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NASA NTRSDate not supplied

First in-situ Nitrogen Isotope Measurements in Martian Meteorites

The origin and timing of the accretion of volatile elements on the terrestrial planets remains a subject of controversy. Nitrogen and hydrogen isotopes are powerful tools to constrain the source(s) of primordial volatiles accreted by planetary bodies because their isotope ratios (15N/14N; D/H) differ significantly between different solar system reservoirs (e.g., solar, chondritic, cometary). Hf-W data of martian samples indicate that Mars accreted very rapidly in the inner solar system and reached half ofits size in 1.8 Myr [1]. Therefore, martian samples are key to understand the distribution of volatile elements in the inner solar system during the early stages of planetary formation. Since no space missions have yet returned samples from Mars, martian meteorites (Shergottites, Nakhlites, Chassignites) are unique samples to constrain the source(s) of volatiles present in the martian mantle. The goal of this study was to target pristine phases(e.g., melt inclusions, mesostasis) for in-situ measurements of their nitrogen content and isotopic ratios to access the most primitive melt of the Chassignites and Nakhlites reservoirs. Five different Nakhlites (Nakhla, NWA 998, MIL 03346, Y 000593,NWA 6148) and Chassigny were analysed [2] using a recent high-resolution analytical technique that allows constraining the nitrogen composition of both carbon-bearing and carbon-free phases in natural and synthetic samples. Nitrogen was measured in the form of 14N16O- and 15N16O- with the CAMECA 1280-HR2 at the CRPG [3]. A significant amount of nitrogen was detected in melt inclusions in Chassigny and in the mesostasis of Nakhla, Y000593, MIL 03346, and NWA 6148. Nitrogen isotope signatures of Chassigny and Nakhlites exhibit a heavy isotope enrichment compared to Earth's mantle, and are consistent with a carbonaceous chondrite-like source [4]. This suggests that Earth and Mars accreted nitrogen from different chondritic sources. Overall, our in-situ technique is a unique and powerful tool to characterize the nitrogen abundance and isotopic composition of natural samples.

C Deligny↗
NASA NTRS1979

Li, Be, and B in minerals of a refractory-rich Allende inclusion

The abundances of Li, Be, and B and the isotopic ratios of Li and B have been measured by ion microprobe in melilite, pyroxene, anorthite, and spinel grains in a coarse-grained inclusion from the Allende meteorite. Based on the measurements, it is estimated that the bulk inclusion contains 200 ppb Li, 310 ppb Be, and 18 ppm B. The B is probably due to contamination. The Li-7/Li-6 ratios in spinels, pyroxene, and melilite are indistinguishable at the + or - 15% level and lie within the uncertainty (+ or - 15%) of the range of values reported for samples of the earth and meteorites. It has been determined that this inclusion contains an excess of Al-correlated Mg-26, implying that Al-26 was once present in it. The Li-Be-B effects for two solar-system proton-irradiation models which propose to account for Al-26 in Allende inclusions have been calculated. It is found that the predicted Li-Be-B abundances and isotopic ratios are grossly different from those observed in any solar-system materials.

Phinney, D.↗
NASA NTRSDate not supplied

Predicting the Seawater Chemistry of an Ocean World Using Machine Learning on Isotopic Measurements of Volatile CO2

Introduction: Given the long time intervals required for data transmission to and from ocean worlds targets, low bandwidth for data transmission, time required for data processing and analysis, and potentially extreme radiation environments (e.g., Europa), it is clear that ocean worlds missions will need more autonomous flight instruments and software in order to achieve established science goals. Protracted time intervals for data analysis (e.g., Europa Lander) strongly motivates the development of rapid, consistent and streamlined methods for interpreting data from flight mass spectrometers to e.g., determine how mass spectra from a plume or surface liquid/ice relates to the surface/subsurface. Since mass spectrometry also has the potential to correctly identify biosignatures[1], it is imperative that such methods for interpreting data are consistent and accurate. We used 848 isotope ratio mass spectra from laboratory analyses of CO2 that interacted with ocean worlds-relevant seawaters as a ‘training’ dataset for ‘unsupervised’ machine learning. In unsupervised learning, characteristics of the data are not labeled or linked, and any similarities found only result from the neural network. CO2 isotopologues analyzed for this dataset mimic the remote measurements of CO2 by a flight mass spectrometer, and are detailed in Theiling [2]. From this dataset, we used measured features of the spectra, such as retention time, intensity, and (isotopologue) mass ratios as inputs for our autoencoder neural network. Our neural network was trained to find similarities in these and other spectral features for seawaters of a particular composition and amount of initial CO2. Successful training then created an output of these similarities for various seawaters, which included MgSO4, Na2SO4, NaCl, MgCl2, KCl, and NaHCO3, and combinations of these salts. We then applied dimensionality reduction techniques such as Principal Component Analysis (PCA), T-Distributed Stochastic Neighbor Embedding (TSNE), and Uniform Manifold Approximation and Projection (UMAP) to demonstrate latent data features as a two-dimensional projection in a unitless, high-dimensional space. In this projection, a data point represents the combined effect of spectral features such as intensity, retention time, and isotope ratio. Our initial UMAP demonstrates data clustering (organization of the data by the neural network) based on the amount of CO2 that had initially interacted with each seawater. Further training using more ‘supervised’ learning techniques demonstrate strong clustering of preliminary data based on initial CO2 concentration, seawater chemical composition, and ionic strength (salinity). Our preliminary work therefore suggests that machine learning has the potential to identify compositional variants of an ocean world seawater based on mass spectra from volatile CO2 measurements. Acknowledgments: This work was funded through a Strategic Task Group at NASA Goddard Space Flight Center. The training dataset was collected through funding from the Oklahoma Space Grant Consortium. References: [1] Pappalardo, R. et al. (2013) Astrobiology, 13, 740–773. [2] Theiling (2020) Icarus, 114216.

Europa↗
NASA NTRS2016

Cupid's Arrow: An Innovative Nanosat to Sample Venus' Upper Atmosphere

In NASA's Discovery 2014 AO, the opportunity to propose a Technology Demonstration Opportunity (TDO) to enhance the primary mission was specified. For the Venus Emissivity, Radio Science, InSAR, Topography, and Spectroscopy (VERITAS) mission, we elected to include the Cupid's Arrow nanosat TDO to sample and measure the abundances of noble gases and their isotopic ratios in Venus's upper atmosphere below the homopause. This paper will provide a basic overview of the VERITAS mission, with a focus on the Cupid's Arrow concept including a description of the mission, spacecraft design, and JPL's quadrupole ion trap mass spectrometer (QITMS) instrument specifications and design. In previous planetary entry probe mission designs, particularly at Venus, engineers w ere focused on entry and descent. A landed probe was also proposed for the New Frontiers SAGE mission. For Cupid's Arrow, the nanosat is designed to skim through the upper atmosphere, just below the homopause, in order to sample the atmosphere, perform the analysis, and then exit the atmosphere to transmit its data to the orbiting VERITAS spacecraft. Cupid's Arrow is a compelling addition to the VERITAS geology mission. A key missing link in our understanding of Venus' evolution is the noble gas abundances and their isotopic ratios. Not since Pioneer Venus have these measurements been made in the Venus atmosphere and never in the upper atmosphere, just below the homopause, to the degree of accuracy that will be accomplished by VERITAS' Cupid's Arrow nanosat.Such measurements were ranked as the number 1 investigation of the number 1 objective of the goal "Atmospheric Formation, Evolution, and Climate History ".

Discovery↗
NASA NTRS2014

In Situ Probe Science at Saturn

A fundamental goal of solar system exploration is to understand the origin of the solar sys-tem, the initial stages, conditions, and processes by which the solar system formed, how the formation pro-cess was initiated, and the nature of the interstellar seed material from which the solar system was born. Key to understanding solar system formation and subsequent dynamical and chemical evolution is the origin and evolution of the giant planets and their atmospheres. Several theories have been put forward to explain the process of solar system formation, and the origin and evolution of the giant planets and their atmospheres. Each theory offers quantifiable predictions of the abundances of noble gases He, Ne, Ar, Kr, and Xe, and abundances of key isotopic ratios 4He3He, DH, 15N14N, 18O16O, and 13C12C. Detection of certain dis-equilibrium species, diagnostic of deeper internal pro-cesses and dynamics of the atmosphere, would also help discriminate between competing theories. Measurements of the critical abundance profiles of these key constituents into the deeper well-mixed at-mosphere must be complemented by measurements of the profiles of atmospheric structure and dynamics at high vertical resolution and also require in situ explora-tion. The atmospheres of the giant planets can also serve as laboratories to better understand the atmospheric chem-istries, dynamics, processes, and climates on all planets including Earth, and offer a context and provide a ground truth for exoplanets and exoplanetary systems. Additionally, Giant planets have long been thought to play a critical role in the development of potentially habitable planetary systems. In the context of giant planet science provided by the Galileo, Juno, and Cassini missions to Jupiter and Sat-urn, a small, relatively shallow Saturn probe capable of measuring abundances and isotopic ratios of key at-mospheric constituents, and atmospheric structure in-cluding pressures, temperatures, dynamics, and cloud locations and properties not accessible by remote sens-ing can serve to test competing theories of solar system and giant planet origin, chemical, and dynamical evolution.

Interstellar↗
NASA NTRS2008

Mid-Infrared OPO for High Resolution Measurements of Trace Gases in the Mars Atmosphere

The Martian atmosphere is composed primarily (>95%) of CO2 and N2 gas, with CO, O2, CH4, and inert gases such as argon comprising most of the remainder. It is surprisingly dynamic with various processes driving changes in the distribution of CO2, dust, haze, clouds and water vapor on global scales in the meteorology of Mars atmosphere [I]. The trace gases and isotopic ratios in the atmosphere offer important but subtle clues as to the origins of the planet's atmosphere, hydrology, geology, and potential for biology. In the search for life on Mars, an important process is the ability of bacteria to metabolize inorganic substrates (H2, CO2 and rock) to derive energy and produce methane as a by-product of anaerobic metabolism. Trace gases have been measured in the Mars atmosphere from Earth, Mars orbit, and from the Mars surface. The concentration of water vapor and various carbon-based trace gases are observed in variable concentrations. Within the past decade multiple groups have reported detection of CH4, with concentrations in the 10's of ppb, using spectroscopic observations from Earth [2]. Passive spectrometers in the mid-infrared (MIR) are restricted to the sunlit side of the planet, generally in the mid latitudes, and have limited spectral and spatial resolution. To accurately map the global distribution and to locate areas of possibly higher concentrations of these gases such as plumes or vents requires an instrument with high sensitivity and fine spatial resolution that also has global coverage and can measure during both day and night. Our development goal is a new MIR lidar capable of measuring, on global scales, with sensitivity, resolution and precision needed to characterize the trace gases and isotopic ratios of the Martian atmosphere. An optical parametric oscillator operating in the MIR is well suited for this instrument. The sufficient wavelength tuning range of the OPO can extend the measurements to other organic molecules, CO2, atmospheric water vapor, clouds, temperature, dust, and aerosols, as well as possibly polar-cap properties. Our OPO-approach may allow a new capability for active remote sensing of the outer planets and moons, where the weaker sunlight further limit passive instruments. Here we report on the OPO development effort for this lidar instrument.

Yu, Anthony W.↗
NASA NTRS1986

Measurements of hydrogen and helium isotopes in Galactic cosmic rays from 1978 through 1984

The propagation of light cosmic rays is examined using measurements of the relative abundances of the isotopes H-1, H-2 and He-3 and He-4 made with the ISEE 3 instrumentation. It is believed that cosmic ray particles experience spallation in traveling through the interstellar medium, thereby producing the isotopes examined in the present study. The isotopic ratios are therefore expected to yield data on outward migrating particles, which lose energy while moving toward extragalactic space, i.e., the 'leaky box approximation'. The energy ranges covered are 26-138 MeV/nucleon for H-1 and He-4, 24-89 MeV/nucleon for H-2 and 43-146 MeV/nucleon for He-3. Solar activity ranged from minimum to maximum over the observational period. Details of the experimental strategies, instrumentation features and calibration techniques employed with the particle detectors are provided. Histograms were geneated of the energies attributable to each particle track and mass ratios of the various isotopes were calculated over the measured energy ranges. Account was taken of errors introduced by solar modulation, and an escape path length of 5.6-7.8 g/sq cm was estimated for particle propagation through the Galaxy. The projected path length agrees with previous estimates based on data from heavier cosmic ray nuclei.

Kroeger, R.↗
NASA NTRS1989

Isotopic microanalysis of returned comet nucleus samples

If isotopic measurements of interplanetary dust particles (IDPs) and primitive meteorites can serve as a guide to the isotopic analysis of returned comet nucleus material, an essential requirement will be the capability for microanalysis. The reason is that in both types of extraterrestrial samples large isotopic heterogeneities on a small spatial scale have become apparent once it was possible to measure isotopes in small samples. In the discovery of large isotopic anomalies the ion microprobe has played a significant role because of its high spatial resolution for isotopic ratio measurements. The largest isotopic anomalies in C, N, O, Mg, Si, Ca and Ti found to date were measured by ion microprobe mass spectrometry. The most striking examples are D/H measurements in IDPs and isotopic measurements of C, N and Si in SiC from the CM chondrites Murray and Murchison.

Zinner, Ernst↗
NASA NTRS2001

K-Capture Cosmic Ray Secondaries and Reacceleration

We have investigated the effect of reacceleration on interstellar flux of K-capture secondaries V-49 and Cr-51. Several isotopic ratios for these two isotopes are calculated using the galactic diffusion model with and without distributed reacceleration. It is found that the statistical accuracy of the ACE experiment on itself is high enough to see a signature of reacceleration. However, the uncertainties in nuclear production cross sections are probably too large to conclude that reacceleration process took place.

Jones, F. C.↗
NASA NTRS2011

Ground-Based Centimeter, Millimeter, and Submillimeter Observations of Comet 103P/Hartley 2

Comets provide important clues to the physical and chemical processes that occurred during the formation and early evolution of the Solar System, and could also have been important for initiating prebiotic chemistry on the early Earth [1]. Comets are comprised of molecular ices, that may be pristine interstellar remnants of Solar System formation, along with high-temperature crystalline silicate dust that is indicative of a more thermally varied history in the protosolar nebula [2]. Comparing abundances of cometary parent volatiles, and isotopic fractionation ratios, to those found in the interstellar medium, in disks around young stars, and between cometary families, is vital to understanding planetary system formation and the processing history experienced by organic matter in the so-called interstellar-comet connection [3]. We have conducted observations, at primarily millimeter and submillimeter wavelengths, where molecular emission is easily resolved, towards comets to determine important cosmogonic quantities, such as the ortl1o:pal'a ratio and isotope ratios, as well as probe the origin of cometary organics. Comets provide important clues to the processes that occurred during the formation and early evolution of the Solar System. Past observations, as well as laboratory measurements of cometary material obtained from Stardust, have shown that comets appear to contain a mixture of the products from both interstellar and nebular chemistries. A major observational challenge in cometary science is to quantify the extent to which chemical compounds can be linked to either reservoir.

Milam, S. N.↗
NASA NTRS2012

Ground-Based Centimeter, Millimeter, and Submillimeter Observations of Recent Comets

Comets provide important clues to the physical and chemical processes that occurred during the formation and early evolution of the Solar System, and could also have been important for initiating prebiotic chemistry on the early Earth [I]. Comets are comprised of molecular ices, that may be pristine interstellar remnants of Solar System formation, along with high-temperature crystalline silicate dust that is indicative of a more thermally varied history in the protosolar nebula [2]. Comparing abundances of cometary parent volatiles, and isotopic fractionation ratios, to those found in the interstellar medium, in disks around young stars, and between cometary families, is vital to understanding planetary system formation and the processing history experienced by organic matter in the so-called interstellar-comet connection [3]. In the classical picture, the long-period comets probably formed in the nebular disk across the giant planet formation region (5-40 AU) with the majority of them originating from the Uranus-Neptune region. They were subsequently scattered out to the Oort Cloud (OC) by Jupiter. The short-period comets (also known as ecliptic or Jupiter Family Comets - JFC) reside mainly in the Edgeworth-Kuiper belt where they were formed. Given the gradient in physical conditions expected across this region of the nebula, chemical diversity in this comet population is to be expected [4,5]. We have conducted observations of comets I 03P/Hartley 2 (JFC) and C/2009 PI (Garradd) (OC), at primarily millimeter and submillimeter wavelengths, to determine important cosmogonic quantities, such as the ortho:para ratio and isotope ratios, as well as probe the origin of cometary organics and if they vary between the two dynamic reservoirs.

Milam, S. N.↗
NASA NTRS1994

Results of partial melting experiments on chondritic precursors of basaltic achondrites

Recent partial melting experiments on Murchison produced eucrite like glasses at reducing conditions. Although the glasses were remarkably similar to eucrites, the Fe/Mn ratio of the glasses was too high and the O isotopes cannot match eucrites. Mixing 70% H chondrite with 30% CM chondrite makes a potential precursor that satisfies the O isotope constraint on the eucrites. From experiments on both synthetic Murchison and a simplified version of the H70-CM30 mixture, simple partial melting of any individual or combination of known chondritic meteorites is incapable of producing eucritic glasses that have the appropriate Fe/Mn, Fe/(Fe + Mg), and O isotope ratios. In order to satisfy the Fe-Mn-Mg constraints imposed by the eucrites, both reduction of FeO to Fe-metal and olivine fractionation must occur in the precursor before partial melting is allowed to occur and produce the eucritic glass. To test this hypothesis, partial melting experiments on both Murchison and a mixture of 70% Allegan (H6)-30% Murchison (CM2) were conducted. The results of these new experiments show that to satisfy the O isotopes, Fe/Mn ratio, and Fe/(Fe + Mg) ratio, approximately 12% reduction of FeO to Fe-metal (in the silicate portion) and 20% olivine fractionation is required within the H-CM precursor to permit the formation of eucrites by partial melting. The sequence of FeO reduction and mantle fractionation permits very eucritic glasses to be produced. The problem that many remain with the H-CM precursor, however, is an overabundance of alkali elements. Correlations between temperature, O fugacity, and composition have also been found within our experiments. A basaltic achondrite precursor formed by mixing H and CM chondrites and constrained by O isotopes and Fe-Mn-Mg is compatible with a model of natural eucrites having formed by partial melting after metal and olivine fractionation in that precursor.

Boesenberg, J. S.↗
NASA NTRS1993

Mass Spectrometric Measurement of Martian Krypton and Xenon Isotopic Abundance

The Viking gas chromatograph mass spectrometer experiment provided significant data on the atmospheric composition at the surface of Mars, including measurements of several isotope ratios. However, the limited dynamic range of this mass spectrometer resulted in marginal measurements for the important Kr and Xe isotopic abundance. The Xe-129 to Xe-132 ratio was measured with an uncertainty of 70%, but none of the other isotope ratios for these species were obtained. Accurate measurement of the Xe and Kr isotopic abundance in this atmosphere provides an important data point in testing theories of planetary formation and atmospheric evolution. The measurement is also essential for a stringent test for the Martian origin of the SNC meteorites, since the Kr and Xe fractionation pattern seen in gas trapped in glassy nodules of an SNC (EETA 79001) is unlike any other known solar system resevoir. Current flight mass spectrometer designs combined with the new technology of a high-performance vacuum pumping system show promise for a substantial increase in gas throughput and the dynamic range required to accurately measure these trace species. Various aspects of this new technology are discussed.

Mahaffy, P.↗
NASA NTRS1978

The energetics of molecular clouds. II - The S140 molecular cloud

Techniques of analysis which allow estimates of kinetic temperature, gas density, gas cooling rate, and dust cooling rate are applied to the S140 molecular cloud. Maps of this cloud in various molecular lines are examined which reveal the existence of a strong temperature and density peak near the H-alpha rim and the presence of a strong near-IR source very near that peak. This source is found to have an energy distribution which is very similar to that of the Becklin-Neugebauer object, including the silicate feature at 9.5 microns. The heating and cooling rates for the gas and dust in S140 are estimated, and the predicted cooling rate for dust is shown to be much greater than that for gas. The molecular-line observations are compared with a spherical large-velocity-gradient trapping calculation. An optimum cloud model is developed which indicates that: (1) (C-13)O, HCO(+), and H2CO are about 10 times less abundant in S140 than in dark clouds; (2) the HCN abundance is approximately 4 times the H2CO abundance in S140, compared with roughly equal values in dark clouds; and (3) the (C-13)O/C(O-18) ratio is consistent with terrestrial isotope ratios.

Blair, G. N.↗
NASA NTRS1997

Interchange for Joint Research Entitled: Measurement of Stable Nitrogen and Sulfur Isotopes

Viking measurements of the Martian atmosphere indicate a value of N-15/N-14 which is markedly greater than that found in Earth's atmosphere. These isotopic measurements provide a powerful diagnostic tool which may be used to derive valuable information regarding the past history of Mars and they have been used to place important constraints on the evolution of Mars' atmosphere. Initial partial pressures of nitrogen, outgassing rates, and integrated deposition of nitrogen into minerals have been calculated from this important atmospheric data (McElroy et al., 1976 and 1977; Fox and Dalgarno, 1983). The greater precision obtained in laser spectrometer isotopic measurements compared to the Viking data will greatly improve these calculated values. It has also been proposed that the N-15/N-14 value in Mars' atmosphere has increased monotonically over time (McElroy et al., 1977; Fox and Dalgarno, 1983; Wallis, 1989) owing to preferential escape of atmospheric 14N to space. Nitrogen isotopic ratios might be used to identify relatively ancient crustal rocks (R. Mancinelli, personal communication), and perhaps determine relative aces of surface samples. As a first step in successfully measuring nitrogen isotopes optically we have demonstrated the measurement of 15NI14N to a precision of 0.1% (See Figures 1-4) using a tunable diode laser and an available gas (N-,O) with spectral lines in the 2188 cm-1 region. The sample and reference gas cells contained gases of identical isotopic composition so that the 15NI14N absorption ratio determined from the sample cell, when divided by the 15NI14N absorption ratio determined from the reference cell, should yield an ideal value of unity. The average measured value of this "ratio of ratios" was 0.9983 with a standard deviation (20 values) of 0.0010. This corresponds to a precision of 0.1% (1 per mil) for nitrogen isotopes, a value sufficiently precise to provide important isotopic data of interest to exobiologists. The precision presently attainable in gases is sufficient to permit the instrument to be used in the measurement of isotopic ratios of interest to exobiologists as well as geologists and planetary scientists.

Becker, Joseph F.↗
NASA NTRS1989

Isotopic abundances of stratospheric ozone from balloon-borne high-resolution infrared solar spectra

IR solar absorption spectra at 0.002-0.0003/cm resolution in the 10-micron region obtained during two balloon flights near 32 deg N latitude are examined to determine the isotopic ratios of (O-16)(O-16)(O-18) and (O-16)(O-18)(O-16) relative to normal ozone in the stratosphere. For November 18, 1987, the results show column-averaged isotopic enhancement ratios of 1.20 + or - 0.14 and 1.40 + or - 0.18 for (O-16)(O-18)(O-16)/(O-16)(O-16)(O-16) and (O-16)(O-16)(O-18)/(O-16)(O-16)(O-16), respectively. The corresponding values for June 6, 1988, show ratios of 1.16 + or - 0.08 and 1.25 + or - 0.12. The results are compared with heavy-to-normal O3 ratios obtained using other techniques.

Goldman, A.↗