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At least 613 records · Page 34

Sub-Diurnal Methane Variations on Mars Driven by Barometric Pumping and Planetary Boundary Layer Evolution

In recent years, the Tunable Laser Spectrometer within the Sample Analysis at Mars (TLS-SAM) instrument on board the Mars Science Laboratory (MSL) Curiosity rover has detected methane variations in the atmosphere at Gale crater. Methane concentrations appear to fluctuate seasonally as well as sub-diurnally, which is difficult to reconcile with an as-yet-unknown transport mechanism delivering the gas from underground to the atmosphere. To potentially explain the fluctuations, we consider barometrically induced transport of methane from an underground source to the surface, modulated by temperature-dependent adsorption. The subsurface fractured-rock seepage model is coupled to a simplified 1-D atmospheric mixing model to provide insights on the pattern of atmospheric methane concentrations in response to transient surface methane emissions, as well as to predict sub-diurnal variation in methane abundance for the northern summer period, which is a candidate time frame for a MSL Curiosity sampling campaign. Our analysis suggests that there is a lower limit to the subsurface fracture density that can produce the observed methane patterns, below which the atmospheric methane variations would be out of phase with the observations. The best-performing model scenarios indicate a significant, short-lived methane pulse just prior to sunrise, the detection of which by TLS-SAM would be a potential indicator of the contribution of barometric pumping to Mars' atmospheric methane variations.

54 ENVIRONMENTAL SCIENCES↗

Time‐Series Analysis: A Cautionary Tale

Time-series analysis has often been a useful tool in atmospheric science for deriving long-term trends in various atmospherically important parameters (e.g., temperature or the concentration of trace gas species). In particular, time-series analysis has been repeatedly applied to satellite datasets in order to derive the long-term trends in stratospheric ozone, which is a critical atmospheric constituent. However, many of the potential pitfalls relating to the non-uniform sampling of the datasets were often ignored and the results presented by the scientific community have been unknowingly biased. A newly developed and more robust application of this technique is applied to the Stratospheric Aerosol and Gas Experiment (SAGE) II version 7.0 ozone dataset and the previous biases and newly derived trends are presented.

Damadeo, Robert↗

Sample Analysis at Mars

The next landed missions to Mars, such as the planned Mars Science Laboratory and ExoMars, will require sample analysis capabilities refined well beyond what has been flown to date. A key science objective driving this requirement is the determination of the carbon inventory of Mars, and particularly the detection of organic compounds. While the gas chromatograph mass spectrometers (GC/MS) on the Viking landers did not detect any indigenous organics in near surface fines, it is possible that these measurements were not representative of Mars on the whole. That is, those compounds to which the GC/MS was sensitive would likely not have survived the strong oxidative decomposition in the regolith at the landing sites in question. The near surface fines could very well contain a significant quantity of refractory compounds that would not have been volatilized in the sample ovens on Viking. It is also possible that volatile organics exist on Mars in sedimentary, subsurface, or polar niches.

W B Brinckerhoff↗

Sample Analysis At Mars

The next landed missions to Mars, such as the planned Mars Science Laboratory and ExoMars, will require sample analysis capabilities refined well beyond what has been flown to date. A key science objective driving this requirement is the determination of the carbon inventory of Mars, and particularly the detection of organic compounds. While the gas chromatograph mass spectrometers (GCMS) on the Viking landers did not detect any indigenous organics in near surface fines, it is possible that these measurements were not representative of Mars on the whole. That is, those compounds to which the GC/MS was sensitive would likely not have survived the strong oxidative decomposition in the regolith at the landing sites in question. The near surface fines could very well contain a significant quantity of refractory compounds that would not have been volatilized in the sample ovens on Viking. It is also possible that volatile organics exist on Mars in sedimentary, subsurface, or polar niches.

Brinckerhoff, W. B.↗

Complete Round-Robin Hydrogen Gas Analysis Capability Comparison (Milestone 2.6)

The Department of Energy (DOE) is currently evaluating strategies for the extended dry storage of aluminum-clad spent nuclear fuel (ASNF). Part of this assessment concerns the extent of radiolytic molecular hydrogen (H2) generation from the aluminum cladding’s oxyhydroxide corrosion layers. Understanding this radiation-induced process and the factors effecting it (e.g., system conditions such as temperature and gaseous environment) are essential for the development of predictive computer models to support the Technical Considerations and Challenges for Extended (> 50 yrs) Dry Storage of ASNF program. To achieve this goal and ensure that the experimental data gathered by Task 2 (Oxyhydroxide Layer Radiolytic Gas Generation Resolution) research groups (Idaho National Laboratory and Savannah River National Laboratory) are consistent, a round-robin H2 analysis capability comparison was initiated. Here we present the results from said round-robin and conclude that despite differences in sample preparation, irradiation parameters, and analytical procedures, the measured data are sufficiently consistent between the two laboratories (= 15%).

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Xenon Isotopic Analysis of Individual Intermediate Particles From the OSIRIS-REx Sample of Asteroid Bennu

The OSIRIS-REx mission sampled material from the B-type asteroid Bennu and delivered the sample to Earth on 24 September 2023. Here we present initial xenon isotopic analysis of individual intermediate particles of Bennu material collected by the OSIRIS-REx mission. Noble gases are key tracers of Solar System evolution. Xenon is particularly useful among the noble gases because its nine isotopes allow multiple contributing sources to be unambiguously identified. The sun, asteroids (as measured in meteorites), and comets (measured in the coma of comet 67P) have distinct xenon isotopic signatures reflecting different mixtures of nucleosynthetic components. In addition, 129 I, 238 U, and 244 Pu decay with different half-lives, producing characteristic xenon signatures. Exposure of samples containing light rare earth elements and barium to cosmic rays produces xenon from spallation and secondary neutron capture reaction. Noble gas analyses help address several of the driving hypotheses of the mission [9]. Particle-by-particle analysis can elucidate the diversity of material present and reveal distinct noble gas compositions, including the potential to detect presolar or cometary noble gas signatures on a small scale. The isotopic signature provides a fingerprint that can be used to constrain the sources of volatiles in planetary reservoirs and combined with other information (e.g. mineralogy and petrology of the material analyses) contributes to our understanding of the initial constituents, formation, and history of Bennu and its parent asteroid.

S A Crowther↗

UV-filters and musk fragrances in seafood commercialized in Europe Union: Occurrence, risk and exposure assessment

Highlights: • Largest survey on UV-Fs and musks in seafood commercialized in Europe. • Farmed seabream showed the highest average concentration of UV-Fs. • Wild mackerel showed the highest average concentration of polycyclic musks. • UV-Fs and musks in raw samples were far below the estimated toxicological reference value. In the framework of the FP7 ECsafeSeafood project, 62 seafood samples commercialized in Europe Union from several representative species – mackerel, tuna, salmon, seabream, cod, monkfish, crab, shrimp, octopus, perch and plaice – were analysed for residues of 21 personal care products (PCPs), including 11 UV-filters (UV-Fs) and 10 musk fragrances (musks). PCPs analysis were performed by Quick, Easy, Cheap, Effective Rugged, Safe (QuEChERS), combined with liquid-liquid extraction (LLE) or dispersive solid-phase extraction (dSPE), followed by gas chromatography-tandem mass spectrometry (GC-MS/MS). The results showed the presence in a wide range of samples of nine out of eleven UV-Fs compounds analysed, namely 2-ethylhexyl salicylate (EHS), 2-ethylhexyl,4-methoxycinnamate (EHMC), 4-methylbenzylidenecamphor (4-MBC), benzophenone-1 (BP1), benzophenone-3 (BP3), isoamyl-4-methoxycinnamate (IMC), 2,2′-dihydroxy-4,4′-dimethoxybenzophenone (DHMB), homosalate (HS), and octocrylene (OC), whereas galaxolide (HHCB), galaxolide lactone (HHCB-lactone), and tonalide (AHTN) were the most found musks. The potential risks to human health associated with the exposure to eight of the more prevalent PCPs – EHS, EHMC, 4-MBC, BP1, BP3, IMC, HHCB, and AHTN - through seafood consumption were assessed for consumers from five European countries (Belgium, Ireland, Italy, Portugal and Spain). Results showed that the human exposure to UV-Fs and musks estimated from the concentration values found in seafood and the daily consumption of concerned seafood species, were far below toxicological reference values.

54 ENVIRONMENTAL SCIENCES↗

Impact of Lubricant Oil Additives on the Performance of Pd-Based Three-Way Catalysts

As alternative lubricant anti-wear additives are sought to reduce friction and improve overall fuel economy, it is important that these additives are also compatible with current emissions control catalysts. In the present work, a second-generation oil-miscible phosphorous-containing ionic liquid (IL), is evaluated for its impact on Pd-based three-way catalyst (TWC) reactivity and benchmarked against the industry standard zinc dialkyl-dithio-phosphate (ZDDP). The TWCs are exposed to the lubricant additives in an engine bench under four different scenarios: base case with no additive (NA), ZDDP-only, IL-only, and IL + ZDDP. The engine-aged TWC samples, along with the as-received TWC, are characterized through various analytical techniques including catalyst reactivity evaluation in a bench-flow reactor. The temperature of 50% conversion (T 50 ) for the ZDDP-aged TWC increases by 11, 21, and 36 °C for CO, C 3 H 6 , and C 3 H 8 , respectively, as compared with the no-additive case. Similarly, the T50 for IL-only and IL + ZDDP-aged TWCs also increase as compared with the no-additive case. Even though the water-gas-shift (WGS) reactivity is similar for all engine-aged samples, the IL-aged TWC had higher oxygen storage capacity than the ZDDP-aged TWC. EPMA analysis reveals penetration of phosphorus deep into the washcoat for all engine-aged TWCs. Results from XRD indicate the presence of CePO 4 and AlPO 4 on the washcoat of IL, ZDDP, and IL + ZDDP-aged TWC samples but not on the fresh and NA TWC samples. Additionally, ICP-OES results show a large amount of phosphorus in the washcoat of IL, ZDDP and IL + ZDDP-aged TWC samples and a lesser amount in NA TWC samples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Vitrification of Hanford Tank Waste 241-AP-107 in a Continuous Laboratory-Scale Melter

Low-activity waste (LAW) stored in underground tanks on the Hanford Site in Washington State is planned to be filtered for solids removal and processed through ion exchange columns for cesium removal. These pretreatment steps will allow the waste to be transferred to the Hanford Tank Waste Treatment and Immobilization Plant’s LAW Facility for immobilization into glass. The liquid waste will be combined with glass-forming chemicals (GFCs) to form a waste feed slurry that can be fed to electric melters for vitrification. The process of continuously converting the aqueous feed slurry into a melt is dynamic and includes multiple reactions, degassing, and dissolution processes that depend on heat from the melt below. In this conversion process, waste components are partitioned into one of two streams: glass and off-gas. Washington River Protection Solutions has requested processing information and chemical information associated with these waste products for actual waste from Hanford tank 241-AP-107 (referred to herein as AP-107). To acquire this type of information, a small-scale melter system was designed that would not require high volumes of input waste or the large resource commitment of a full-scale melter system, while also providing dynamic information that would be difficult to determine from batch reactions in a crucible system. A continuous laboratory-scale melter (CLSM) has been designed to operate with a continuous feeding process while periodically pouring glass product and collecting off-gas. The CLSM vessel has been sized to collect the relevant process and chemical information from obtainable volumes of AP-107 waste samples. A total 8.6 L of actual AP-107 tank waste were received after filtering for solids removal and ion exchange for cesium removal. This volume of AP-107 waste was mixed with GFCs to form an estimated 11.8 L of melter feed slurry. A mass of 7.01 kg of glass product were poured from the CLSM vessel during 10.07 hours of charging the AP-107 melter feed, indicating that about 15.0 kg of melter feed was vitrified into glass. The CLSM system was also designed with the capability to fully divert the flow of off-gas produced in the CLSM vessel to a sampling line that could capture the volatile species of interest, such as technetium-99 ( 99 Tc). This novel sampling system avoided the difficulties of slipstream sampling and could be activated once the feeding reached a steady state within the CLSM vessel. Off-gas product samples captured via high-efficiency particulate air (HEPA) filters using this method, as well as selected glass product samples were sent to an analytical lab for chemical analysis.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

UT-GOM2-1 Hydrate Pressure Coring Expedition Volume

From 2-May-2017 to 22-May-2017, the UT-GOM2-1 Hydrate Pressure Coring Expedition drilled two wells in Green Canyon Block 955 (GC 955) in the deepwater Gulf of Mexico: Hole GC 955 H002 (H002) and Hole GC 955 H005 (H005). 21 10 ft (3.05 m) pressure cores were attempted in and near the methane hydrate reservoir. In the first hole, H002, 1 of the 8 cores were recovered under pressure and there was 34% recovery of sediment (both pressurized and depressurized). In the second hole, H005, 12 of the 13 cores were recovered under pressure and there was 72% recovery of sediment. The pressure cores were imaged and logged under pressure. Samples were quantitatively degassed either on-board or on-shore to determine the hydrate concentration and the gas composition. Pore water analyses were performed on depressurized samples, and sediment samples were collected to enable characterization of the microbial community. 21 3.3 ft (1 m) vessels containing pressure core sections were returned to the University of Texas for storage, distribution, and further analysis. These cores will provide a foundation for scientific exploration by the greater hydrate research community.

03 NATURAL GAS↗

BISON TRISO Modeling Advancements and Validation to AGR-1 Data

BISON is a finite element-based nuclear fuel performance code. Among its unique characteristics are its ability to model 1D, 2D, and 3D geometries and its applicability to a wide variety of nuclear fuels. For the last eight years, BISON has included a beginning capability to model tri-structural isotropic (TRISO) fuel. Recently, interest in TRISO fuel has grown, and a significant effort has been made to improve BISON’s capabilities in this area. Capability development has occurred for each material present in TRISO fuel particles: the buffer, inner pyrolytic carbon, silicon carbide, and outer pyrolytic carbon layers, as well as the fuel kernel. New elastic, creep, swelling, thermal expansion, thermal conductivity, and fission gas release (FGR) models are available. New models for the graphite matrix are also now available. Another important addition is the ability to perform statistical failure analysis of large samples of fuel particles. This new capability, which continues to grow, enables evaluation of failure due to pressure or crack formation by analyzing many thousands of particles. This enables realistic calculations of fission product release from the many particles in a TRISO-fueled reactor. These capabilities were checked via regression and verification tests. A large number of code benchmarking problems were also run, showing that BISON’s results closely match those of other software tools. Finally, a significant validation effort was completed in which fission product release, measured as part of the AGR-1 capsule experiments, was compared to BISON outputs. BISON outputs compared very well to the experimental data and to PARFUME results. Interest in BISON’s TRISO capabilities is growing, with the U.S. Nuclear Regulatory Commission (NRC) and Westinghouse Electric Company receiving training during the past year. Multiple other entities have expressed interest in or are actively using BISON. Kairos Power, LLC, has a strong partnership with Idaho National Laboratory (INL) regarding the use of BISON for TRISO analysis. While its capabilities still continue to grow, BISON has already become a powerful tool for TRISO analysis.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Improving Hydrocarbon Separation In Gas Chromatography

Modified solica spheres enhance chromatographic separation. Commercially available silica spheres are modified by reacting them with molecules containing isocyante and isothiocyanate groups. Applications of surface derivatized spheres that result from reaction include analysis of samples prouced by atmospheric or soil probes.

Pollock, G. E.↗

A survey of the properties of early-type galaxies

A compilation of the properties of elliptical and early disk galaxies was completed. In addition to material from the literature, such as Infrared Astronomy Satellite (IRAS) fluxes, the compilation includes recent measurements of HI and CO, as well as a review of the x ray properties by Forman and Jones. The data are used to evaluate the gas content of early systems and to search for correlations with x ray emission. The interstellar medium in early-type galaxies is generally dominated by hot interstellar gas (T approx. 10 to the 7th power K; c.f. the review by Fabbiano 1989 and references therein). In addition, a significant fraction of these galaxies show infrared emission (Knapp, et al., 1989), optical emission lines, and visible dust. Sensitive studies in HI and CO of a number of these galaxies have been completed recently, resulting in several detections, particularly of the later types. Researchers wish to understand the connection among these different forms of the interstellar medium, and to examine the theoretical picture of the fate of the hot gas. To do so, they compiled observations of several forms of interstellar matter for a well-defined sample of early-type galaxies. Here they present a statistical analysis of this data base and discuss the implications of the results.

Bregman, Joel N.↗

Fixture For Sampling Volatile Materials In Containers

Fixture based on T-connector enables mass-spectrometric analysis of volatile contents of cylindrical containers without exposing contents to ambient conditions. Used to sample volatile contents of pressurized containers, contents of such enclosed processing systems as gas-phase reactors, gases in automotive emission systems, and gas in hostile environments.

Melton, Donald↗

Analysis of Screen Channel LAD Bubble Point Tests in Liquid Oxygen at Elevated Temperature

The purpose of this paper is to examine the key parameters that affect the bubble point pressure for screen channel Liquid Acquisition Devices in cryogenic liquid oxygen at elevated pressures and temperatures. An in depth analysis of the effect of varying temperature, pressure, and pressurization gas on bubble point is presented. Testing of a 200 x 1400 and 325 x 2300 Dutch Twill screen sample was conducted in the Cryogenics Components Lab 7 facility at the NASA Glenn Research Center in Cleveland, Ohio. Test conditions ranged from 92 to 130K and 0.138 - 1.79 MPa. Bubble point is shown to be a strong function of temperature with a secondary dependence on pressure. The pressure dependence is believed to be a function of the amount of evaporation and condensation occurring at the screen. Good agreement exists between data and theory for normally saturated liquid but the model generally under predicts the bubble point in subcooled liquid. Better correlation with the data is obtained by using the liquid temperature at the screen to determine surface tension of the fluid, as opposed to the bulk liquid temperature.

Hartwig, Jason↗

Fluid Phase Separation (FPS) experiment for flight on a space shuttle Get Away Special (GAS) canister

The separation of fluid phases in microgravity environments is of importance to environmental control and life support systems (ECLSS) and materials processing in space. A successful fluid phase separation experiment will demonstrate a proof of concept for the separation technique and add to the knowledge base of material behavior. The phase separation experiment will contain a premixed fluid which will be exposed to a microgravity environment. After the phase separation of the compound has occurred, small samples of each of the species will be taken for analysis on the Earth. By correlating the time of separation and the temperature history of the fluid, it will be possible to characterize the process. The experiment has been integrated into space available on a manifested Get Away Special (GAS) experiment, CONCAP 2, part of the Consortium for Materials Complex Autonomous Payload (CAP) Program, scheduled for STS-42. The design and the production of a fluid phase separation experiment for rapid implementation at low cost is presented.

Peters, Bruce↗