have pieces of all these worlds in our laboratories, and their continued study provides incredibly valuable "ground truth" to complement space exploration missions. Extensive information about these unique materials, as well as actual lunar samples and meteorites, are available for display and education. The Johnson Space Center (JSC) has the unique responsibility to curate NASA's extraterrestrial samples from past and future missions. Curation includes documentation, preservation, preparation, and distribution of samples for research, education, and public outreach. At the current time JSC curates six types of extraterrestrial samples: (1) Moon rocks and soils collected by the Apollo astronauts (2) Meteorites collected on US expeditions to Antarctica (including rocks from the Moon, Mars, and many asteroids including Vesta) (3) "Cosmic dust" (asteroid and comet particles) collected by high-altitude aircraft (4) Solar wind atoms collected by the Genesis spacecraft (5) Comet particles collected by the Stardust spacecraft (6) Interstellar dust particles collected by the Stardust spacecraft These rocks, soils, dust particles, and atoms continue to be studied intensively by scientists around the world. Descriptions of the samples, research results, thousands of photographs, and information on how to request research samples are on the JSC Curation website: http://curator.jsc.nasa.gov/ NASA provides a limited number of Moon rock samples for either short-term or long-term displays at museums, planetariums, expositions, and professional events that are open to the public. The JSC Public Affairs Office handles requests for such display samples. Requestors should apply in writing to Mr. Louis Parker, JSC Exhibits Manager. Mr. Parker will advise successful applicants regarding provisions for receipt, display, and return of the samples. All loans will be preceded by a signed loan agreement executed between NASA and the requestor's organization. Email address: louis.a.parker@nasa.gov Sets of twelve thin sections of Apollo lunar samples and sets of twelve thin sections of meteorites are available for short-term loan from JSC Curation. The thin sections are designed for use in college and university courses where petrographic microscopes are available for viewing. Requestors should contact the Ms. Mary Luckey, Education Sample Curator. Email address: mary.k.luckey@nasa.gov

Allen, Carlton C.↗

Apollo Next Generation Sample Analysis (ANGSA): A Segue to the Next Era of Lunar Exploration and Sample Return Activities

In the fifty years since the first lunar samples were collected on Apollo 11, significant advancements have taken place in laboratory analysis, planetary science, and astromaterials curation. These advances are now being leveraged for the Apollo Next Generation Sample Analysis (ANGSA) Program, which aims to study specially curated Apollo samples that have never been studied before. Since Apollo 17 in 1972, a great deal has been learned about the Moon, including the unique environments of the poles. Building upon Apollo and remote sensing studies since then, the Artemis Program aims to explore the cold environments near the lunar south pole while achieving the concurrent goals of landing the first woman and the next man on the Moon by 2024. Recent developments for ANGSA have significantly accelerated our readiness for Artemis sample return, particularly in the area of cold sample studies. Four science teams were selected to study cold and/or volatile-bearing samples collected during the Apollo program. These samples have special storage and handling requirements that necessitate their processing in a -20°C environment that meets the Apollo materials and cleanliness requirements. NASA has recently undertaken the development and implementation of a cold sample processing facility to support ANGSA. A similar facility will be needed to process the cold, volatile-bearing samples planned to be returned by Artemis missions; therefore, ANGSA provides excellent preparation for Artemis’ future cold sample processing efforts. We will outline the goals of the ANGSA and Artemis programs, illustrating the complementary nature of the work for both. We will describe the efforts to date in designing, testing, and implementing a cold curation facility that meets the requirements of ANGSA and Apollo curation. We will then outline future work for that facility to reach operational readiness. Finally, we will present the sample collection and curation strategies for Artemis, showing how they overlap and build on ANGSA efforts. The development of cold curation at NASA represents a significant leap in the knowledge, experience, and technologies used in astromaterials curation, opening the door for new investigations of lunar volatiles, impacts, formation processes, prebiotic chemistry, and resource utilization, among many others.

Julie Mitchell↗

Oxidation of Palladium-Chromium Alloys for High Temperature Applications

An alloy consisting of Pd with 13 wt % Cr is a promising material for high temperature applications. High temperature performance is degraded by the oxidation of the material, which is more severe in the fine wires and thin films used for sensor applications than in the bulk. The present study was undertaken to improve our understanding of the physical and chemical changes occurring at these temperatures and to identify approaches to limit oxidation of the alloy. The alloy was studied in both ribbon and wire forms. Ribbon samples were chosen to examine the role of grain boundaries in the oxidation process because of the convenience of handling for the oxidation studies. Wire samples 25 microns in diameter which are used in resistance strain gages were studied to correlate chemical properties with observed electrical, physical, and structural properties. Overcoating the material with a metallic Cr film did prevent the segregation of Pd to the surface; however, it did not eliminate the oxidation of the alloy.

Piltch, Nancy D.↗

Sample Return Systems for Extreme Environments (SaRSEE)

Sample return missions offer a greater science yield when compared to missions that only employ in situ experiments or remote sensing observations, since they allow the application of more complex technological and analytical methodologies in controlled terrestrial laboratories,that are both repeatable and can be independently verified. The successful return of extraterrestrial materials over the last four decades has contributed to our understanding of the solar system, but retrieval techniques have largely depended on the use of either soft-landing, or touch-and-go procedures that result in high V requirements, larger spacecraft mass ratios, and return yields typically limited to a few grams of surface materials that have experienced varying degrees of alteration from space weathering. Hard-landing methods using planetary penetrators offer an alternative for sample return that significantly reduce a mission's V and mass ratios,increase sample yields, and allow for the collection of subsurface materials, and lessons can be drawn from previous sample return missions. The following details progress in the design,development, and testing of penetrator/sampler technology capable of surviving subsonic and low, supersonic impact velocities (<700 m/s) that would enable the collection of geologic materials using tether technology to return the sample to a passing spacecraft. The testing of energy absorbing material for protecting the sample, design evolution and field testing of the penetrator, and dynamic modeling of tether behavior during sampling are discussed. It is shown through both modeling and field testing that penetrators at speeds between 300-600 m/s (~Mach 1-2) can penetrator into the ground to depths of 1-2 m with overall structural integrity attained.The first flight tests demonstrated the potential for survivability at these speeds. The second flight series demonstrated core sample collection with partial ejection of the sample return canister. The 3rd flight series demonstrated self-ejection of the sample return system fully intact and with the core retaining the full stratigraphy of the rock bed. The tether analysis shows that the forces on the tether during release and return of the sample to the main spacecraft are all at levels that can easily be handled by existing tether materials. The mass analysis of the requirements indicates that sample return form the asteroids could be handled with Discovery or New Frontier range of missions dependent on the number of samples to be returned to the Earth.

Winglee, R. M.↗

Gene Expression Measurement Module (GEMM) - A Fully Automated, Miniaturized Instrument for Measuring Gene Expression in Space

The capability to measure gene expression on board spacecraft opens the door to a large number of high-value experiments on the influence of the space environment on biological systems. For example, measurements of gene expression will help us to understand adaptation of terrestrial life to conditions beyond the planet of origin, identify deleterious effects of the space environment on a wide range of organisms from microbes to humans, develop effective countermeasures against these effects, and determine the metabolic bases of microbial pathogenicity and drug resistance. These and other applications hold significant potential for discoveries in space biology, biotechnology, and medicine. Supported by funding from the NASA Astrobiology Science and Technology Instrument Development Program, we are developing a fully automated, miniaturized, integrated fluidic system for small spacecraft capable of in-situ measurement of expression of several hundreds of microbial genes from multiple samples. The instrument will be capable of (1) lysing cell walls of bacteria sampled from cultures grown in space, (2) extracting and purifying RNA released from cells, (3) hybridizing the RNA on a microarray and (4) providing readout of the microarray signal, all in a single microfluidics cartridge. The device is suitable for deployment on nanosatellite platforms developed by NASA Ames' Small Spacecraft Division. To meet space and other technical constraints imposed by these platforms, a number of technical innovations are being implemented. The integration and end-to-end technological and biological validation of the instrument are carried out using as a model the photosynthetic bacterium Synechococcus elongatus, known for its remarkable metabolic diversity and resilience to adverse conditions. Each step in the measurement process-lysis, nucleic acid extraction, purification, and hybridization to an array-is assessed through comparison of the results obtained using the instrument with those from standard laboratory protocols. Once developed, the system can be used with minor modifications for multiple experiments on different platforms in space, including extension to higher organisms and microbial monitoring. A proposed version of GEMM that is capable of handling both microbial and tissue samples on the International Space Station will be briefly summarized.

Pohorille, Andrew↗

Genesis Solar Wind Sample Curation Documentation

Introduction: A scientist with experience as a sample science analyst, provider of flight hardware for multiple missions, and senior engineer in an ISO 2000-rated manufacturing plant has described the timeline of key participants in any PI-led sample return mission, the breadth of the organizations involved [1,2], and, of interest to this meeting, choosing the types of data to preserve and issues of future data accessibility. This work broadens that perspective by giving similar lessons from Genesis sample curation point-of-view. Curation participation regarding data gathering was part of the mission review process from the beginning. Genesis’ story illustrates outcome of several choices about types of data to record and preserve. Precision analysis of solar wind atoms captured in pure, ultraclean substrates is the driving science goal; therefore, detailed documentation was captured from all mission and curation phases and from investigator laboratories because these processes affect the final analytical results [3]. Pre-flight: Design and fabrication of the spacecraft. Like many modern small sample return missions, Genesis was a tightly managed team integrated across science, engineering and curation. Communication across the team was excellent, and, for the most part, the hands-on engineering technicians understood the impacts of “small choices” they routinely make, and the eyes-on oversight of manufacturing processes by scientists was mindful of details. The payload was designed by the Jet Propulsion Laboratory and the spacecraft by Lockheed Martin. Solar wind collectors and instruments were fabricated by multiple vendors and laboratories. The main portion of the payload was assembled at JSC. Fabrication procedures and contamination-control data (with witness coupons) were stored primarily at JSC. The original composition, dimensions and configuration of components, results of thermal testing, etc. are still needed for interpretation of analytical data. At times, these must be estimated from secondary information acquired pre-flight. Moreover, some files (e.g., original 3-D models and early Powerpoint) cannot be opened using software. Archived curation data includes 2-D drawings, material usage lists, QA documentation and analyses of consumables used during fabrication. Important chemical information still resides in archived hardware, paints and lubricants, material coupons, cleaning coupons, environmental witness plates and reference materials from manufacturing facilities. Purity and cleanliness of collector substrates. Semi-conductor vendors provided surface cleanliness data and some purity data. Purity for specific elements of interest was verified by science team members in their laboratories [4]. Curation archived procurement and shipping records, analysis reports, and non-proprietary fabrication data. A physical archive of flight collector reference materials is maintained for future use so additional data can be collected as analytical techniques improve. These are of increased value due to the hard landing upon re-entry. Cleaning and cleanliness assessments of flight hardware. Cleaning of the science canister payload was performed at JSC in a dedicated ISO 4 cleanroom using ultrapure water (UPW). The cleanliness of this UPW was monitored throughout processing. The archive for the clean lab also includes airborne particle counts, airborne molecular and inorganic contamination measurements as well as cleanroom construction material coupons and witness coupons. Hardware cleanliness was assessed by particle counts in rinse water batches. This information is recorded in batch cleaning forms and logbooks, and are, perhaps, of decreased value due to the hard landing. Post-flight: Curation-generated data. The curation handling history of each Genesis sample is documented in a typical astromaterials sample database which captures sample location, physical description and characterization data. Samples have a “shelf life”. Crucial to the preservation of samples is ongoing documentation of the sample environment, initially under curatorial control but is now a separate facility function with requires coordination. PI-generated data. Data on sample characterization and cleaning techniques continues to be generated by sample users [5]. These are often captured in LPSC abstracts, but these “engineering” results often are not publishable as stand-alone papers. We are actively looking for ways to make this information more accessible to users. Ion implants into samples have aided science return and can be shared among investigators. These (and similar) materials should be added to the curatorial collection with appropriate process and characterization data generated externally. Summary: Complete data archives for returned astromaterial samples must be broad in types and formats, and inclusive of environmental monitoring.

Genesis↗

Introducing controlled matter into a fluid system

Device consisting of capsule holder and glass inner tube has been developed to handle controlled particulate-contamination samples. Premeasured quantity of particles can be injected into closed fluid system without contamination.

Hoffman, C. E.↗

Multivariate-normality goodness-of-fit tests

Computer program applies chi-square Pearson test to multivariate statistics for application in any field in which data of two or more variables (dimensions) are sampled for statistical purposes. Program handles dimensions two through five, with up to thousand data sets.

Falls, L. W.↗

Trace Gas Analyzer (TGA) program

The design, fabrication, and test of a breadboard trace gas analyzer (TGA) is documented. The TGA is a gas chromatograph/mass spectrometer system. The gas chromatograph subsystem employs a recirculating hydrogen carrier gas. The recirculation feature minimizes the requirement for transport and storage of large volumes of carrier gas during a mission. The silver-palladium hydrogen separator which permits the removal of the carrier gas and its reuse also decreases vacuum requirements for the mass spectrometer since the mass spectrometer vacuum system need handle only the very low sample pressure, not sample plus carrier. System performance was evaluated with a representative group of compounds.

Source record↗

SAVLOC, computer program for automatic control and analysis of X-ray fluorescence experiments

A program for a PDP-15 computer is presented which provides for control and analysis of trace element determinations by using X-ray fluorescence. The program simultaneously handles data accumulation for one sample and analysis of data from previous samples. Data accumulation consists of sample changing, timing, and data storage. Analysis requires the locating of peaks in X-ray spectra, determination of intensities of peaks, identification of origins of peaks, and determination of a real density of the element responsible for each peak. The program may be run in either a manual (supervised) mode or an automatic (unsupervised) mode.

Leonard, R. F.↗

Proton irradiation of simple gas mixtures: Influence of irradiation parameters

In order to get information about the influence of irradiation parameters on radiolysis processes of astrophysical interest, methane gas targets were irradiated with 6.5 MeV protons at a pressure of 1 bar and room temperature. Yields of higher hydrocarbons like ethane or propane were found by analysis of irradiated gas samples using gas chromatography. The handling of the proton beam was of great experimental importance for determining the irradiation parameters. In a series of experiments current density of the proton beam and total absorbed energy were shown to have a large influence on the yields of produced hydrocarbons. Mechanistic interpretations of the results are given and conclusions are drawn with regard to the chemistry and the simulation of various astrophysical systems.

Sack, Norbert J.↗

Use of microgravity to improve the efficiency and power output of Nd-doped laser glasses

The objectives of this research are to: (1) obtain further evidence and understand the science for the reported improvement in chemical homogeneity in glasses prepared in microgravity; and (2) study the feasibility of improving the optical and fluorescence properties, particularly, the limit for Nd(+3) concentration quenching and threshold energy for laser action for laser glasses prepared in microgravity. Attention was directed to ground based investigation whose primary purpose was to determine the suitability and conditions for processing these laser glasses in space. This report describes that the scientific and technical information required for planning flight experiments for these glasses have been obtained, and the preparation for handling and analyzing post flight samples have also been taken. Instruments required for measuring the fluorescence properties of interest have been constructed. The optical and fluorescence properties for the glasses have been measured and made available for comparative property analysis.

Ray, Chandra S.↗

Interchange for Joint Research Entitled: Miniature Laser Spectrometer for Stable Isotope Measurements

As a first step in successfully measuring carbon isotopes optically we have previously demonstrated the measurement of C-13/C-12 to a precision of 0.1% using a tunable diode laser and CO2 spectral lines in the 2300/cm spectral region. This precision of 0.1% (1 per mil) for carbon isotopes is a value sufficiently precise to provide important isotopic data of interest to astrobiologists. The precision presently attainable in gases is sufficient to permit our instrument to be used in the measurement of isotopic ratios of interest to astrobiologists as well as geologists and planetary scientists. A small stable isotope laser spectrometer with a 10 cm path gas cell was designed and constructed. The cell was integrated with a liquid nitrogen cooled tunable diode laser and indium antimonide detector for evaluation. Using the small gas cell, preliminary measurements of 13C/12C in CO2 were made employing single-beam sequential acquisitions of the required spectral data. The results indicate an accuracy of 0.1% which is sufficiently high to make meaningful measurements of martian samples. In addition, improvements in the spectrometer gas handling system have been made to markedly reduce C-13/C-12 isotopic fractionation during sample gas cell loading which we expect will lead to further improvements in precision and accuracy. An important part of making isotopic ratio measurements in solid samples using diode lasers is the conversion of the elements of interest to molecules that have absorption spectra in the mid-ir spectral range accessible by tunable diode lasers. In this project we have investigated the necessary sample preparation procedures to extract carbon, an element of astrobiological importance, from model soil compounds and to convert it to CO2, a molecule with appropriate optical absorption characteristics for reliable laser spectrometer isotopic ratio measurements of 13C/12C. We have considered calcium carbonate as a model for a component of the martian regolith, and we have formulated a simple heating protocol for extracting carbon in the form of CO2.

Becker, J. F.↗

Analysis of lunar samples for carbon compounds.

Description of one approach to the analysis for carbon compounds in lunar materials from the Apollo 11 mission. The sequential scheme followed generally accepted organic geochemical practices, but was unusual in its application to a single sample. The procedures of the scheme were designed to minimize handling of the solids and extracts or hydrolysates. The solid lunar sample was retained in all steps of the sequential analysis in the vessel in which it was originally placed. Centrifugation was used to separate solid and liquid phases after extraction or refluxing. Liquids were recovered from solids by decantation.

Kvenvolden, K. A.↗

Discovery and Analysis of Rare High-Impact Failure Modes using Adversarial RL-Informed Sampling

Adaptive learning agents have tremendous potential to handle critical tasks currently performed by humans. Unfortunately, due to their complexity, it can be difficult to verify that these learning agents do not have critical failure modes. Standard verification and validation methods often do not apply directly to learning agents and Monte Carlo methods have difficulty covering even a small fraction of the state space, especially in multiagent systems or over long time horizons. To overcome this difficulty, we demonstrate an adaptive stress-testing method based on reinforcement learning of correlations that raise the probability of failure. This approach has three key properties: (1) it is able to find rare failure modes with far greater sample efficiency than Monte Carlo methods, (2) it can estimate the true probability of a failure mode despite the inherent bias in the learning method, and (3) it is capable of learning and resampling compact representations of multimodal failure spaces. These properties are important in practice as we need to find disparate failure modes while accounting for their actual relevance. This is a significant advantage over traditional adaptive stress testing methods that give abstract likelihoods of particular failure instances, but cannot estimate the probability of a broader failure mode. We test our algorithm on a simple problem from the aviation domain where an autonomous aircraft lands in gusty wind conditions. The results suggest that we can find failure modes with far fewer samples than the Monte Carlo approach and simultaneously estimate the probability of failure.

reinforcement learning↗