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At least 1,099 records · Page 61

Mass spectrometer-pyrolysis experiment for atmospheric and soil sample analysis on the surface of Mars

Results from the Viking mission will form the foundation for future in-depth investigations of atmosphere-surface interactions on Mars. The two Viking landers carried impressive instrumentation to obtain and analyze soil samples: the sites were observed by cameras, and the collector head was located on a long boom and allowed the collection of large samples at various depths. A selection of grain sizes was possible and a distribution system supplied a number of experiments with soil material. Despite stationary vehicles, a wide sampling field was reachable. The GCMS system, responsible for atmospheric as well as surface soil analysis, worked well on both landers. Atmospheric measurements resulted in the determination of the abundance of noble gases as well as of other molecular species. Isotopic composition measurements included the important ratios of C-13/C-12, N-15/N-14, and Ar-36/Ar-40. To verify these past results and to advance detailed studies of noble gas isotope ratios and minor constituents, better instrument sensitivities, higher precision, and lower background contributions are required in future Mars missions. Soil analysis during the Viking mission concentrated on organic material. Heating cycles were performed to 500 C and only water and carbon dioxide were identified. Higher pyrolysis temperatures are of primary importance to advance our understanding of the mineralogy and gas loading of surface material and atmospheric exchange.

Mauersberger, Konrad↗

Determining the Covering Factor of Compton-Thick Active Galactic Nuclei with NuSTAR

The covering factor of Compton-thick (CT) obscuring material associated with the torus in active galactic nuclei (AGNs) is at present best understood through the fraction of sources exhibiting CT absorption along the line of sight (N(sub H) greater than 1.5 x 10(exp 24) cm(exp −2)) in the X-ray band, which reveals the average covering factor. Determining this CT fraction is difficult, however, due to the extreme obscuration. With its spectral coverage at hard X-rays (greater than 10 keV), Nuclear Spectroscopic Telescope Array (NuSTAR) is sensitive to the AGNs covering factor since Compton scattering of X-rays off optically thick material dominates at these energies. We present a spectral analysis of 10 AGNs observed with NuSTAR where the obscuring medium is optically thick to Compton scattering, so-called CT AGNs. We use the torus models of Brightman and Nandra that predict the X-ray spectrum from reprocessing in a torus and include the torus opening angle as a free parameter and aim to determine the covering factor of the CT gas in these sources individually. Across the sample we find mild to heavy CT columns, with N(sub H) measured from 10(exp 24) to 10(exp 26) cm(exp −2), and a wide range of covering factors, where individual measurements range from 0.2 to 0.9. We find that the covering factor, f(sub c), is a strongly decreasing function of the intrinsic 2-10 keV luminosity, L(sub X), where f(sub c) = (−0.41 +/- 0.13)log(sub 10)(L(sub X)/erg s(exp −1))+18.31 +/- 5.33, across more than two orders of magnitude in L(sub X) (10(exp 41.5) - 10(exp 44) erg s(exp −1)). The covering factors measured here agree well with the obscured fraction as a function of LX as determined by studies of local AGNs with L(sub X) greater than 10(exp 42.5) erg s(exp −1).

NGC 4945↗

ANALYTICAL LABORATORY AT IDAHO NATIONAL LABORATORY COUNTING EQUIPMENT STANDARDIZATION AND QUALITY CONTROL IMPROVEMENT

The Analytical Laboratory at Idaho National Laboratory (INL) is a growing program with an emphasis on providing high quality results to customers, and an increasing focus on independent research. The Analytical Laboratory Counting Group has a number of capabilities: six gamma-ray counters, one gamma-ray sample changer, four gas flow proportional counter drawers, an auto-changing gas flow proportional counter, two liquid scintillation counters, and an alpha spectroscopy system. Other capabilities within the Analytical Laboratory include quadrupole inductively coupled plasma mass spectrometry (ICP-MS), high resolution ICP-MS, multi-collector ICP-MS, ICP atomic emission spectrometry (ICP-AES), gas mass spectrometry, thermal ionization mass spectrometry (TIMS), several glove boxes and fume hoods for sample preparation, and six interconnected hot cells for sample receipt and dissolution. In order to position the Analytical Laboratory as a world-class research institution, the Counting Group has recently begun making improvements to its analytical techniques, calibrations, standardization, and quality control procedures. A large part of this effort is to increase the level of documentation of instrument work. One project is to re-calibrate all of the gamma systems with newly purchased standards. One of the changes made in the purchase of the new standards was to lower the total activity so that the dead time of the calibration would more closely match the dead time of typical samples. Similarly, another planned project is to use new standards to re-calibration the gas flow proportional counters. Additional work has focused on testing and improving alpha spectroscopy sample preparation techniques. Plutonium separations have been tested to improve tracer recovery and to verify the separation technique in the presence of typical sample matrices. A final planned area of improvements has focused on liquid scintillation counting. One difficulty the Counting Group has encountered in liquid scintillation counting is an inflated gross alpha count relative to other analysis methods in the presence of high gross beta activity. Ideas include investigating the impact of choice of scintillation cocktail, as well as the effects of sample dilution.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Development of Multilayer Films Obtained From Epoxidized Methyl Esters, Polyhydroxyalkanoates and Their Combinations

The aim of this work was the production and characterization of films prepared from starch, gelatin and methyl esters of epoxidized macauba (Acrocomia aculeata), corn (Zea mays), pacu (Piaractus mesopotamicus), pintado (Pseudoplatystoma corruscans) and soybean (Glycine max) and also multilayer films of polyhydroxyalkanoates (PHA) conjugated with two of the epoxides that presented the best results in characterizations. The two types of films EEF (Epoxidized esters films) and EEFPHA (Epoxidized esters and PHA conjugated films) were both characterized for their visual aspects, solubility in water and acid, width, color, opacity, water vapor permeability, tensile strength and elongation. EEFPHA were also characterized by differential scanning calorimetry, scanning electron microscopy and X-ray diffraction analyses. The epoxidation reaction was successfully carried out; with the GC-MS analysis indicating the formation of epoxidized esters derived from linoleic and oleic acids. The addition of the epoxidized esters to the EEF films caused an increase in film thickness, opacity, solubility in water, tensile strength and elongation, while the solubility in acid presented the same value as compared to the blank sample. In the EEFPHA samples, addition of filmogenic solution of epoxidized esters from corn and macauba presented a value exceeding the standard in the thickness, opacity, water solubility, water vapor permeability and tensile strength analyses. In the analysis of solubility in acid these samples showed results below the standard, and the elongation test showed values very close. DSC, SEM and XRD results showed that there was a polymeric incorporation between the starch and the PHA.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Hydrogen leak detection in the Space Shuttle

This study focuses on a helium gas jet flowing into room air. Measurements of helium concentration and velocity in the jet-air mixture are reported. The objective is to learn about jet characteristics so that dynamically similar hydrogen leaks may be located in the Space Shuttle. The hazardous gas detection system (HGDS) in the mobile launch pad uses mass spectrometers to monitor the shuttle environment for leaks. The mass spectrometers are fed by long sample tubes which draw gas from the payload bay, mid body, aft engine compartment and external tank. The overall purpose of this study is to improve the HGDS especially in its potential for locating hydrogen leaks. A rapid-response leak detection experiment was designed, built, and tested, following on the work done in this program last summer. The apparatus included a Perkin Elmer MGA-1200 mass spectrometer and air velocity transducer, both monitored by a Macintosh IIFX computer using LabVIEW software. A jet of helium flowing into the lab air simulated a gas leak. Steady helium or hydrogen-nitrogen jets were logged for concentration and velocity, and the power spectral density of each was computed. Last year, large eddies and vortices were visually seen with Schlieren imaging, and they were detected in the time plots of the various instruments. The response time of the MGA-1200 was found in the range of 0.05 to 0.1 sec. Pulsed concentration waves were clearly detected at 25 cycles per sec by spectral analysis of MGA data. No peaks were detected in the power spectrum, so in the present study, 10 Hz bandwidth-averaged power levels were examined at regular frequency intervals. The practical consequences of last year's study are as follows: sampling frequency should be increased above the present rate of 1 sample per second so that transients could be observed and analyzed with frequency response methods. Many more experiments and conditions were observed in this second summer, including the effects of orifice diameter, jet velocity, sample tube design, radial effects, vertical flow, and low hydrogen concentrations (1 percent). A frequent observation was that the power spectrum, calculated from the Fourier transform of concentration fluctuations, gives a separate piece of information from concentration. Many of the tests suggest that power is high where mixing occurs at the helium-air interface. This fact is apparently independent of the concentration level, which could be high or low, but depends on the sample location relative to the jet (leak) origin, whereas high concentration may be due to a strong leak far away or a small leak close to the sample tube. If the power is low for any concentration level, this would signify helium is arriving at the sample tube by diffusion, not chaotic mixing caused by the jet interaction with air. The practical result is to propose a modification of the HGDL mass spectrometer data sampling and software so that sampling rates could be capable of observing at least 25 Hz fluctuations.

Barile, Ronald G↗

Coordinated Stem and NanoSIMS Analysis of Enstatite Whiskers in Interplanetary Dust Particles

Enstatite whiskers (less than 10 micrometer length, less than 200 nanometer width) occur in chondritic-porous interplanetary dust particles (CP IDPs), an Antarctic micrometeorite and a comet 81P/Wild-2 sample. The whiskers are typically elongated along the [100] axis and contain axial screw dislocations, while those in terrestrial rocks and meteorites are elongated along [001]. The unique crystal morphologies and microstructures are consistent with the enstatite whiskers condensing above approximately 1300 K in a low-pressure nebular or circumstellar gas. To constrain the site of enstatite whisker formation, we carried out coordinated mineralogical, chemical and oxygen isotope measurements on enstatite whiskers in a CP IDP.

Nakamura-Messenger, K.↗

Effect of secondary gas-phase reactions (SGR) in pyrolysis of carbon feedstocks for anisotropic carbon materials production – 1: Controlling SGR to modify intermediate coal tar species to improve pitch anisotropy

To meet the increasing demand for graphitizable carbon products, such as needle coke and carbon fiber, more carbon feedstocks capable of forming anisotropy should be utilized. Non-coking coals are widely available but are not typically suitable for producing anisotropic carbons due to lacking proper coal chemistry. This work used secondary gas-phase reactions (SGR) during coal pyrolysis to improve the coal tar chemistry of a non-coking coal for anisotropic carbon production. SGR pyrolysis temperatures and residence times were varied (T = 800–900°C and τ = 0–2.5 s), and analysis of the intermediate coal tar products showed that as these SGR pyrolysis conditions increased, the oxygen and aliphatic concentrations decreased, whereas aromatic contents and molecular weights increased. Without any SGR, microscopy of the thermally-treated coal tar pitch product revealed that the coal tar pitch was isotropic; however, upon using increased SGR pyrolysis conditions, the resulting coal tar pitch samples substantially increased in the percentage and quality of anisotropy formation. Further, the products' analyses show clear trends of modified chemical properties in the intermediate coal tar and improved anisotropy results. Thus, the results presented in this work show that by controlling the SGR during pyrolysis of a non-coking coal, this approach can modify the coal tar chemistry towards a precursor more suitable for quality anisotropic carbon material production.

01 COAL, LIGNITE, AND PEAT↗

UT-GOM2-2 Preliminary Report: Terrebonne Basin Northern Gulf of Mexico, 30 July-28 September 2023

In the summer and fall of 2023, the Gulf of Mexico Deepwater Hydrate Coring Expedition (UT-GOM2-2) drilled, cored, made downhole measurements, and analyzed samples from the seafloor to the base of the gas hydrate stability zone in one location (Site H, WR313) in the Terrebonne basin, deepwater Gulf of Mexico. Analyses of data and samples from the expedition will inform biological, geochemical, and geomechanical models to constrain the role of gas hydrates in the carbon cycle and the potential for gas hydrates as an energy resource. Pressure and conventional cores were collected continuously to a depth of 155.1 meters below the seafloor (mbsf). At deeper depths, cores were taken periodically from hydrate-bearing sands and their bounding muds to a total depth of 861.3 mbsf. 162.6 m of conventional core and 54.8 m of pressure core were obtained. Twelve temperature measurements were made between 27.1 and 144.5 mbsf to determine the geothermal gradient. At the seafloor, more than 4 m of sandy silt of unknown origin was encountered. Beneath this sand, to a depth of ~200 mbsf, the section was composed of interbedded mud and biogenic carbonate ooze. The biogenic ooze correlated to low density and high porosity intervals observed in the previously acquired logging while drilling (LWD) data and as measured. Calcareous nannofossil biostratigraphy constrains the entire record to the Pleistocene (< 0.91 million years) with a pronounced increase in sedimentation rate with depth. Beneath 200 mbsf, the section was predominantly composed of mud with two thicker, hydrate-bearing coarse-grained intervals, which are commonly known as the Blue and Orange sands. The dissolved gas concentration was quantified from pressure cores. In the shallow section, dissolved methane concentration increased below the sulfate-methane transition zone (SMTZ) and reaches saturation (the limit of solubility for methane) at 147 mbsf. Gas expansion was very common in conventional and depressurized pressure (conventionalized) cores below the SMTZ. At deeper depths, the methane concentration within muds bounding the Blue and Orange reservoirs was generally found to be less than saturation. The dissolved and hydrate gas composition is consistent with a microbial source, containing greater than 99.99% methane and only trace concentrations of ethane, propane, and butane. The methane to ethane ratio (C 1 /C 2 ) and the methane to ethane plus propane (C 1 /(C 2 +C 3 )) decrease with depth down to at least 678 mbsf, mainly driven by the increase in ethane with depth. It is unclear if this trend continues through the Orange sand interval. The δ 13 C isotopic signature of methane ranges between -69.9 and -78.5 ‰ Vienna Pee Dee Belemnite (VPDB). Pressure core recovery of all sandy intervals was poor. However, pressure core logs of the Orange sand show intervals of low density and high velocity, which are indicative of high hydrate saturation. One core from within the Orange sand was composed of interbedded graded sandy silt and mud. The sandy silts from this core are composed of mainly quartz and feldspar with some lithics. Most of the recovered pressure core samples are maintained at near in-situ pressure and temperature (within the hydrate stability field) at the University of Texas Pressure Core Center awaiting analysis. In the shallow section, samples will be used to determine the flux of organic carbon through the basin system, find the rate at which that carbon was consumed, and understand the microbial population responsible for these processes. In the deeper section, samples from in and around the hydrate reservoirs will be used to determine the petrophysical properties of the reservoir and bounding seals in these systems.

03 NATURAL GAS↗

TChem v2.0 - A Software Toolkit for the Analysis of Complex Kinetic Models

TChem is an open source software library for solving complex computational chemistry problems and analyzing detailed chemical kinetic models. The software provides support for: complex kinetic models for gas-phase and surface chemistry; thermodynamic properties based on NASA polynomials; species production/consumption rates; stable time integrator for solving stiff time ordinary differential equations; and, reactor models such as homogenous gas-phase ignition (with analytical Jacobian matrices), continuously stirred tank reactor, plug-flow reactor. This toolkit builds upon earlier versions that were written in C and featured tools for gas-phase chemistry only. The current version of the software was completely refactored in C++, uses an object-oriented programming model, and adopts Kokkos as its portability layer to make it ready for the next generation computing architectures i.e., multi/many core computing platforms with GPU accelerators. We have expanded the range of kinetic models to include surface chemistry and have added examples pertaining to Continuously Stirred Tank Reactors (CSTR) and Plug Flow Reactor (PFR) models to complement the homogenous ignition examples present in the earlier versions. To exploit the massive parallelism available from modern computing platforms, the current software interface is designed to evaluate samples in parallel, which enables large scale parametric studies, e.g. for sensitivity analysis and model calibration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Non-Contact Vapor Detection of Illicit Drugs via Atmospheric Flow Tube-Mass Spectrometry

Real-time, non-contact detection of illicit drugs is a desirable goal for the interdiction of these controlled substances, but the relatively low vapor pressures of such species present a challenge for trace vapor detection technologies. The introduction of atmospheric flow tube-mass spectrometry (AFT-MS), which has previously been demonstrated to detect gas-phase analytes at low parts-per-quadrillion levels for explosives and organophosphorus compounds, also enables the potential for non-contact drug detection. With AFT-MS, direct vapor detection of cocaine and methamphetamine from ~5 µg residues at room temperature is demonstrated herein. Furthermore, thermal desorption of low- to sub-picogram levels of cocaine, methamphetamine, fentanyl, and heroin is observed via AFT-MS using a carrier flow rate of several L/min of air. These low levels can permit non-contact sampling through collection of vapor, effectively preconcentrating the analyte before desorption and analysis. Quantitative evaluation of the thermal desorption approach has yielded limits of detection (LODs) on order of 10 fg for cocaine and fentanyl, 100 fg for methamphetamine, and 1.6 pg for heroin. The LOD for heroin was lowered to 200 fg by using tributyl phosphate as a dopant to form a proton-bound heterodimer with heroin. When used with AFT-MS, the intentional formation of specific drug-dopant adducts has the potential to enhance detection limits and selectivity of additional drug species. Species that are prone to form adducts present a challenge to analysis, but that difficulty can be overcome by the intentional addition of a dopant. Molecules unlikely to form adducts will remain essentially unimpacted, but the adduct-forming species will interact with the dopant to compress the analyte signal into a single peak. This approach would be valuable in the application of non-contact screening for illicit substances via vapor collection followed by thermal desorption for analysis.

methamphetamine, cocaine, heroin, fentanyl, atmosp↗

Amino acid analysis

The process and apparatus for qualitative and quantitative analysis of the amino acid content of a biological sample are presented. The sample is deposited on a cation exchange resin and then is washed with suitable solvents. The amino acids and various cations and organic material with a basic function remain on the resin. The resin is eluted with an acid eluant, and the eluate containing the amino acids is transferred to a reaction vessel where the eluant is removed. Final analysis of the purified acylated amino acid esters is accomplished by gas-liquid chromatographic techniques.

Winitz, M.↗

The effects of ultraviolet light on the degradation of organic compounds - A possible explanation for the absence of organic matter on Mars

The analysis of the top layer of the Martian regolith at the two Viking landing sites did not reveal any indigenous organic compounds. However, the existence of such compounds at deeper layers cannot be ruled out. Cosmochemical considerations indicate various potential sources for organic matter on Mars, such as comets and meteorites. The study tested the stability of a sample of the Murchison meteorite and various organic substances which have been detected in carbonaceous chondrites, such as glycine, adenine and naphthalene, to the action of ultraviolet light. The compounds were adsorbed on powdered quartz and on California desert soil and were irradiated in the presence or absence of oxygen. The organic content, before and after irradiation, was measured by carbon elementary analysis, UV-absorption, amino acid analysis or pyrolysis-gas chromatography-mass spectrometry. In the absence of oxygen, adenine and glycine appear to be stable over the given part of irradiation. A definite degradation was noticed in the case of naphtalene and the Murchison meteorite. In the presence of oxygen in amounts comparable to those on Mars all compounds were degraded. The degree of degradation was influenced by the irradiation time, temperature and oxygen content.

Oro, J.↗

Qualification of a Multi-Channel Infrared Laser Absorption Spectrometer for Monitoring CO, HCl, HCN, HF, and CO2 Aboard Manned Spacecraft

Monitoring of specific combustion products can provide early-warning detection of accidental fires aboard manned spacecraft and also identify the source and severity of combustion events. Furthermore, quantitative in situ measurements are important for gauging levels of exposure to hazardous gases, particularly on long-duration missions where analysis of returned samples becomes impractical. Absorption spectroscopy using tunable laser sources in the 2 to 5 micrometer wavelength range enables accurate, unambiguous detection of CO, HCl, HCN, HF, and CO2, which are produced in varying amounts through the heating of electrical components and packaging materials commonly used aboard spacecraft. Here, we report on calibration and testing of a five-channel laser absorption spectrometer designed to accurately monitor ambient gas-phase concentrations of these five compounds, with low-level detection limits based on the Spacecraft Maximum Allowable Concentrations. The instrument employs a two-pass absorption cell with a total optical pathlength of 50 cm and a dedicated infrared semiconductor laser source for each target gas. We present results from testing the five-channel sensor in the presence of trace concentrations of the target compounds that were introduced using both gas sources and oxidative pyrolysis (non-flaming combustion) of solid material mixtures.

environmental monitoring↗

Organics and Ices in the Outer Solar System: Connections to the Interstellar Medium

The solar nebula, that aggregate of gas and dust that formed the birthplace of the Sun, planets and plethora of small bodies comprising the Solar System, originated in a molecular cloud that is thought to have spawned numerous additional stars, some with their own planets and attendant small bodies. The question of the chemical and physical reprocessing of the original interstellar materials in the solar nebula has challenged both theory and observations. The acquisition and analysis of samples of comet and asteroid solids, and a growing suite of in-situ and close-up analyses of relatively unaltered small Solar System bodies now adds critical new dimensions to the study of the origin and evolution of the early solar nebula. Better understanding the original composition of the material from which our solar nebula formed, and the processing that material experienced, will aid in formulations of chemistry that might occur in other solar systems. While we seek to understand the compositional history of planetary bodies in our own Solar System, we will inevitably learn more about the materials that comprise exoplanets and their surrounding systems.

SOLAR NEBULA↗

Elliptic Cylinder Airborne Sampling and Geostatistical Mass Balance Approach for Quantifying Local Greenhouse Gas Emissions

In this paper, we explore observational, experimental, methodological, and practical aspects of the flux quantification of greenhouse gases from local point sources by using in situ airborne observations, and suggest a series of conceptual changes to improve flux estimates. We address the major sources of uncertainty reported in previous studies by modifying (1) the shape of the typical flight path, (2) the modeling of covariance and anisotropy, and (3) the type of interpolation tools used. We show that a cylindrical flight profile offers considerable advantages compared to traditional profiles collected as curtains, although this new approach brings with it the need for a more comprehensive subsequent analysis. The proposed flight pattern design does not require prior knowledge of wind direction and allows for the derivation of an ad hoc empirical correction factor to partially alleviate errors resulting from interpolation and measurement inaccuracies. Finally, the modified approach is applied to a use-case for quantifying CH 4 emission from an oil field south of San Ardo, CA, and compared to a bottom-up CH 4 emission estimate.

54 ENVIRONMENTAL SCIENCES↗

Iron Ore Reduction by Hydrogen Using a Laboratory Scale Fluidized Bed Reactor: Kinetic Investigation—Experimental Setup and Method for Determination

The reduction kinetics of hematite iron ore fines to metallic iron by hydrogen using a laboratory fluidized bed reactor were investigated in a temperature range between 873 K and 1073 K, by measuring the weight change of the sample portion during reduction. The fluidization conditions were checked regarding plausibility within the Grace diagram and the measured pressure drop across the material during experiments. The apparent activation energy of the reduction was determined against the degree of reduction and varied along an estimated two-peak curve between 11 and 55 kJ mol{sup −1}. Conventional kinetic analysis for the reduction of FeO to metallic iron, using typical models to describe gas–solid reactions, does not show results with high accuracy. Multistep kinetic analysis, using the Johnson–Mehl–Avrami model, shows that the initial stage of reduction from Fe{sub 2}O{sub 3} to Fe{sub 3}O{sub 4}, and partly to FeO, is controlled by diffusion and chemical reaction, depending on the temperature. Further reduction can be described by a combination of nucleation and chemical reaction, whereby the influence of nucleation increases with an increasing reduction temperature. The results of the kinetical analysis were linked to the shape of the curve from apparent activation energy against the degree of reduction.

36 MATERIALS SCIENCE↗

Kinetics of the Carbothermic Reduction of Manganese Oxide from Slag

Experiments were performed using a range of test conditions to elucidate the rate controlling step during the reaction of liquid iron-carbon droplets and slags containing manganese oxide. Four conditions were tested in the system: initial MnO content in the slag (5, 10, and 15 wt pct), initial carbon content of the metal (1, 2.5, 4.3 wt pct), initial droplet mass (0.5, 1.0, and 1.5 g), and reaction temperature (1823 K [1550 °C], 1873 K [1600 °C], and 1923 K [1650 °C]). Data were collected using the Constant Volume Pressure Increase (CVPI) technique which tracked the continuous pressure increase in the sealed furnace over time. Samples were quenched at the end of each experiment and chemistry was checked using LECO Carbon Analysis and ICP (Inductively Coupled Plasma) for manganese. The rate of reaction can be broken into a faster initial period related to internal CO formation, and a slower second reaction controlled by a complex mechanism involving transport of oxygen from slag to metal via CO{sub 2} and decomposition of the CO{sub 2} at the gas–metal interface.

36 MATERIALS SCIENCE↗