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At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Ambient Mass Spectrometry Rapid Analysis Methods for Trace Inorganics

The ability to rapidly detect and characterize the chemistry of trace quantities of inorganic species has multiple potential applications, including nuclear safeguards, nuclear forensics, and environmental monitoring. Some mass spectrometric methods currently exist, but they are costly and time-intensive, often destroying chemical information in the process of ionization. Ambient mass spectrometry is a relatively new analytical method in which samples are introduced to the mass spectrometer from atmospheric pressure, rather than from high vacuum. Ambient MS can operate with gentler ionization methods such as electrospray ionization (ESI) and paper-spray ionization (PSI), reducing fragmentation and preserving the chemical information of the analyte. This may be useful for determining the intended purpose of material in a sample. Strontium, part of nuclear fallout, is analyzed here to test these new analytical methods for viability. Electrospray ionization mass spectrometry functions by spraying the sample as a solution through a needle charged to a few kV. A nebulizing gas flows out along with the sample to create the spray before droplets enter a drying chamber with heated drying gas to remove the solvent molecules. From there bare analyte ions enter the mass spectrometer. This method has the advantage of relatively fast sample preparation and stable ionization. More stable ionization produces higher-quality data. Paper-spray ionization mass spectrometry operates by applying sample to a paper triangle. The paper triangle is then electrified in a metal clamp to a few kV before spray solvent is applied. The spray solvent transports analyte in the sample to the tip, where it is ionized and enters the mass spectrometer. One advantage of this method is reduced sample preparation - an analyst can even swipe a surface and cut a triangle directly from the swipe. The data analysis serves to rapidly process tens of samples all at once. The mass spectrometer outputs a file containing a few hundred spectra for each sample. The pipeline processes each one to identify peaks of interest. A full palette of data analysis metrics are generated, including plots of the raw data and plots of calculated values such as isotopic ratios. The pipeline filters the raw data to remove noise and background peaks, as well as peaks representing detector saturation. A heat map is generated to show the overall spectrum in mass-time- intensity space. Post-processing, we obtained the desired calibration curves, demonstrating that both ESI-MS and PSI-MS are viable methods for quantifying trace amounts of inorganics while retaining their chemical speciation information. ESI-MS demonstrated a linear response region of 100 ppb to 20 ppm, with a limit-of-detection of around 100 ppb. At top left is an example spectrum with the {sup 88}SrNO{sub 3} peak identified to show the retention of chemical speciation. PSI-MS showed a linear response region of around 1 ppb to 1 ppm, with a limit-of-detection of near 1 ppb. PSI-MS produced more erratic results than ESI-MS, likely due to the variability in ionization resulting from manual positioning of the paper triangle near the MS inlet. Future efforts will focus on improving the repeatability of PSI-MS as well as analyzing other species of interest such as cerium and uranium. Improvements will also be made to create more reliable data extraction and intelligent data filtering.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRSDate not supplied

VALENTInE: A Concept for a New Frontiers Class Long Duration In-Situ Balloon Mission to Venus

Venus and Earth are similar in bulk composition, size, density, and approximate distance from the Sun, yet Venus’s modern-day climate and surface geology is distinctly different [1]. Previous missions to Venus revealed unusual volcanic features, possible continental crust, widespread volcanic plains, a weak magnetic field [2], and insights into the Venusian atmosphere [3,4]. Unfortunately, data from these missions were limited in spatial and temporal resolution and global extent. A future mission to Venus is critical to address fundamental questions surrounding the chemical composition and dynamics of the Venusian atmosphere [5], its geologic history [6,7], its internal structure [8,9], and its habitability throughout time [10,11]. We present the Venus Air and Land Expedition: a Novel Trailblazer for In situ Exploration (VALENTInE) mission to meet this need. VALENTInE is a variable altitude balloon that will passively float in Venus’s atmosphere between 45 and 55 km altitude. VALENTInE will acquire atmospheric data at varying latitudes and longitudes in addition to mapping the surface geomorphology and mineralogy across multiple terrains. Mission Objectives: The VALENTInE mission concept is driven by four main science objectives: 1. Determine whether the driving force of the superrotation of Venus’s atmosphere is caused by horizontal or vertical momentum transport. 2. Determine whether the atmospheric composition and noble gas inventory of the Venusian atmosphere is a product of outgassing from the initial protoplanetary source or if there are significant contributions from exogenic sources. 3. Determine whether the tesserae regions (particularly Aphrodite Terra) are felsic and relatively older than surrounding regions. 4. Determine if there is any evidence of a recent dynamo preserved in the rock record of Venus. Mission Overview: A balloon architecture provides a robust system that can survive long-term in the Venusian environment while taking accurate measurements of the lower cloud deck and surface. Two prior balloon missions to Venus, VEGA 1 and VEGA 2 in 1984, have demonstrated the potential for such planetary exploration; however, these missions were short-lived (46 hr), with limited range (54 km). Our spacecraft concept consists of a battery powered balloon with a gondola and flyby carrier stage (Fig. 1). Our novel design allows for at least 15 days of atmospheric exploration, including multiple ascents and descents in the Venus atmosphere. VALENTInE is baselined to launch in 2032, cruise on solar power for 128 days, enter, descend, and inflate (EDI) into Venus’s atmosphere above Aphrodite Terra, and float in Venus’s atmosphere for a total nominal mission duration of 15 days. The balloon, able to control its altitude by changing its buoyancy, will make one full circumnavigation every 4–8 days and move poleward ~1 o latitude per day; it will be passively directed by the horizontal air currents on Venus. The balloon can only be controlled in the z direction, and the expected latitude range is ±10° from EDI. The balloon itself will be a tracer for atmospheric structures such as zonal winds [5, 12]. During the 15-day operational period, there will be five dips to 45 km for a compositional study of the lower atmosphere and geological and magnetic mapping of the surface. Dips are used to take images and measurements closer to the surface and to obtain in situ vertical atmospheric profiles between 45 and 55 km. Instruments: The VALENTInE instrument payload will allow for extensive study of the geology, atmosphere, and interior of Venus. The instrument suite consists of six instruments. The mission profile for each instrument is shown in Fig. 2. Lower Atmosphere Meteorology Analyzer (LAMA) is an atmospheric structure instrument consisting of a thermometer, barometer, and accelerometer to continuously measure temperature and pressure as a function of altitude, longitude, and latitude. TracE and Noble Gas Investigator (TENGI) is aneutral mass spectrometer used to sample the dense atmosphere. TENGI will operate continuously at 45 km and 55 km and will measure D/H ratios, as well as Ne, Ar, and O isotopic ratios. Kilometer Scale Spectral Imager (KSSI) is amultispectral imager (850-1150 nm) used to resolve surface features on the order of km. Near InfraRed Multispectral Photometer (NIRMP) is an Infrared (IR) photometer used to image the surface through the clouds to characterize mineral assemblages at five different areas of the surface. NIRMP will be operated during dwell. ELevation REConnaissance (ELREC) is a light detection and ranging (LIDAR) instrument used for measuring topography at five different areas of the surface. The ELREC data will be combined with those of NIRMP to determine mineral assemblages and how they correlate to topography. Magnetic Exploration and Interior Detective (MEID) is a magnetometer used to detect any near-surface magnetic anomalies. The magnetometer will continuously operate at all altitudes. Mission Design: The spacecraft’s propulsion system will have a wet mass of 930 kg and will be launched on an Atlas V rocket. The spacecraft will jettison the payload upon arrival in Venus’s atmosphere before decelerating to orbital velocity. Figure 2. Notional power-dip profile while the balloon is on the dayside. Risks and Challenges: Raising and lowering the spacecraft to dip beneath the haze layer require a large amount of energy. This issue was partly compensated by limiting the number of dips over the 15 day prime mission. Power needs for pumping helium are reduced by slowing the descent speed, which consequently increases spatial resolution of in situ measurements between 45 and 55 km. The main limitation for the duration of the mission is the need to carry 15 days’ worth of batteries. The bus experiences external Venusian temperatures ranging from ~27°C at 55 km altitude to ~110°C at 45 km altitude. These high atmospheric temperatures require thermal protection for the bus (instruments, electronics, and flight systems) during its descent, dwell at 45 km, and ascent. The bus is maintained at a mechanically safe temperature range of -10°C to 50°C using white external paint, multi-layer insulation (MLI), mechanical/thermal isolation (e.g. Ti, composites), and ~57 kg of Phase Change Materials (PCM). Images and spectra taken below the haze dominate the available data transmission regardless of the time spent at 45 km. Therefore, less time at the lower altitude mainly reduces the coverage of in situ measurements there. Further, we assumed an unrealistically low-density material for the helium storage tanks on the gondola. However, this issue is partially resolved if we were to jettison 75% of the spent helium storage tanks. After the entry process, the balloon volume remains mostly inflated and storage tanks are required only for reducing balloon volume in dipping to 45 km. This mission was planned against an expected New Frontiers 5 (NF5) cost cap of $1B, as the NF5 call had not yet been released. The mission we describe fits within the predicted cost cap if the flyby carrier stage, responsible for powering the spacecraft during cruise and for relaying in situ measurements back to Earth, can be contributed by another space agency. Acknowledgments: We thank the JPL Planetary Science Summer School, especially A. Nash, J. Scully, K. Mitchell, L. Lowes, and J. Armijo, and our mentors from JPL Team X. Thank you to our review panel for their insightful review. References: [1] Kane, S. et al. (2019) JGR:Ps, 124 , 2015–2028. [2] Phillips, J. L., & Russell, C. T. (1987). JGR: Space Physics , 92 (A3), 2253-2263. [3] Nakamura, M. et al. (2018) Earth Planets Space, 70 (1), 144. [4] Svedhem, H. et al. (2009) JGR:P 114 (E5). [5] Limaye et al. (2009) Decadal Survey White Paper . [6] Ivanov, M. and Head, J. (2011) PSS, 59 (13) , 1559-1600. [7] Smrekar, S. et al. (2018) Space Sci Rev, 214 (5), 88. [8] O’Rourke, J. et al. (2018) EPSL, 502 , 46-56. [9] O’Rourke J. et al. (2019) GRL , (46), 5768–5777 [10] Way, M. et al. (2016) GRL, 43 (16), 8376-8383. [11] Way, M. et al. (2020) JGR:P, 125 (5), e2019JE006276. [12] Preston, R. A. et al. (1986) Science, 231 (4744), 1414-1416.

Mission Concept↗
NASA NTRSDate not supplied

Bulk Oxygen Isotopic Compositions of Anhydrous Interplanetary Dust Particles: Indication of an 16O-Poor Reservoir In The Outer Solar System

The oxygen isotopic ratios of ancient solar system materials reflect the isotopically distinct reservoirs in which they formed or were altered. These compositions are generally explained by mixing of material derived from an 16O-rich reservoir and material from an 16O-poor reservoir thought to be isotopically heavy H2O. Evidence of this 16O-poor reservoir is scarce and includes cosmic symplectite (COS), probable silicates in an interplanetary dust particle (IDP), and sulfates in a cometary xenolith. These materials have 17O and 18O enrichments between ~150–200 ‰, which agree with predictions for self-shielding and photodissociation of CO. The ‘cometary’ 16O-poor materials indicate alteration or formation in the outer solar system. The bulk O isotopic compositions of IDPs thought to have cometary origins may also harbor evidence of this primordial 16O-poor reservoir. Here we report the bulk O compositions of anhydrous IDPs and discuss the nebular reservoirs from which they derived

A N Nguyen↗
NASA NTRS1993

Determination of (C-12)/(C-13) in the interstellar medium toward Zeta Ophiuchi and Xi Persei

The Lick Observatory Reticon (LOR) data presented in Hawkins et al. (1985) are reanalyzed in order to determine the cause of the significant discrepancy in (C-12)/(C-13) isotope ratios determined on the basis of observations of this isotope in the interstellar medium toward Zeta Ophiuchi and Xi Persei. A new set of Lick Observatory observations toward Zeta Oph are obtained using a CCD detector. The KPNO coude feed echelle spectrograph and a CCD detector are used to carry out high-resolution, high SNR ratio observations toward Zeta Oph and Xi Per. The LOR results for Zeta Oph are uncertain, ranging to 40 to 60, owing to the error in continuum placement. The KPNO results toward Zeta Oph are (C-12)H/(C-13)H(+)(0, 0) = 63 +/- 8, (C-12)H(+)/(C-13)H(+)(1, 0) = 67 +/- 19, and (C-12)N/(C-13)N = 100 + 88/- 33. Toward Xi Per, the KPNO measurements yield (C-12)H(+)/(C-13)H(+) = 49 +/- 15 from the 4232-A band, and a lower limit of 45 from the 3957-A observations.

Hawkins, Isabel↗
DOE OSTI2021

Direct analysis of cotton swipes for plutonium isotope determination by microextraction-ICP-MS

This study demonstrates a method for determining the isotopic composition of low-level (sub-pg) plutonium (Pu) directly from a cotton swipe. Environmental sample (ES) swipes are routinely employed as a tool for monitoring activities in nuclear facilities. Traditional ES swipe analysis, as employed in nuclear safeguards, utilizes laborious ashing, digestion, and chemical separation procedures prior to mass spectrometric (MS) analysis. Here, an innovative sample introduction technique employing a microextraction probe to extract Pu directly from the swipe surface is described. The microextraction probe lowers onto the swipe surface, seals on a small area (8 mm 2 ), and delivers solvent (2% HNO 3 ) to extract actinide material that may be present. The extracted analyte is subsequently directed into a sector field inductively coupled plasma (ICP)-MS for isotope ratio determination. This microextraction-ICP-MS method successfully determined the isotopic composition ( 240 Pu/ 239 Pu and 242 Pu/ 239 Pu) of three Pu certified reference materials (CRM 136, 137, and 138) that were deposited (1 pg) onto ES swipes. The percent relative difference from the certified value, uncorrected for instrumental fractionation, was <2% for the 240 Pu/ 239 Pu ratio on all three CRMs and <10% for the 242 Pu/ 239 Pu ratio on CRM 136 and 138. Here, the percent relative standard deviation, an estimate of the sample-to-sample isotopic precision, was <4% for the 240 Pu/ 239 Pu and <15% for the 242 Pu/ 239 Pu. Method limits of detection were determined, based on measurements of an enriched 244 Pu material, to be ~7 fg. Additionally, a mixed uranium (U) and Pu deposition was made to determine the method's ability to simultaneously extract U and Pu and determine the isotopic composition of both analytes.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
NASA NTRS1992

Fractionation of CO in the diffuse clouds toward Zeta Ophiuchi

An analysis of CO A-X bands in diffuse clouds toward Zeta Ophiuchi is presented. The results provide isotopic ratios that constitute the strongest observational evidence for highly localized isotopic fractionation of CO in diffuse portions of an interstellar cloud. The value of the fractionation implies that selective photodissociation is the controlling influence of the fractionation. The molecule's excitation temperature is discussed and a lower limit to the O-16/O-18 ratio is provided. The absence of CO lines from the gas that provides broad CH+ and CH lines commonly attributed to warm gas behind a shock front is addressed.

Sheffer, Yaron↗
NASA NTRS2017

Volatile Concentrations and H-Isotope Composition of Unequilibrated Eucrites

Eucrites are among the oldest and best studied asteroidal basalts (1). They represent magmatism that occurred on their parent asteroid, likely 4-Vesta, starting at ~ 4563 Ma and continuing for approx. 30 Myr. Two hypotheses are debated for the genesis of eucrites, a magma ocean model (2), and a mantle partial melting model. In general, volatiles (H, C, F, Cl) have been ignored for eucrites and 4-Vesta, but solubility of wt% levels of H2O are possible at Vestan interior PT conditions. Targeted measurements on samples could aid our understanding considerably. Recent studies have found evidence of volatile elements in eucrites, but quantifying the abundance of volatiles remains problematic (6). Volatile elements have a disproportionately large effect on melt properties and phase stability, relative to their low abundance. The source of volatile elements can be elucidated by examining the hydrogen isotope ratio (D/H), as different H reservoirs have drastically different H isotope compositions. Recent studies of apatite in eucrites have shown that the D/H of 4-Vesta matches that of Earth and carbonaceous chondrites, however, the D/H of apatites may not represent the D/H of a primitive 4-Vesta melt due to the possibility of degassing prior to the crystallization of apatite. Therefore, the D/H of early crystallizing phases must be measured to determine if the D/H of 4-Vesta is equal to that of the Earth and carbonaceous chondrites.

Sarafian, Adam R.↗
NASA NTRS2014

The Deuterium to Hydrogen Ratio in the Water that Formed the Yellowknife Bay Mudstones in Gale Crater

A suite of isotope ratios of light elements in the present martian atmosphere (13C/12C, 15N/14N, 18O/16O, 38Ar/36Ar, and D/H) are all substantially enriched in the heavy element suggesting atmospheric loss to space over the past billions of years with preferential loss of the lighter isotope from each pair. In situ measurements from MSL's Sample Analysis at Mars (SAM) instrument [e.g. 1,2,3] have considerably refined previous measurements from the Viking mass spectrometers [e.g. 4], from remote spectroscopic observations [e.g. 5,6], and from martian meteorite studies [e.g. 7,8]. The persistence of habitable environments such as the ancient Yellowknife Bay lake recently revealed by measurements from the Curiosity rover [9] depends on the surface temperatures and the duration of an atmosphere thicker than that at present. Current and planned measurements from orbit with the Mars Express and MAVEN missions respectively intend to study the processes of atmospheric escape including solar wind interaction, sputtering, thermal escape, and dissociative recombination, and determine or refine the current rate of atmospheric loss caused by these and other mechanisms. The goal of these programs is to understand the physical processes sufficiently well so that robust extrapolations over the past billions of years can be made D/H is measured by both the Tunable Laser Spectrometer (TLS) and the Quadrupole Mass Spectrometer (QMS) of the SAM suite. to predict the atmospheric and surface conditions on early Mars. However, the study of the history of martian atmospheric evolution will be greatly facilitated if we are able to also directly measure the isotopic composition of volatiles captured in rocks that are representative of the ancient atmosphere. To date, D/H is one of the most promising candidates for this study since water is the most abundant volatile thermally released from the Yellowknife Bay phylosilicates discovered by the SAM and CheMin experiments of MSL and its

Yellowknife Bay↗
NASA NTRS1980

Ancient solar wind in lunar microbreccias

Possible components of the ancient solar wind, particularly the N-15/N-14 ratio, are investigated on the basis of lunar microbreccia studies. Nitrogen contents and isotope ratios were determined for Apollo 11 and 15 microbreccia samples by means of vacuum pyrolysis techniques. The Apollo 11 soil breccias, which had been closed to the addition of recent solar wind due to their compaction, are found to contain the lowest N-15/N-14 ratios yet reported for the solar wind, extending the range of variation of the ratio to between a delta N-15 of -190% in the past to +120% at present. Nitrogen isotope analysis of the Apollo 15 drill core, which had undergone two episodes of solar wind exposure, also support the secular variation in the N-15 content of the solar wind, which is attributed to spallation reactions in the sun. The formation of the breccias at the Apollo 11 and 15 sites is discussed on the basis of the observed nitrogen systematics, and differences between N-15 and Ne-21 cosmic ray exposure ages implied are attributed to the diffusive loss of neon from lunar soils.

Thiemens, M. H.↗
DOE OSTI2025

Natural isotopic compositions of titanium, iron, and nickel observed in commercial fuel pellets – Promising candidate elements for stable isotope tagging

Stable isotope taggants would constitute unique identifiers for nuclear fuel cycle materials, resulting in expedited timelines and high confidence provenance assessments for nuclear forensics investigations. However, reliably identifying and interpreting stable isotope taggants in nuclear materials recovered from outside of regulatory control will largely be predicated on the assumption that the taggant element intrinsic to the untagged nuclear material exhibits natural isotopic ratios. Here, we present high-precision Ti, Fe, and Ni isotope compositions in 13 commercial low-enriched uranium (LEU) fuel pellets to assess the suitability of these transition metals as stable isotope taggants. Our investigations reveal limited isotope variations among the fuel pellets in all three elements, which are consistent with small mass-dependent isotope fractionations, comparable to variations previously reported for natural samples. In practice, isotopically tagged nuclear materials are expected to fall along isotopic mixing lines, since intrinsic background levels of taggant elements dilute the taggant towards natural isotope compositions. Furthermore, the observation that Ti, Fe, and Ni isotope compositions in a suite of LEU fuel pellets are close to or indistinguishable from estimates for the Bulk Silicate Earth demonstrates that a two end-member mixing assumption would be valid for these transition metals, indicating that all three are promising candidate elements for stable isotope tagging. Finally, we present mass balance calculations to quantify isotopic perturbations expected from admixing isotopically anomalous Ti, Fe, and Ni taggants to assess the interplay between elemental and taggant concentrations and find favorable compromises for facilitating successful taggant identification with current analytical methods.

Intentional forensics↗
NASA NTRS1979

Venus upper atmosphere neutral composition - Preliminary results from the Pioneer Venus orbiter

Measurements in situ of the neutral composition and temperature of the thermosphere of Venus are being made with a quadrupole mass spectrometer on the Pioneer Venus orbiter. The presence of many gases, including the major constituents CO2, CO, N2, O, and He has been confirmed. Carbon dioxide is the most abundant constituent at altitudes below about 155 kilometers in the terminator region. Above this altitude atomic oxygen is the major constituent, with O/CO2 ratios in the upper atmosphere being greater than was commonly expected. Isotope ratios of O and C are close to terrestrial values. The temperature inferred from scale heights above 180 kilometers is about 400 K on the dayside near the evening terminator at a solar zenith angle of about 69 deg. It decreases to about 230 K when the solar zenith angle is about 90 deg.

Niemann, H. B.↗
NASA NTRS1998

Development of a High Resolution-High Sensitivity Ion Microprobe Facility for Cosmochemical Applications

NASA NAGW-4112 has supported development of the CAMECA ims 1270 ion microprobe at UCLA for applications in cosmochemistry. The instrument has been brought to an operational status and techniques developed for accurate, precise microbeam analysis of oxygen isotope ratios in polished thin-sections. We made the first oxygen isotopic (delta(18)O and delta(17)O) measurements of rare mafic silicates in the most chemically primitive meteorites, the a chondrites (Leshin et al., 1997). The results have implications for both high temperature processing in the nebula and low-T aqueous alteration on the CI asteroid. We have performed measurements of oxygen isotopic compositions of magnetite and co-existing olivine from carbonaceous (Choi et al., 1997) and unequilibrated ordinary chondrites (Choi et al., in press). This work has identified a significant new oxygen isotope reservoir in the early solar system: water characterized by a very high Delta(17)) value of approx. 5 % per thousand. We have determined the spatial distributions of oxygen isotopic anomalies in all major mineral phases of a type B CAI from Allende. We have also studied an unusual fractionated CAI from Leoville and made the first oxygen isotopic measurements in rare CAIs from ordinary chondrites.

McKeegan, Kevin D.↗
NASA NTRS2003

Infrared Spectroscopy of Anhydrous Interplanetary Dust Particles

Infrared (IR) spectroscopy is the primary means of mineralogical analysis of materials outside our solar system. The identity and properties of circumstellar grains are inferred from spectral comparisons between astronomical observations and laboratory data from natural and synthetic materials. These comparisons have been facilitated by the Infrared Space Observatory (ISO), which obtained IR spectra from numerous astrophysical objects over a wide spectral range (out to 50/cm) where crystalline silicates and other phases have distinct features. The anhydrous interplanetary dust particles (IDPs) are particularly important comparison materials because some IDPs contain carbonaceous material with non-solar D/H and N-15/N-14 ratios and amorphous and crystalline silicates with non-solar 0- isotopic ratios, demonstrating that these IDPs contain preserved interstellar material. Here, we report on micro- Fourier transform (FT) IR spectrometry of IDPs, focusing on the inorganic components of primitive IDPs (FTIR spectra from the organic/carbonacecous materials in IDPs are described elsewhere).

Keller, L. P.↗
NASA NTRS2012

Carbon Isotopic Fractionation in Fischer-Tropsch Type Reactions and Relevance to Meteorite Organics

Fischer-Tropsch-Type (FTT) reactions have been hypothesized to contribute to the formation of organic compounds in the early solar system, but it has been difficult to identify a signature of such reactions in meteoritic organics. The work reported here examined whether temperature-dependent carbon isotopic fractionation of FTT reactions might provide such a signature. Analyses of bulk organic deposits resulting from FTT experiments show a slight trend towards lighter carbon isotopic ratios with increasing temperature. It is unlikely, however, that these carbon isotopic signatures could provide definitive provenance for organic compounds in solar system materials produced through FTT reactions, because of the small scale of the observed fractionations and the possibility that signatures from many different temperatures may be present in any specific grain.

Johnson, Natasha M↗
NASA NTRS2022

Noble Gases and Stable Isotopes Track the Origin and Early Evolution of the Venus Atmosphere

The composition the atmosphere of Venus results from the integration of many processes entering into play over the entire geological history of the planet. Determining the elemental abundances and isotopic ratios of noble gases (He, Ne, Ar, Kr, Xe) and stable isotopes (H, C, N, O, S) in the Venus atmosphere is a high priority scientific target since it could open a window on the origin and early evolution of the entire planet. This chapter provides an overview of the existing dataset on noble gases and stable isotopes in the Venus atmosphere. The current state of knowledge on the origin and early and long-term evolution of the Venus atmosphere deduced from this dataset is summarized. A list of persistent and new unsolved scientific questions stemming from recent studies of planetary atmospheres (Venus, Earth and Mars) are described. Important mission requirements pertaining to the measurement of volatile elements in the atmosphere of Venus as well as potential technical difficulties are outlined.

noble gases↗
NASA NTRSDate not supplied

Carbon Tracers of Aqueous Processes: Isotopic Analysis of Cr Carbonate Grains With Implications for Bennu Samples

Carbonate grains in carbonaceous chondrites record aqueous alteration events on the asteroidal parent bodies, including evidence for episodic alteration, timing of alteration, and time and temperature evolution of volatiles. Spectral features in the 3.4 μm region at asteroid Bennu have been interpreted as coming from carbonate minerals. Coordinated analysis of carbonate grains will be a valuable tool for analysis of Bennu samples, and related analysis of analog materials provides important context for understanding aqueous alteration of carbonaceous asteroids more broadly. To that end, our team is analyzing carbonates in Bennu analog materials, using Raman spectroscopy to identify carbonates and assess the maturity of related organic materials, vacuum reflectance spectroscopy from the ultraviolet through thermal infrared range to constrain contributions from carbonates and organics, X-ray microtomography and electron probe microanalysis (EPMA) to assess the distribution of void space, transmission electron microscopy to characterize space weathering effects, and EPMA and secondary ion mass spectrometry (SIMS) to measure composition and isotopic ratios. Here, we describe in situ analysis of carbon and oxygen isotopes from carbonates in Grosvenor Mountains (GRO) 95577.

K E Miller↗
DOE OSTI2023

Establishing the accuracy of position–specific carbon isotope analysis of propane by GC–pyrolysis–GC–IRMS

Rationale: Position-specific (PS) δ 13 C values of propane have proven their ability to provide valuable information on the evolution history of natural gases. Two major approaches to measure PS δ 13 C values of propane are isotopic 13 C nuclear magnetic resonance (NMR) and gas chromatography-pyrolysis-gas chromatography-isotope ratio mass spectrometry (GC-Py-GC-IRMS). Measurement accuracy of the isotopic 13 C NMR has been verified, but the requirements of large sample size and long experimental time limit its applications. GC-Py-GC-IRMS is a more versatile method with a small sample size, but its accuracy has not been demonstrated. Methods: We measured the PS δ 13 C values of propane from nine natural gases using both 13 C NMR and GC-Py-GC-IRMS, then evaluated the accuracy of the GC-Py-GC-IRMS method. Results: The results show that large carbon isotope fractionations occurred for both terminal and central carbons within propane during pyrolysis. The isotope fractionations during the pyrolysis are reproducible at optimum conditions, but vary between the two GC-Py-GC-IRMS systems tested, affected by experimental conditions (e.g., pyrolysis temperature, flow rate, and reactor conditions). Conclusions: It is necessary to evaluate and calibrate each GC-Py-GC-IRMS system using propane gases with accurately determined PS δ 13 C values. Finally, this study also highlights a need for PS isotope standards for propane and other molecules (e.g., butane and acetic acid).

03 NATURAL GAS↗
DOE OSTI2020

Sr-Nd-Pb isotope systematics of Australasian tektites: Implications for the nature and composition of target materials and possible volatile loss of Pb

The Australasian tektite (AAT) strewn field is the largest strewn field on the Earth with about ~10–30% coverage, both land and ocean, but a clearly identified source impact crater is absent despite the young age of AAT of ca. 790 ka. A genetic link between the Australasian tektites and their unequivocal parental materials is therefore largely impossible to establish. Nevertheless, the nature of the parental materials and the extent of volatilization can be constrained using the splash form tektites, carrying the chemical signatures of high-temperature processes, and the layered (so-called Muong Nong-type) tektites, which are less chemically homogenized and exceptionally abundant in the AAT field. New high-precision Sr, Nd and Pb isotopic measurements were obtained for a chemically and petrographically well-characterized suite of AAT, which included the Muong Nong-type (MN-AAT) with precisely known field locations in Laos and splash forms (SF-AAT) from different parts of the strewn field. Additionally, optically dark and light zones of the MN-AAT were also separately analyzed. Homogeneous ε Nd values from -11.8 to -11.2, combined with a narrow range of two-stage Nd model ages from 1.67 to 1.72 Ga for the entire AAT suite, point to a well-mixed source, in terms of REE, of the crustal segment from which the sedimentary material for tektites was ultimately derived. The Sr isotopic data largely overlap for SF-AAT and MN-AAT ( 87 Sr/ 86 Sr = 0.71636–0.72021) and indicate Paleozoic to Mesozoic sedimentary parentage. However, late Neogene to early Quaternary re-deposition and formation of a thick silt-sized sedimentary section with vertical stratification is required to comply with 10Be data. Lead isotope systematics documents at least three different components which can perhaps be represented by different mineral phases, such as feldspar, zircon, organic matter adsorbed on young sediments etc., sorted during fluvial transport and final deposition. In addition, the SF-AAT have systematically lower Pb contents than the MN-AAT, and generally show isotopically heavier Pb isotopic ratios. This is theoretically consistent with a preferential volatilization of lighter Pb isotopes during evaporation and considerably larger Pb loss from SF-AAT when compared to MN-AAT. Nevertheless, further experimental work would be necessary to unambiguously distinguish kinetic fractionation from source mixing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗