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At least 793 records · Page 44

Evaluating and modeling the effects of surface sampling factors on the recovery of organic chemical attribution signatures using the accelerated diffusion sampler and solvent extraction

In this study, an experimental design matrix was created and executed in order to test the effects of various real-world factors on the ability of the (1) accelerated diffusion sampler with solid phase micro-extraction (ADS-SPME) and (2) solvent extraction to capture organic chemical attribution signatures (CAS) from dimethyl methylphosphonate (DMMP) spiked onto painted wall board (PWB) surfaces. The DMMP CAS organic impurities sampled by ADS-SPME and solvent extraction were analyzed by gas chromatography/mass spectrometry (GC/MS). The number of detected DMMP CAS impurities and their respective GC/MS peak areas were determined as a function of DMMP stock, DMMP spiked volume, exposure time, SPME sampling time, and ADS headspace pressure. Based on the statistical analysis of experimental results, several general conclusions are made: (1) ADS-SPME with vacuum (i.e., reduced pressure) increased the amount of detected CAS impurity, as measured by GC/MS peak area, by a factor of 1.7 to 1.9 for PWB under certain experimental conditions, (2) the amount of detected CAS impurity was most influenced by spiked volume, stock, and ADS headspace pressure, (3) the ADS had no measurable effect on the number of detected DMMP impurities, that is, the ADS (with and without reduced pressure) had no practical effect on the DMMP impurity profile collected from spiked PWB, and (4) solvent extraction out performed ADS-SPME in terms of consistently capturing all or most of the targeted DMMP impurities from spiked PWB.

36 MATERIALS SCIENCE↗

Martian gas, soil sampler tested.

A gas chromatograph mass spectrometer (GCMS) is scheduled to be carried aboard the Mars Viking lander, which is to make a soft landing on the Martian surface. The GCMS has two distinct tasks including a sampling of the Martian atmosphere and an analysis of Martian soil. The instrument is designed to be highly sensitive. It can detect 0.1 part per million of organic compounds in the soil and from 10 to 100 parts per million of atmospheric constituents.

Miller, B.↗

Development of free-piston Stirling engine performance and optimization codes based on Martini simulation technique

A FORTRAN computer code is described that could be used to design and optimize a free-displacer, free-piston Stirling engine similar to the RE-1000 engine made by Sunpower. The code contains options for specifying displacer and power piston motion or for allowing these motions to be calculated by a force balance. The engine load may be a dashpot, inertial compressor, hydraulic pump or linear alternator. Cycle analysis may be done by isothermal analysis or adiabatic analysis. Adiabatic analysis may be done using the Martini moving gas node analysis or the Rios second-order Runge-Kutta analysis. Flow loss and heat loss equations are included. Graphical display of engine motions and pressures and temperatures are included. Programming for optimizing up to 15 independent dimensions is included. Sample performance results are shown for both specified and unconstrained piston motions; these results are shown as generated by each of the two Martini analyses. Two sample optimization searches are shown using specified piston motion isothermal analysis. One is for three adjustable input and one is for four. Also, two optimization searches for calculated piston motion are presented for three and for four adjustable inputs. The effect of leakage is evaluated. Suggestions for further work are given.

Martini, William R.↗

Chemical composition measurements of the atmosphere of Jupiter with the Galileo Probe mass spectrometer

The Galileo Probe entered the atmosphere of Jupiter on December 7, 1995. Measurements of the chemical and isotopic composition of the Jovian atmosphere were obtained by the mass spectrometer during the descent over the 0.5 to 21 bar pressure region over a time period of approximately 1 hour. The sampling was either of atmospheric gases directly introduced into the ion source of the mass spectrometer through capillary leaks or of gas, which had been chemically processed to enhance the sensitivity of the measurement to trace species or noble gases. The analysis of this data set continues to be refined based on supporting laboratory studies on an engineering unit. The mixing ratios of the major constituents of the atmosphere hydrogen and helium have been determined as well as mixing ratios or upper limits for several less abundant species including: methane, water, ammonia, ethane, ethylene, propane, hydrogen sulfide, neon, argon, krypton, and xenon. Analysis also suggests the presence of trace levels of other 3 and 4 carbon hydrocarbons, or carbon and nitrogen containing species, phosphine, hydrogen chloride, and of benzene. The data set also allows upper limits to be set for many species of interest which were not detected. Isotope ratios were measured for 3He/4He, D/H, 13C/12C, 20Ne/22Ne, 38Ar/36Ar and for isotopes of both Kr and Xe.

unmanned↗

NASA PS400: A New Temperature Solid Lubricant Coating for High Temperature Wear Applications

A new solid lubricant coating, NASA PS400, has been developed for high temperature tribological applications. This plasma sprayed coating is a variant of the patented PS304 coating and has been formulated to provide higher density, smoother surface finish and better dimensional stability than PS304. PS400 is comprised of a nickel-molybdenum binder that provides strength, creep resistance and extreme oxidative and dimensional stability. Chromium oxide, silver and barium-calcium fluoride eutectic are added to the binder to form PS400.Tribological properties were evaluated with a pin-on-disk test rig in sliding contact to 650 C. Coating material samples were exposed to air, argon and vacuum at 760 C followed by cross section microscopic analysis to assess microstructure stability. Oil-Free microturbine engine hot section foil bearing tests were undertaken to assess PS400 s suitability for hot foil gas bearing applications. The preliminary results indicate that PS400 exhibits tribological characteristics comparable to the PS304 coating but with enhanced creep resistance and dimensional stability suitable for demanding, dynamic applications.

DellaCorte, C.↗

Time-Resolved Rayleigh Scattering Measurements in Hot Gas Flows

A molecular Rayleigh scattering technique is developed to measure time-resolved gas velocity, temperature, and density in unseeded gas flows at sampling rates up to 32 kHz. A high power continuous-wave laser beam is focused at a point in an air flow field and Rayleigh scattered light is collected and fiber-optically transmitted to the spectral analysis and detection equipment. The spectrum of the light, which contains information about the temperature and velocity of the flow, is analyzed using a Fabry-Perot interferometer. Photomultipler tubes operated in the photon counting mode allow high frequency sampling of the circular interference pattern to provide time-resolved flow property measurements. Mean and rms velocity and temperature fluctuation measurements in both an electrically-heated jet facility with a 10-mm diameter nozzle and also in a hydrogen-combustor heated jet facility with a 50.8-mm diameter nozzle at NASA Glenn Research Center are presented.

Mielke, Amy F.↗

First Optical Constants from 0.4 to 1.6 µm of Titan Aerosol Analogs Produced in the NASA Ames COSmIC Facility and Their Use in a New Analysis of Cassini VIMS Observations

We have determined the real and imaginary refractive indices (n and k, respectively), from the visible to the near infrared (0.4 to 1.6 μm), of five laboratory-generated organic refractory materials produced from gas-phase chemistry with the NASA Ames COSmIC facility. The solid samples were produced using a plasma discharge in the stream of a 200-K supersonic jet-cooled expansion of different gas mixtures to study the impact of the molecular precursors on the solid sample optical properties. Three samples were produced from N2:CH4 (95:5) gas mixtures using three different high voltages (700V, 800V and 1000V) to vary the energy in the plasma discharge. One sample was produced from a N2:CH4:C2H2 (94:5:5:0.5) gas mixture, with a high voltage of 1000 V. The fifth sample was produced in an Ar:CH4 (95:5) gas mixture with a high voltage of 1000 V to produce a nitrogen-free hydrocarbon sample. The optical constants, n and k, of these five samples were determined using spectral reflectance measurements. They appear to be positively correlated with the nitrogen content in the solid sample, i.e., a sample with larger nitrogen content exhibits higher n and k values. We have used these refractive indices as input parameters in a radiative transfer model to analyze Cassini Visible Infrared Mapping Spectrometer (VIMS) observations of Titan’s atmosphere. The results show that using the tholin samples with higher n and k values (higher nitrogen content) provides a better fit to the observational data than using the samples with lower n and k values (lower nitrogen content). The Titan tholins with higher nitrogen content therefore appear to be more representative of the Titan aerosols observed by VIMS.

Titan Aerosol Analogs↗

Diverse organic molecules on Mars revealed by the first SAM TMAH experiment

The search for organic matter on Mars has rapidly evolved in the past decade with simple aromatic, S-heterocycles, and aliphatic organic molecules detected in Gale crater. We report the in situ detection of >20 organic molecules from clay-bearing sandstones in the ~3.5-billion-year-old Knockfarrill Hill member of Glen Torridon, Gale crater, by the Sample Analysis at Mars instrument suite onboard the Curiosity rover. These molecules were liberated by the onboard tetramethylammonium hydroxide wet chemistry experiment. Diverse thermochemolysis products, including benzothiophene, methyl benzoate, and single and dicyclic aromatic molecules were released and detected by evolved gas analysis and gas chromatography-mass spectrometry. Results indicate the experiment successfully released molecules preserved in ancient macromolecular or free organic matter within Martian bedrock despite ~3.5 billion years of diagenesis and radiation exposure.

Amy J Williams↗

A high precision gas flow cell for performing in situ neutron studies of local atomic structure in catalytic materials

Gas-solid interfaces enable a multitude of industrial processes, including heterogeneous catalysis; however, there are few methods available for studying the structure of this interface under operating conditions. Here, we present a new sample environment for interrogating materials under gas-flow conditions using time-of-flight neutron scattering under both constant and pulse probe gas flow. Outlined are descriptions of the gas flow cell and a commissioning example using the adsorption of N 2 by Ca-exchanged zeolite-X (Na 78–2x Ca x Al 78 Si 144 O 384 ,x ≈ 38). We demonstrate sensitivities to lattice contraction and N 2 adsorption sites in the structure, with both static gas loading and gas flow. A steady-state isotope transient kinetic analysis of N 2 adsorption measured simultaneously with mass spectrometry is also demonstrated. In the experiment, the gas flow through a plugged-flow gas-solid contactor is switched between 15 N 2 and 14 N 2 isotopes at a temperature of 300 K and a constant pressure of 1 atm; the gas flow and mass spectrum are correlated with the structure factor determined from event-based neutron total scattering. As a result, available flow conditions, sample considerations, and future applications are discussed.

36 MATERIALS SCIENCE↗

Carbon-isotopic analysis of dissolved acetate

Heating of dried, acetate-containing solids together with oxalic acid dihydrate conveniently releases acetic acid for purification by gas chromatography. For determination of the carbon-isotopic composition of total acetate, the acetate-containing zone of the chromatographic effluent can be routed directly to a combustion furnace coupled to a vacuum system allowing recovery, purification, and packaging of CO2 for mass-spectrometric analysis. For analysis of methyl carbon, acetic acid can be cryogenically trapped from the chromatographic effluent, then transferred to a tube containing excess NaOH. The tube is evacuated, sealed, and heated to 500 degrees C to produce methane by pyrolysis of sodium acetate. Subsequent combustion of the methane allows determination of the 13C content at the methyl position in the parent acetate. With typical blanks, the standard deviation of single analyses is less than 0.4% for acetate samples larger than 5 micromoles. A full treatment of uncertainties is outlined.

Non-NASA Center↗

Fluid Phase Separation (FPS) experiment for flight on the shuttle in a Get Away Special (GAS) canister: Design and fabrication

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 that 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 Earth. By correlating the time of separation and the temperature history of the fluid, it will be possible to characterize the process. The phase separation experiment is totally self-contained, with three levels of containment on all fluids, and provides all necessary electrical power and control. The controller regulates the temperature of the fluid and controls data logging and sampling. An astronaut-activated switch will initiate the experiment and an unmaskable interrupt is provided for shutdown. 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 in April 1991. Presented here are the design and the production of a fluid phase separation experiment for rapid implementation at low cost.

Source record↗

Age and thermochronology of K-feldspars from the Manson Impact Structure

As a contribution to the effort to obtain a precise age for the Manson Impact Structure, we are approaching the problem from a thermo chronological perspective, with the goal of extracting an age from Ar-40/Ar-39 age-spectrum analysis of partially overprinted K-feldspars taken from granitoid clasts. We find that shocked feldspars from Manson generally show a strong overprint in their age spectra, with more than 50 percent of each spectrum being reset. The reset portions of the age spectra correspond to gas lost from very small diffusion domains, and a characteristic of the Manson samples is the very large range in apparent diffusion dimensions that they display, with the smallest domains being some 400 times smaller than the largest domains. It is also noteworthy that the small domains comprise a substantial portion of the volume of the feldspars (50 percent or more). These observations are consistent with the extreme shock experienced by these samples. In detail, the spectra we have measured to date are saddle-shaped and show minimum ages of between 67 and 72 Ma, which we interpret to be maximum estimates for the age of the impact. In the case of one sample (M1-678.3; K-feldspar from a large syenite block located well below the apparent melt-matrix breccia in the M1 borehole), isotope correlation analysis suggests the presence of a non-atmospheric trapped Ar component (Ar-40/Ar-36 of 660 plus or minus 40), and an age of about 65.3 plus or minus 0.5 Ma (2 sigma). Our interpretation of our results is that the shock of impact greatly reduced the diffusion-domain sizes of our samples, making them susceptible to significant Ar loss during heating associated with impact. It appears that while our feldspars were partially open to Ar loss, they equilibrated with a non-atmospheric Ar component, probably related to impact-related degassing of old basement around the impact site.

Zeitler, P. K.↗

Evidence for large baryonic feedback at low and intermediate redshifts from kinematic Sunyaev-Zel’dovich observations with ACT and DESI photometric galaxies

Recent advances in cosmological observations have provided an unprecedented opportunity to investigate the distribution of baryons relative to the underlying matter. In this work, we show that the gas is more extended than the dark matter, and the amount of baryonic feedback at $z \lesssim 1$ disfavors low-feedback models such as that of state-of-the-art hydrodynamical simulation IllustrisTNG compared with high-feedback models such as that of the original Illustris simulation. This has important implications for bridging the gap between theory and observations and understanding galaxy formation and evolution. Furthermore, a better grasp of the baryon-dark matter link is critical to future cosmological analyses, which are currently impeded by our limited knowledge of baryonic feedback. Here, we measure the kinematic Sunyaev-Zel'dovich (kSZ) effect from the Atacama Cosmology Telescope (ACT), stacked on the luminous red galaxy (LRG) sample of the Dark Energy Spectroscopic Instrument (DESI) imaging survey. This is the first analysis to use photometric redshifts for reconstructing galaxy velocities. Due to the large number of galaxies comprising the DESI imaging survey, this is the highest signal-to-noise stacked kSZ measurement to date: we detect the signal at 13$σ$, finding strong evidence that the gas is more spread out than the dark matter, as well as a preference for larger feedback compared to some commonly used state-of-the-art hydrodynamical simulations. Here, our work opens up the possibility of recalibrating large hydrodynamical simulations using the kSZ effect. In addition, our findings highlight the importance of properly accounting for baryonic feedback with future surveys such as LSST through direct probes such as the kSZ, and shed light on long-standing enigmas in astrophysics, such as the “missing baryon” problem.

79 ASTRONOMY AND ASTROPHYSICS↗

The Microbial Community and Functional Potential in the Midland Basin Reveal a Community Dominated by Both Thiosulfate and Sulfate-Reducing Microorganisms

The Permian Basin is the highest producing oil and gas reservoir in the United States. Hydrocarbon resources in this region are often accessed by unconventional extraction methods, including horizontal drilling and hydraulic fracturing. Despite the importance of the Permian Basin, there is no publicly available microbiological data from this region. We completed an analysis of Permian produced water samples to understand the dynamics present in hydraulically fractured wells in this region. We analyzed produced water samples taken from 10 wells in the Permian region of the Midland Basin using geochemical measurements, 16S rRNA gene sequencing, and metagenomic sequencing. Compared to other regions, we found that Permian Basin produced water was characterized by higher sulfate and lower total dissolved solids (TDS) concentrations, with a median of 1,110 mg/L and 107,000 mg/L. Additionally, geochemical measurements revealed the presence of frac hits, or interwell communication events where an established well is affected by the pumping of fracturing fluid into a new well. The occurrence of frac hits was supported by correlations between the microbiome and the geochemical parameters. Our 16S rRNA gene sequencing identified a produced water microbiome characterized by anaerobic, halophilic, and sulfur reducing taxa. Interestingly, sulfate and thiosulfate reducing taxa including Halanaerobium, Orenia, Marinobacter, and Desulfohalobium were the most prevalent microbiota in most wells. We further investigated the metabolic potential of microorganisms in the Permian Basin with metagenomic sequencing. We recovered 15 metagenome assembled genomes (MAGs) from seven different samples representing 6 unique well sites. These MAGs corroborated the high presence of sulfate and thiosulfate reducing genes across all wells, especially from key taxa including Halanaerobium and Orenia. The observed microbiome composition and metabolic capabilities in conjunction with the high sulfate concentrations demonstrate a high potential for hydrogen sulfide production in the Permian Basin. Additionally, evidence of frac hits suggests the possibility for the exchange of microbial cells and/or genetic information between wells. This exchange would increase the likelihood of hydrogen sulfide production and has implications for the oil and gas industry.

16S RNA↗

Crystallographic Study of Product Phases of Carbothermic Reduction and Nitridation of Hafnium Dioxide

Details of the carbothermic reduction/nitridation to synthesize hafnium nitride (HfN) and hafnium carbide (HfC) are scarce in the literature. Therefore, this current study was carried out to evaluate two pathways for synthesizing these two refractory materials: direct nitridation and carbothermic reduction/nitridation. Two mixtures of hafnium dioxide and carbon with C/HfO 2 molar ratios of 2.15 and 3.1 were nitridized directly using flowing nitrogen gas at elevated temperatures (1300–1700 °C). The 3.1 C/HfO 2 molar ratio mixture was also carbothermically reduced under flowing argon gas to synthesize HfC, which was converted into HfN by introducing a nitridation step under both N 2(g ) and N 2(g) -10% H 2(g) . X-ray diffraction results showed the formation of HfN at 1300 and 1400 °C and HfC 1–y N y at ≥1400 °C under direct nitridation of samples using a C/HfO 2 molar ratio of 2.15. These phase analysis data together with lower lattice strain and greater crystallite sizes of HfC 1–y N y that formed at higher temperatures suggested that the HfC 1–y N y phase is preferred over HfN at those temperatures. Carbothermic reduction of 3.1 C/HfO 2 molar ratio samples under an inert atmosphere produced single-phased HfC with no significant levels of dissolved oxygen. In conclusion, carbothermic reduction nitridation made two phases of different carbon levels (HfC 1–y N y and HfC 1–y 'N y ', where y' < y), while direct nitridation produced a single HfC 1–y N y phase under both N 2 and N 2 -10% H 2 cover gas environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Comprehensive Single-Shot Proteomics with FAIMS on a Hybrid Orbitrap Mass Spectrometer

Liquid chromatography (LC) prefractionation is often implemented to increase proteomic coverage; however, while effective, this approach is laborious, requires considerable sample amount, and can be cumbersome. We describe how interfacing a recently described high-field asymmetric waveform ion mobility spectrometry (FAIMS) device between a nanoelectrospray ionization (nanoESI) emitter and an Orbitrap hybrid mass spectrometer (MS) enables the collection of single-shot proteomic data with comparable depth to that of conventional two-dimensional LC approaches. This next generation FAIMS device incorporates improved ion sampling at the ESI–FAIMS interface, increased electric field strength, and a helium-free ion transport gas. With fast internal compensation voltage (CV) stepping (25 ms/transition), multiple unique gas-phase fractions may be analyzed simultaneously over the course of an MS analysis. We have comprehensively demonstrated how this device performs for bottom-up proteomics experiments as well as characterized the effects of peptide charge state, mass loading, analysis time, and additional variables. We also offer recommendations for the number of CVs and which CVs to use for different lengths of experiments. Internal CV stepping experiments increase protein identifications from a single-shot experiment to >8000, from over 100 000 peptide identifications in as little as 5 h. In single-shot 4 h label-free quantitation (LFQ) experiments of a human cell line, we quantified 7818 proteins with FAIMS using intra-analysis CV switching compared to 6809 without FAIMS. Single-shot FAIMS results also compare favorably with LC fractionation experiments. Furthermore, a 6 h single-shot FAIMS experiment generates 8007 protein identifications, while four fractions analyzed for 1.5 h each produce 7776 protein identifications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Speciation of methylmercury and ethylmercury by gas chromatography cold vapor atomic fluresence spectroscopy

Existing models and simulants of tank disposition media at SRS have presumed the presence of high concentrations of inorganic mercury. However, recent quarterly tank analyses show that mercury is present as organomercurial species at concentrations that may present challenges to remediation and disposition and may exceed the Saltstone Waste Acceptance Criteria (WAC). To-date, methylmercury analysis for Savannah River Remediation (SRR) has been performed off-site by Eurofins Scientific (Lancaster, PA). A series of optimization and validation experiments has been performed at SRNL, which has resulted in the development of on-site organomercury speciation capabilities using purge and trap gas chromatography coupled with thermal desorption cold vapor atomic fluorescence spectroscopy (P&T GC/CVAFS). Speciation has been achieved for methylmercury, with a method reporting limit (MRL) values of 1.42 pg for methylmercury. Results obtained by SRNL from the analysis of past quarterly samples from tanks 21, 40, and 50 have demonstrated statistically indistinguishable concentration values compared with the concentration data obtained from Eurofins, while the data from SRNL has demonstrated significantly improved precision and processing time.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Test evaluation of potential heat shield contamination of an Outer Planet Probe's atmospheric sampling system

An Outer Planets Probe which retains the charred heatshield during atmospheric descent must deploy a sampling tube through the heatshield to extract atmospheric samples for analysis. Once the sampling tube is deployed, the atmospheric samples ingested must be free of contaminant gases generated by the heatshield. Outgassing products such as methane and water vapor are present in planetary atmospheres and hence, ingestion of such species would result in gas analyzer measurement uncertainties. This paper evaluates the potential for, and design impact of, the extracted atmospheric samples being contaminated by heatshield outgassing products. Flight trajectory data for Jupiter, Saturn and Uranus entries are analyzed to define the conditions resulting in the greatest potential for outgassing products being ingested into the probe's sampling system. An experimental program is defined and described which simulates the key flow field features for a planetary flight in a ground-based test facility. The primary parameters varied in the test include: sampling tube length, injectant mass flow rate and angle of attack. Measured contaminant levels predict the critical sampling tube length for contamination avoidance. Thus, the study demonstrates the compatibility of a retained heatshield concept and high quality atmospheric trace species measurements.

Kessler, W. C.↗