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Mars aqueous chemistry experiment

Mars Aqueous Chemistry Experiment (MACE) is designed to conduct a variety of measurements on regolith samples, encompassing mineral phase analyses, chemical interactions with H2O, and physical properties determinations. From these data, much can be learned or inferred regarding the past weathering environment, the contemporaneous soil micro-environments, and the general chemical and physical state of the Martian regolith. By analyzing both soil and duricrust samples, the nature of the latter may become more apparent. Sites may be characterized for comparative purposes and criteria could be set for selection of high priority materials on future sample return missions. The second year of the MACE project has shown significant progress in two major areas. MACE Instrument concept definition is a baseline design that has been generated for the complete MACE instrument, including definition of analysis modes, mass estimates and thermal model. The design includes multiple reagent reservoirs, 10 discrete analysis cells, sample manipulation capability, and thermal control. The MACE Measurement subsystems development progress is reported regarding measurement capabilities for aqueous ion sensing, evolved gas sensing, solution conductivity measurement, reagent addition (titration) capabilities, and optical sensing of suspended particles.

Clark, Benton C.↗

Glass-Ampoule Breaker

Device breaks glass ampoule in repeatable manner and retains gaseous content so pressure of gas measured accurately. In addition, protects technician from gaseous contents, which can be hazardous. Broken glass and sample materials easily removed for disposal or analysis. Apparatus developed for use in experiments on compatibility of materials.

Christianson, R. C.↗

Effect of the Presence of Chlorates and Perchlorates on the Pyrolysis of Organic Compounds: Implications for Measurements Done with the SAM Experiment Onboard the Curiosity Rover

The Mars Science Laboratory (MSL) Curiosity Rover carries a suite of instruments, one of which is the Sample Analysis at Mars (SAM) experiment. SAM is devoted to the in situ molecular analysis of gases evolving from solid samples collected by Curiosity on Mars surface/sub-surface. Among its three analytical devices, SAM has a gaschromatograph coupled to a quadrupole mass spectrometer (GC-QMS). The GC-QMS is devoted to the separation and identification of organic and inorganic material. Before proceeding to the GC-QMS analysis, the solid sample collected by Curiosity is subjected to a thermal treatment thanks to the pyrolysis oven to release the volatiles into the gas processing system. Depending on the sample, a derivatization method by wet chemistry: MTBSTFA of TMAH can also be applied to analyze the most refractory compounds. The GC is able to separate the organic molecules which are then detected and identified by the QMS (Figure 1). For the second time after the Viking landers in 1976, SAM detected chlorinated organic compounds with the pyrolysis GC-QMS experiment. The detection of perchlorates salts (ClO4-) in soil at the Phoenix Landing site suggests that the chlorohydrocarbons detected could come from the reaction of organics with oxychlorines. Indeed, laboratory pyrolysis experiments have demonstrated that oxychlorines decomposed into molecular oxygen and volatile chlorine (HCl and/or Cl2) when heated which then react with the organic matter in the solid samples by oxidation and/or chlorination processes.

Millan, M.↗

Mass Spectra Deconvolution of Gaseous Mixtures Containing Volatile Organic Compounds

The Spacecraft Atmosphere Monitor (S.A.M.) analyzes all gaseous pollutants in the 1-150Th mass-to-charge range based on their positive-ion mass spectra. Of particular interest is the Trace Gas Analysis (TGA) mode of operation in which S.A.M detects minute amounts of volatile organic compounds (VOC). Pollutant component of the ambient air is sampled on demand in twenty full mass spectra per second. All spectra is accumulated in two-second intervals by an on-board Field Programmable Gate Arrays (FPGA) unit. Mass spectra represents the number of detected fragment ions in a given mass-to-charge ratio channel. Electron impact ionization of neutral molecules results in creation of numerous fragment ions and most of organic compounds will contribute several identical fragments. Despite the presence of these molecular isobars, we developed the deconvolution algorithm capable of identifying target species based on their characteristic fragmentation patterns. We investigate the efficiency of deconvolution algorithm as a function of mass resolution with which mass spectrum is acquired. Higher the mass resolution, better the chances are to distinguish between stereoisomers using their fragmentation propensities, but also results in higher data volumes to be processed by a set of small footprint software stacks hosted by an on-board computer. Finding the balance between deconvolution accuracy and generated data volume under time constrains and limited computing resources is the main topic of this study.

Darrach, M.↗

Influences of Hillslope Biogeochemistry on Anaerobic Soil Organic Matter Decomposition in a Tundra Watershed

In this work, we investigated rates and controls on greenhouse gas (CO 2 and CH 4 ) production in two contrasting water-saturated tundra soils within a permafrost-affected watershed near Nome, Alaska, United States. Three years of field sample analysis have shown that soil from a fen-like area in the toeslope of the watershed had higher pH and higher porewater ion concentrations than soil collected from a bog-like peat plateau at the top of the hillslope. The influence of these contrasting geochemical and topographic environments on CO 2 and CH 4 production was tested in soil microcosms by incubating both the organic- and mineral-layer soils anaerobically for 55 days. Additionally, nitrogen (as NH 4 Cl) was added to half of the microcosms to test potential effects of N limitation on microbial greenhouse gas production. We found that the organic toeslope soils produced more CO 2 and CH 4 , fueled by higher pH and higher concentrations of water-extractable organic C (WEOC). Our results also indicate N limitation on CO 2 production in the peat plateau soils but not the toeslope soils. Together these results suggest that the weathering and leaching of ions and nutrients from tundra hillslopes can increase the rate of anaerobic soil organic matter decomposition in downslope soils by (1) increasing the pH of soil porewater; (2) providing bioavailable WEOC and fermentation products such as acetate; and (3) relieving microbial N limitation through nutrient runoff. We conclude that the soil geochemistry as mediated by landscape position is an important factor influencing the rate and magnitude of greenhouse gas production in tundra soils.

58 GEOSCIENCES↗

In-Lab Rapid Analytical Detection of Lunar Volatiles By Universal Gas Analyzer With Comparison to GC-MS System

Introduction: The curation of permanently shadowed regions (PSRs) [1] on the lunar surface is centered around studies based upon the observed volatiles from the LCROSS mission [2]. The rapid detection of important volatile gases and vapors present in planetary bodies and Astromaterials by a standalone analytical device is an area of intense research interest in our group and Planetary Exploration & Astromaterials Research Laboratory (PEARL) facility and this work is relevant to the future preparation of viable lunar simulants for testing curation efforts down the road. The groundbreaking results obtained from the LCROSS Mission [2] open the requirements for the direct detection of volatiles present in regolith materials collected from the lunar surface. The mass spectrometry of volatile chemicals is a general technique that utilizes a set of instruments that creates charged ions from a gaseous chemical species and measures the intensities vs. mass-to-charge ratio (m/z) [3]. In this context, we discuss in-lab experimental results and procedures for rapid qualitative analysis of main LCROSS volatiles (water, H2S, NH3, CO2, and CH3OH) by a Universal Gas Analyzer (UGA) instrument. Additionally, the instrument performance was evaluated by measuring the isotopic abundance ratio of atmospheric Ar-40 to Ar-36 present in room air since, argon is a relevant gas in planetary studies as it can provide an insight and reference point to isotope studies [4]. Additional, cross comparisons were attempted and made between the two instruments to develop a robust analytical technique by comparing mass spectral data for H2S headspace samples with a Trace-1310/ ISQ 7000 (ThermoFisher Scientific.) GC-MS system. Background: The benchtop UGA System is equipped with an SRS UGA 300 quadrupole mass spectrometer designed and built by Stanford Research Systems [5]. This system can be configured for several types of gaseous chemical analysis. The inlet line continuously samples gases at low flow rates (several milliliters per minute) through a capillary limiting the intake pressure making the instrument ideal for online analysis of select gases and/or room atmosphere. Moreover, in our current UGA system, a change in composition at the inlet can be detected in about 200 milliseconds and a complete spectrum is acquired (for a range of 1-100 amu) in under 45 sec with masses measured at rates up to 25 msec per point [5]. This system provides a quick upstream analytical data that we can then compare to results obtained by our GC-MS system. Sample Preparation: Small volume (2-4 mL) of analyte sample was taken in a 10 mL glass vial and sealed with a crimped cap and purged with pure Ar or N2 gas to displace air from the top. The headspace sample was scanned by the UGA instrument at analog, histogram, and pressure vs. time modes. The isotopic abundance ratio for 40Ar-to-36Ar was estimated by measuring partial pressure vs. time scans and setting the mass at 40 and 36 respectively. Results and Discussions: In this work, we have investigated the applicability of the UGA system by qualitative analysis of a series of LCROSS volatiles measured individually. Fig. 1 demonstrates a set of vertically offset spectra for the partial pressures measured as a function of mass-to-charge (m/z) ratios. The average acquisition time for each spectrum was less than a minute suggesting that the UGA system is ideal for quick analysis of geochemical volatiles. For the cross-comparison, we analyzed an H2S headspace sample by a Trace-1310/ISQ-7000 system and compared mass spectral data with previously measured UGA histogram scan data (Fig. 2). In both cases, major peak positions are the same, however, the intensities of fragment ions ([1H132S]+ and [32S]+) are higher for UGA suggesting that the fragment ionization process is stronger in UGA compared to that of GC-MS. To investigate how the integrated area under each chromatogram varies with the headspace sample volume, a set of five H2S headspace samples with increasing volumes was analyzed by the GC-MS system (Fig. 3, inset). A small volume (e.g., 200 to 1000 µL) of H2S/H2O vapor was withdrawn from a 20 mL stock sample vial containing ~5 mL of 0.4% H2S in water by a gas-tight syringe and added to another 20 mL vial filled with argon and analyzed by the GC-MS system. Finally, the UGA detector sensitivity was evaluated by calculating the atmospheric 40Ar-to-36Ar isotopic abundance ratio in room air by running a partial pressure vs. time scan with setting the atomic mass at 40, and 36. Fig. 4(a) shows a ~25 min duration “P vs. time” scan for 40Ar (plot for 36Ar is not shown). The partial pressure values (~100 points) were corrected by subtracting the corresponding background pressure value for 37Ar and utilized to calculate 40Ar-to-36Ar isotopic abundance ratios as shown by Fig. 4b. The average isotopic abundance ratio is ~306 with a 2*STDEV ~13. This abundance ratio is significantly close to the previously reported value of 298.56 [6] and the ratio obtained by our GC-MS system (303 for a UHP grade Ar sample). Conclusions: Our study strongly evidenced that the benchtop UGA system is a valuable analytical tool for the detection of major LCROSS volatiles. The rapid scanning capability, the inexpensiveness of the whole system, and impressive detection sensitivity prove its worthiness as an essential device for advanced geochemical applications. Moreover, cross comparisons with the GC-MS provide important bridges into advanced curatorial efforts into the future. References: [1] Bickel, V.T., et al. (2021) Nat Commun 12, 5607. [2] Colaprete, A., et al. (2010) Science, 330, 463-468. [3] Glavin, D. P. et al. (2012) 2012 IEEE Aerospace Conference, 1-11. [4] Willett, C. D., et al. (2022) Geochimica et Cosmochimica Acta 329, 119-134. [5] Operation Manual and Programming Reference. (2018) Universal gas Analyzers, Stanford Research Systems. [6] Lee, J. Y., et al. (2006) Geochimica et Cosmochimica Acta 70, 4507–4512. Notes: (4 figures are attached with text as shown by the attached file)

Curation↗

Development and Demonstration of a Prototype Molten Salt Sampling System

Molten salt reactors (MSRs) offer potential operability and safety advantages when compared to commercial light water reactors (LWRs). However, operating experience with MSRs is sparse in comparison to what exists for LWRs. Further, the chemical and isotopic composition of the fuel and/or coolant salt is dynamic and difficult to characterize continuously, posing potential safety, operability, and safeguards unknowns that need to be addressed. A molten salt sampling system (MSSS) is regarded as a necessary subsystem within first generation MSRs used to obtain samples of salt for chemical and isotopic analysis in support of the need to monitor and control salt composition during operation. The MSSS is being developed using the Safety-in-Design (SiD) methodology, which incorporates incremental integration of safety analysis into the design process. The MSSS conceptual design emerging from the application of the early stages of the SiD methodology consists of a sample collection system and its housing, a freeze port, and inert gas control and delivery systems. This article describes the prototypes developed to test the functions of these MSSS subsystems, presents the results of testing in both dry and molten salt environments (including reliability data collection performed in accordance with the principles of SiD and the development of a semiquantitative fault tree model), and summarizes the opportunities for future design and testing enhancements based on the results of prototype testing.

molten salt reactor↗

Plastic additives in the ocean: Use of a comprehensive dataset for meta-analysis and method development

In excess of 13,000 chemicals are added to plastics (‘additives’) to improve performance, durability, and production of plastic products. They are categorized into numerous chemical classes including flame retardants, light stabilizers, antioxidants, and plasticizers. While research on plastic additives in the marine environment has increased over the past decade, there is a lack of methodological standardization. To direct future measurement of plastic additives, we compiled a first-of-its-kind dataset of literature assessing plastic additives in marine environments, delineated by sample type (plastic debris, seawater, sediment, biota). Using this dataset, we performed a meta-analysis to summarize the state of the science. Currently, our dataset includes 217 publications published between 1978 and May 2023. The majority of publications analyzed plastic additives in biota collected from Europe and Asia. Analyses concentrated on plasticizers, brominated flame retardants, and bisphenols. Common sample preparation techniques included Solvent - Agitation extraction for plastic, sediment, and biota samples, and Solid Phase Extraction for seawater samples with dichloromethane and solvent mixtures including dichloromethane as the organic extraction solvent. Finally, most analyses were performed utilizing gas chromatography/mass spectrometry. There are a variety of data gaps illuminated by this meta-analysis, most notably the small number of compounds that have been targeted for detection compared to the large number of additives used in plastic production. The provided dataset facilitates future investigation of trends in plastic additive concentration data in the marine environment (allowing for comparison to toxicity thresholds) and acts as a starting point for optimizing and harmonizing plastic additive analytical methods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hyperpolarized (129)Xe T (1) in oxygenated and deoxygenated blood

The viability of the new technique of hyperpolarized (129)Xe MRI (HypX-MRI) for imaging organs other than the lungs depends on whether the spin-lattice relaxation time, T(1), of (129)Xe is sufficiently long in the blood. In previous experiments by the authors, the T(1) was found to be strongly dependent upon the oxygenation of the blood, with T(1) increasing from about 3 s in deoxygenated samples to about 10 s in oxygenated samples. Contrarily, Tseng et al. (J. Magn. Reson. 1997; 126: 79-86) reported extremely long T(1) values deduced from an indirect experiment in which hyperpolarized (129)Xe was used to create a 'blood-foam'. They found that oxygenation decreased T(1). Pivotal to their experiment is the continual and rapid exchange of hyperpolarized (129)Xe between the gas phase (within blood-foam bubbles) and the dissolved phase (in the skin of the bubbles); this necessitated a complicated analysis to extract the T(1) of (129)Xe in blood. In the present study, the experimental design minimizes gas exchange after the initial bolus of hyperpolarized (129)Xe has been bubbled through the sample. This study confirms that oxygenation increases the T(1) of (129)Xe in blood, from about 4 s in freshly drawn venous blood, to about 13 s in blood oxygenated to arterial levels, and also shifts the red blood cell resonance to higher frequency. Copyright 2000 John Wiley & Sons, Ltd. Abbreviations used BOLD blood oxygen level dependent NOE nuclear overhouses effect PO(2) oxygen partial pressure RBC red blood cells RF radio frequency SNR signal-to-noise ratio.

NASA Discipline Life Support Systems↗

Mass spectrometric analysis of the volatiles released by heating or crushing rocks

Vacuum extraction with subsequent mass spectrometric analysis of evolved volatiles was selected as the analytical procedure. The high-vacuum gas-handling system was constructed of stainless steel. The system was completely free from mercury, grease, or volatile organic materials. The furnace for heating the samples is discussed together with the high-vacuum crusher, the mass spectrometer, and approaches for water determination. The analytical procedure is considered, giving attention to the extraction of volatiles, adsorption studies, and the analysis of volatiles.

Barker, C.↗

RESOLVE Project

The RESOLVE project is a lunar prospecting mission whose primary goal is to characterize water and other volatiles in lunar regolith. The Lunar Advanced Volatiles Analysis (LAVA) subsystem is comprised of a fluid subsystem that transports flow to the gas chromatograph - mass spectrometer (GC-MS) instruments that characterize volatiles and the Water Droplet Demonstration (WDD) that will capture and display water condensation in the gas stream. The LAVA Engineering Test Unit (ETU) is undergoing risk reduction testing this summer and fall within a vacuum chamber to understand and characterize component and integrated system performance. Testing of line heaters, printed circuit heaters, pressure transducers, temperature sensors, regulators, and valves in atmospheric and vacuum environments was done. Test procedures were developed to guide experimental tests and test reports to analyze and draw conclusions from the data. In addition, knowledge and experience was gained with preparing a vacuum chamber with fluid and electrical connections. Further testing will include integrated testing of the fluid subsystem with the gas supply system, near-infrared spectrometer, WDD, Sample Delivery System, and GC-MS in the vacuum chamber. This testing will provide hands-on exposure to a flight forward spaceflight subsystem, the processes associated with testing equipment in a vacuum chamber, and experience working in a laboratory setting. Examples of specific analysis conducted include: pneumatic analysis to calculate the WDD's efficiency at extracting water vapor from the gas stream to form condensation; thermal analysis of the conduction and radiation along a line connecting two thermal masses; and proportional-integral-derivative (PID) heater control analysis. Since LAVA is a scientific subsystem, the near-infrared spectrometer and GC-MS instruments will be tested during the ETU testing phase.

Parker, Ray↗

Analysis of Volatile Organic Compounds in a Controlled Environment: Ethylene Gas Measurement Studies on Radish

Volatile organic compound(VOC), ethylene gas, was characterized and quantified by GC/FID. 20-50 ppb levels were detected during the growth stages of radish. SPME could be a good analytical tool for the purpose. Low temperature trapping method using dry ice/diethyl ether and liquid nitrogen bath was recommended for the sampling process for GC/PID and GC/MS analysis.

Kong, Suk Bin↗

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.↗

Evaluation of Nuclear Spent Fuel Disposal in Clay-Bearing Rock - Process Model Development and Experimental Studies

The DOE R&D program under the Spent Fuel Waste Science Technology (SFWST) campaign has made key progress in modeling and experimental approaches towards the characterization of chemical and physical phenomena that could impact the long-term safety assessment of heat-generating nuclear waste disposition in deep clay/shale/argillaceous rock. International collaboration activities such as heater tests and postmortem analysis of samples recovered from these have elucidated key information regarding changes in the engineered barrier system (EBS) material exposed to years of thermal loads. Chemical and structural analyses of sampled bentonite material from such tests has as well as experiments conducted on these are key to the characterization of thermal effects affecting bentonite clay barrier performance and the extent of sacrificial zones in the EBS during the thermal period. Thermal, hydrologic, and chemical data collected from heater tests and laboratory experiments has been used in the development, validation, and calibration of THMC simulators to model near-field coupled processes. This information leads to the development of simulation approaches (e.g., continuum vs. discrete) to tackle issues related to flow and transport at various scales of the host-rock and EBS design concept. Consideration of direct disposal of large capacity dual-purpose canisters (DPCs) as part of the back-end SNF waste disposition strategy has generated interest in improving our understanding of the effects of elevated temperatures on the EBS design. This is particularly important for backfilled repository concepts where temperature plays a key role in the EBS behavior and long-term performance. This report describes multiple R&D efforts on disposal in argillaceous geologic media through development and application of coupled THMC process models, experimental studies on clay/metal/cement barrier and host-rock (argillite) material interactions, molecular dynamic (MD) simulations of water transport during (swelling) clay dehydration, first-principles studies of metaschoepite (UO 2 corrosion product) stability, and advances in thermodynamic plus surface complexation database development. Drift-scale URL experiments provides key data for testing hydrological-chemical (HC) model involving strong couplings of fluid mixing and barrier material chemical interactions. The THM modeling focuses on heater test experiments in argillite rock and gas migration in bentonite as part of international collaboration activities at underground research laboratories (URLs). In addition, field testing at an URL involves in situ analysis of fault slip behavior and fault permeability. Pore-scale modeling of gas bubble migration is also being investigated within the gas migration modeling effort. Interaction experiments on bentonite samples from heater test under ambient and elevated temperatures permit the evaluation of ion exchange, phase stability, and mineral transformation changes that could impact clay swelling. Advances in the development, testing, and implementation of a spent nuclear fuel (SNF) degradation model coupled with canister corrosion focus on the effects of hydrogen gas generation and its integration with Geologic Disposal Safety Assessment (GDSA). GDSA integration activities includes evaluation of groundwater chemistries in shale formations.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Test Plan for Reirradiation and 1200°C Heating Test of AGR-3/4 Compact 8-1

Post irradiation examination (PIE) and heating tests of tristructural isotropic (TRISO)-coated fuel particles, fuel compacts, and graphite from Advanced Gas Reactor (AGR) irradiation experiment AGR 3/4 are in progress. The AGR-3/4 test train consisted of twelve separate capsules irradiated in the northeast flux trap of the Advanced Test Reactor (ATR) at Idaho National Laboratory (INL) from December 14, 2011, to April 12, 2014 (Collin 2015b). This test plan describes the reirradiation and subsequent heating test of AGR-3/4 Compact 8-1. One of the main goals of this test is to assess the retention of short-lived fission products I-131 (t1/2 = 8.02 d) and Xe-133 (t1/2 = 5.2 d) in fuel kernels. To generate short-lived fission products, the compact will first be reirradiated in the Neutron Radiography Reactor (NRAD). Following reirradiation, the compact will be removed from NRAD, gamma scanned on the Precision Gamma Scanner (PGS), and then loaded into the Fuel Accident Condition Simulator (FACS) furnace for heating at 1200°C. Fission gases and condensable fission products released from the compact will be collected in the Fission Gas Monitoring System (FGMS) and the FACS condensation plates, respectively. The planned uses of AGR-3/4 compacts (including heating testing and destructive analysis) are discussed in the AGR-3/4 PIE plan (Demkowicz 2017). Significant portions of this plan have been completed and additional samples are being used for purposes not captured in that plan.

42 ENGINEERING↗

Analysis of chemical components from plant tissue samples

Information is given on the type and concentration of sterols, free fatty acids, and total fatty acids in plant tissue samples. All samples were analyzed by gas chromatography and then by gas chromatography-mass spectrometry combination. In each case the mass spectral data was accumulated as a computer printout and plot. Typical gas chromatograms are included as well as tables describing test results.

Laseter, J. L.↗

Extraterrestrial Helium (He@C60) Trapped in Fullerenes in the Sudbury Impact Structure

Fullerenes (C60 and C70) have recently been identified in a shock-produced breccia (Onaping Formation) associated with the 1.85-Ga Sudbury Impact Crater. The presence of parts-per-million levels of fullerenes in this impact structure raises interesting questions about the processes that led to the formation of fullerenes and the potential for delivery of intact organic material to the Earth by a large bolide (e.g., asteroid or comet). Two possible scenarios for the presence of fullerenes in the Sudbury impact deposits are that (1) fullerenes are synthesized within the impact plume from the C contained in the bolide; or (2) fullerenes are already present in the bolide and survived the impact event. The correlation of C and trapped noble gas atoms in meteorites is well established. Primitive meteorites contain several trapped noble gas components that have anomalous isotopic compositions, some of which may have a presolar origin. Several C-bearing phases, including SiC, graphite, and diamond, have been recognized as carriers of trapped noble gases. It has also been suggested that fullerenes (C60 and C70) might be a carrier of noble gas components in carbonaceous chondrites. Recently, fullerenes have been detected in separate samples in the Allende meteorite. Carbon-60 is large enough to enclose the noble gases He, Ne, Ar, Kr, and Xe, but it is too small to contain diatomic gases such as N2 or triatomic gases such as CO2. Recent experimental work has demonstrated that noble gases of a specific isotopic composition can be introduced into synthetic fullerenes at high temperatures and pressures; these encapsulated gases can then be released by the breaking of one or more C bonds during step-heating under vacuum. These thermal-release patterns for He encapsulated within the C60 molecule (He@C60) are similar to the patterns for acid residues of carbonaceous chondrites, suggesting that fullerenes could be an additional carrier of trapped noble gases in acid residues of meteorites. Analysis and Results: In order to characterize the noble gas compositions of the Sudbury fullerenes, we undertook a systematic study of acid-resistant residues throughout the C-rich layer (Black member) of the Onaping Formation. Samples were demineralized and extracted using standard techniques. The Onaping extracts were analyzed using several techniques, including UV-Vis adsorption, electro spray mass spectrometry, and laser desorption (linear and reflectron) time-of-flight (TOF) mass spectrometry (LDMS). The Sudbury fullerenes were then separated and purified using HPLC coupled with a photo diode array detector. The HPLC extracts containing the purified fullerenes were loaded into a metal tube furnace within a glove box under a N atmosphere in preparation for noble gas analyses. The 3-He and 4-He content of the fullerene extracts was measured using previously reported standard techniques . Discussion: Fullerenes (C60 and C70) in the Sudbury Impact Structure have been found to contain trapped He with a 3-He/4-He ratio greater than 5 x 10(exp -4). The 3-He/4-He ratio exceeds the accepted solar value by more than 30% and is more than 10x higher than the maximum reported mantle value. Terrestrial nuclear reactions or cosmic-my bombardment are not sufficient to generate such a high ratio. The 3-He/4-He ratios in the Sudbury fullerenes are similar to those determined for interplanetary dust particles. The greater-than-solar ratios of 3-He/4-He in the Sudbury fullerenes may indicate a presolar origin, although alternative mechanisms occurring in the ISM to explain these high ratios (e.g., spallation reactions, selective He implantation, etc.) cannot be entirely ruled out. We are currently attempting to isolate enough fullerene material to measure anomalous Ne (or Kr or Xe) contained within the C60 (e.g., the "pure" 22-Ne component) and thus determine whether the Sudbury fullerenes are indeed presolar in origin.

Becker, L.↗

Evaluation of subsurface transport processes of delayed gas signatures applicable to underground nuclear explosions

Radioactive gas signatures from underground nuclear explosions (UNEs) result from gas-migration processes occurring in the subsurface. The processes considered in this study either drive or retard upward migration of gases from the detonation cavity. The relative importance of these processes is evaluated by simulating subsurface transport in a dual-permeability medium for the multi-tracer Noble Gas Migration Experiment (NGME) originally intended to study some aspects of transport from a UNE. For this experiment, relevant driving processes include weak two-phase convection driven by the geothermal gradient, over pressuring of the detonation cavity, and barometric pumping while gas sorption, dissolution, radioactive decay, and usually diffusion represent retarding processes. From deterministic simulations we found that over-pressuring of the post-detonation chimney coupled with barometric pumping produced a synergistic effect amplifying the tracer-gas reaching the surface. Bounding simulations indicated that the sorption and dissolution of gases, tending to retard transport, were much smaller than anticipated by earlier laboratory studies. The NGME observations themselves show that differences in gas diffusivity have a larger effect on influencing upward transport than do the combined effects of tracer-gas sorption and dissolution, which is consistent with a Sobol’ sensitivity analysis. Both deterministic simulations and those considering parametric uncertainties of transport-related properties predict that the excess in concentration of SF 6 compared to 127 Xe as might be captured in small volumetric samples should be much smaller than the order-of-magnitude contrast found in the large-volume gas samples taken at the site. While extraction of large-volume subsurface gas samples is shown to be capable of distorting in situ gas compositions, the highly variable injection rate of SF 6 into the detonation cavity relative to that of 127 Xe at the start of the field experiment is the most likely explanation for the large difference in observed concentrations.

58 GEOSCIENCES↗