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NASA NTRS1986

The HD/H2 ratio in the atmosphere of Uranus

High resolution spectra of HD and H2 were brought together to derive the D/H ratio for Uranus. The deuterium concentration in the dominant molecular hydrogen phase is least susceptible to the effects of isotope fractionation in the planetary atmosphere, and the determination of relative abundances of HD and H2 is unambiguous due to nearness and relative weakness of the chosen spectral lines. The HD 5-0 R(0) and R(1) dipole lines and the H2 4-0 S(0), S(1), and S(2) quadrupole lines were obtained with a PEPSIOS instrument at the Palomar 5-meter telescope. The H2 spectra, which resolve the asymmetric line profiles resulting from pressure shifts in the deep stratified Uranus atmosphere, unambiguously define the line-of-sight hydrogen abundance for comparison with the HD spectra. The 5-0 band of HD was chosen to minimize interference from blended CH4 lines. However, weak interfering lines were found in the 5-0 bands from Uranus as well, and some uncertainties remain regarding the intrinsic line strengths in molecular hydrogen, complicating the analysis of the HD/H2 data. Nevertheless, it is established that the D/H ratio in the atmosphere of Uranus is smaller than the Jovian value, and is significantly smaller than recent theoretical predictions for Uranus based on estimates of isotope fractionation in the pre-planetary solar nebulae.

Trauger, J. T.↗
NASA NTRS2003

Microbeam Investigations of Presolar and Early Solar System Materials

This grant provided three years of funding to initiate an independent research program in Cosmochemistry at Arizona State University. Because the new equipment that was installed at ASU took longer than expected to get running, the project was extended for a fourth year with no additional funding. By the time the funds were expended, we had set up an entirely new ion microprobe laboratory at ASU, and we have been fully operational for over two years. This laboratory was funded in almost equal parts by NASA, NSF, and ASU. Papers describing the first results from this new laboratory are being published now, and the results have been making an impact on the Cosmochemistry community. While this laboratory was being built, I continued my research program in collaboration with G. J. Wasserburg at Caltech. As equipment became available, I gradually shifted my research to ASU. Over the lifetime of this grant, my research program resulted in 12 papers and 13 abstracts on topics ranging from presolar grains (2 papers, 3 abstracts), short-lived radionuclides (6 papers, 6 abstracts), chemical compositions of chondritic materials (3 papers, 3 abstracts), silicon isotopic fractionation (1 abstract), and the oxygen composition of the Sun (1 paper). The most important results of this period were the discovery of presolar hibonite in a meteorite residue, the measurement of 26A1 in CAIs from enstatite chondrites, and the measurements of 10Be in type A CAIs from CV chondrites. All of these results have had a significant impact on research in Cosmochemstry.

Huss, Gary R.↗
NASA NTRS1995

An NMR study of microvoids in polymers

An understanding of polymer defect structures, like microvoids in polymeric matrices, is crucial to their fabrication and application potential. In this project guest atoms are introduced into the microvoids in PMR-15 and NMR is used to determine microvoid sizes and locations. Xenon is a relatively inert probe that would normally be found naturally in polymer or in NMR probe materials. There are two NMR active xenon isotopes, Xe-129 and Xe-131. The Xe atom has a very high polarizability, which makes it sensitive to the intracrystalline environment of polymers. Interactions between the Xe atoms and the host matrix perturb the Xe electron cloud, deshielding the nuclei, and thereby expanding the range of the observed NMR chemical shifts. This chemical shift range which may be as large as 5000 ppm, permits subtle structural and chemical effects to be studied with high sensitivity. The Xe(129)-NMR line shape has been found to vary in response to changes in the pore symmetry of the framework hosts line Zeolites and Clathrasil compounds. Before exposure to Xe gas, the PMR-15 samples were dried in a vacuum oven at 150 C for 48 hours. The samples were then exposed to Xe gas at 30 psi for 72 hours and sealed in glass tubes with 1 atmosphere of xenon gas. Xenon gas at 1 atmosphere was used to tune up the spectrometer and to set up the appropriate NMR parameters. A single Xe-129 line at 83.003498 Mhz (with protons at 300 Mhz) was observed for the gas. With the xenon charged PMR-15 samples, a second broader line is observed 190 ppm downfield from the gas line (also observed). The width of the NMR line from the Xe-129 absorbed in the polymer is at least partially due to the distribution of microvoid sizes. From the chemical shift (relative to the gas line) and the line width, we estimate the average void sizes to be 2.74 +/- 0.20 angstroms. Since Xe-129 has such a large chemical shift range (approximately 5000 ppm), we expect the chemical shift anisotropy to contribute to the line width (delta upsilon = 2.5 kHz).

Toy, James↗
NASA NTRS1996

An NMR Study of Microvoids in Polymers

An understanding of polymer defect structures, like microvoids in polymeric matrices, is most crucial to their fabrication and application potential. In this project guest atoms are introduced into the microvoids in PMR-15 and NMR is used to determine microvoid sizes and locations. Xenon is a relatively inert probe that would normally not be found naturally in polymer or in NMR probe materials. There are two NMR active Xenon isotopes, Xe-129 and Xe-131. The Xe atom has a very high polarizability, which makes it sensitive to the intracrystalline environment of polymers. Interactions between the Xe atoms and the host matrix perturb and Xe electron cloud, deshielding the nuclei, and thereby expanding the range of the observed NMR chemical shifts. This chemical shift range which may be as large as 5000 ppm, permits subtle structural and chemical effects to be studied with high sensitivity. The Xe-129-NMR line shape has been found to vary in response to changes in the pore symmetry of the framework hosts in Zeolites and Clathrasil compounds. Before exposure to Xe gas, the PMR-15 samples were dried in a vacuum oven at 150 C for 48 hours. The samples were then exposed to Xe gas at 30 psi for 72 hours and sealed in glass tubes with 1 atmosphere of Xenon gas. Xenon gas at 1 atmosphere was used to tune up the spectrometer and to set up the appropriate NMR parameters. A series of spectra were obtained interspersed with applications of vacuum and heating to drive out the adsorbed Xe and determine the role of Xe-Xe interactions in the observed chemical shift.

Toy, James↗
NASA NTRS1993

Collision cross sections and diffusion parameters for H and D in atomic oxygen

Modeling the behavior of H and D in planetary exospheres requires detailed knowledge of the differential scattering cross sections for all of the important neutral-neutral and ion-neutral collision processes affecting these species over their entire ranges of interaction energies. In the upper atmospheres of Earth, Venus, and other planets as well, the interactions of H and D with atomic oxygen determine the rates of diffusion of escaping hydrogen isotopes through the thermosphere, the velocity distributions of exospheric atoms that encounter the upper thermosphere, the lifetimes of exospheric orbiters with periapsides near the exobase, and the transfer of momentum in collisions with hot O. The nature of H-O and D-O collisions and the derivation of a data base consisting of phase shifts and the differential, total, and momentum transfer cross sections for these interactions in the energy range 0.001 - 10 eV are discussed. Coefficients of mutual diffusion and thermal diffusion factors are calculated for temperatures of planetary interest.

Hodges, R. R., Jr.↗
NASA NTRS2009

Evolved Gas Measurements Planned for the Lower Layers of the Gale Crater Mound with the Sample Analysis at Mars Instrument Suite

The lower mound strata of Gale Crater provide a diverse set of chemical environments for exploration by the varied tools of the Curiosity Rover of the Mars Science Laboratory (MSL) Mission. Orbital imaging and spectroscopy clearly reveal distinct layers of hydrated minerals, sulfates, and clays with abundant evidence of a variety of fluvial processes. The three instruments of the MSL Sample Analysis at aMars (SAM) investigation, the Quadrupole Mass Spectrometer (QMS), the Tunable Laser Spectrometer (TLS), and the Gas Chromatograph (GC) are designed to analyze either atmospheric gases or volatiles thermally evolved or chemically extracted from powdered rock or soil. The presence or absence of organic compounds in these layers is of great interest since such an in situ search for this type of record has not been successfully implemented since the mid-60s Viking GCMS experiments. However, regardless of the outcome of the analysis for organics, the abundance and isotopic composition of thermally evolved inorganic compounds should also provide a rich data set to complement the mineralogical and elemental information provided by other MSL instruments. In addition, these evolved gas analysis (EGA) experiments will help test sedimentary models proposed by Malin and Edgett (2000) and then further developed by Milliken et al (2010) for Gale Crater. In the SAM EGA experiments the evolution temperatures of H2O, CO2, SO2, O2, or other simple compounds as the samples are heated in a helium stream to 1000 C provides information on mineral types and their associations. The isotopic composition of O, H, C, and S can be precisely determined in several evolved compounds and compared with the present day atmosphere. Such SAM results might be able to test mineralogical evidence of changing sedimentary and alteration processes over an extended period of time. For example, Bibring et al (2006) have suggested such a major shift from early nonacidic to later acidic alteration. We will illustrate through a variety of evolved gas experiments implemented under SAM-like gas flow and temperature ramp conditions on terrestrial analog minerals on high fidelity Sam breadboards the type of chemical information we expect SAM to provide.

Mahaffy, Paul↗
NASA NTRS1992

Carbon and hydrogen isotopic characterization of methane from wetlands and lakes of the Yukon-Kuskokwim Delta, Western Alaska

The results are reported of a study of the carbon and hydrogen isotopic composition of methane from tundra environments of the Yukon-Kuskokwin Delta of western Alaska. The delta C-13 value of diffusive methane emissions from wet meadow tundra of the Delta is -65.82 +/- 2.21 per mil (n=18). Detritus-rich sediments of tundra lakes are loaded with methane-rich gas bubbles during the warm season. Spatial trend is the major gas concentration and isotopic values of methane in these gas bubbles appear to reflect processes associated with production rate and mechanisms; high methane concentrations, lightest delta C-13 values, the heaviest delta D value occur in detritus-rich sediments isolated from emergent vegetation. Heavier delta C-13 and lighter delta D values in methane from heavily vegetated lake margins suggest a shift toward a larger role for acetate fermentation in association with aquatic plants and plant detritus. Bubble ebullition is estimated to account for up to 17 percent of total Delta methane emissions.

Martens, Christopher S.↗
NASA NTRS2007

Methylhopane Biomarker and Carbon Isotopic Evidence for Late Archean Aerobic Ecosystems

Molecular fossils are particularly valuable in early Earth studies because they provide information about microbial sources and ecology. Here we report on the distribution of 2- methyl and 3-methylhopanes preserved in a 2.72-2.56 billion-year-old section of shallow and deepwater sediments of the Hamersley Province [Eigenbrode et aI., submitted]. These biomarkers are mostly from cyanobacteria and oxygen-respiring methanotrophs, respectively. The relative abundance of 2-methylhopanes increases with carbonate abundance in shallow-water facies indicating cyanobacteria were key microbes in shallow ecosystems and suggesting they supplied both molecular oxygen and fixed carbon. The relative abundance of 3-methylhopane strongly correlates with kerogen-carbon isotopic values, and is more abundant in the samples with 13C-enriched signatures. Thus, molecular data provides evidence for cycling of methane in shallow settings, even though the anoxic deeper environments bear stronger 13C-depletion, which together suggests a more complex methane cycle than previously envisioned. Detailed facies analysis of the Hamersley carbon-isotope record reveals temporal changes suggesting continued oxidation of shallow settings favoring the expansion of aerobic ecosystems and respiring organisms [Eigenbrode et aI., 2006, PNAS, 103: 15759]. Similar analysis of published carbon-isotopic records suggests similar, but diachronous, expansion of oxygenated habitats in shallow then deep waters as anaerobic microbial communities gave way to respiring communities fueled by oxygenic photosynthesis before the post 2.45-Ga atmospheric oxygenation event [Eigenbrode et aI., 2006]. The robust relationships observed provide geochemical support for methanogenesis, aerobic methanotrophy, and oxygenic photosynthesis in the late Archean, as well as major ecological shifts linked to biogeochemical reorganization.

Eigenbrode, Jennifer L.↗
NASA NTRS2021

A data–model approach to interpreting speleothem oxygen isotope records from monsoon regions

Reconstruction of past changes in monsoon climate from speleothem oxygen isotope (δ 18 O) records is complex because δ 18 O signals can be influenced by multiple factors including changes in precipitation, precipitation recycling over land, temperature at the moisture source, and changes in the moisture source region and transport pathway. Here, we analyse >150 speleothem records of the Speleothem Isotopes Synthesis and AnaLysis (SISAL) database to produce composite regional trends in δ 18 O in monsoon regions; compositing minimises the influence of site-specific karst and cave processes that can influence individual site records. We compare speleothem δ 18 O observations with isotope-enabled climate model simulations to investigate the specific climatic factors causing these regional trends. We focus on differences in δ 18 O signals between the mid-Holocene, the peak of the Last Interglacial (Marine Isotope Stage 5e) and the Last Glacial Maximum as well as on δ 18 O evolution through the Holocene. Differences in speleothem δ 18 O between the mid-Holocene and the Last Interglacial in the East Asian and Indian monsoons are small, despite the larger summer insolation values during the Last Interglacial. Last Glacial Maximum δ 18 O values are significantly less negative than interglacial values. Comparison with simulated glacial–interglacial δ 18 O shows that changes are principally driven by global shifts in temperature and regional precipitation. Holocene speleothem δ 18 O records show distinct and coherent regional trends. Trends are similar to summer insolation in India, China and southwestern South America, but they are different in the Indonesian–Australian region. Redundancy analysis shows that 37 % of Holocene variability can be accounted for by latitude and longitude, supporting the differentiation of records into individual monsoon regions. Regression analysis of simulated precipitation δ 18 O and climate variables show significant relationships between global Holocene monsoon δ 18 O trends and changes in precipitation, atmospheric circulation and (to a lesser extent) source area temperature, whereas precipitation recycling is non-significant. However, there are differences in regional-scale mechanisms: there are clear relationships between changes in precipitation and δ 18 O for India, southwestern South America and the Indonesian–Australian regions but not for the East Asian monsoon. Changes in atmospheric circulation contribute to δ 18 O trends in the East Asian, Indian and Indonesian–Australian monsoons, and a weak source area temperature effect is observed over southern and central America and Asia. Precipitation recycling is influential in southwestern South America and southern Africa. Overall, our analyses show that it is possible to differentiate the impacts of specific climatic mechanisms influencing precipitation δ 18 O and use this analysis to interpret changes in speleothem δ 18 O.

speleothem oxygen isotope records↗
NASA NTRS1977

The trapped mercury ion frequency standard

Singly ionized mercury atoms have a structure similar to neutral alkali atoms. They can be maintained as ions for very long times in an RF quadrupole ion trap. Thus, their ground state hyperfine structure can be used to make a frequency standard using optical pumping techniques similar to the well-known rubidium standard. The mass 199 isotope of mercury has an ionic hyperfine structure of 40.5 GHz. In a trap system a linewidth of 10 Hz has been measured. An expression is presented for the short-term stability of a proposed mercury standard as set by the achieved signal to noise ratio. There is prospect of further improvement. Long-term stability is affected by second order doppler effect, and by pressure, light, and Stark shifts. However, these appear either sufficiently small or sufficiently controlable that the proposed mercury ion standard would be competitive with existing standards.

Mcguire, M. D.↗
NASA NTRS1992

Self-, N2, O2, H2, Ar, and He broadening in the nu3 band Q branch of CH4

Self-, N2-, O2-, H2-, Ar-, and He-broadening coefficients, pressure shifts, and integrated intensities have been measured for most transitions in the Q branch of the nu3 fundamental band of methane using a difference-frequency laser spectrometer. A systematic dependence of the broadening coefficients on the tetrahedral symmetry species and order index is observed with striking similarities for N2, O2, and Ar and for H2 and He buffer gases. Comparison with earlier measurements on other bands and branches of methane indicates very little vibrational, branch, or carbon isotope dependence. Dicke narrowing is evident at intermediate pressures, yielding an average narrowing coefficient and an optical diffusion constant for each gas mixture.

Pine, A. S.↗
NASA NTRS1971

Research investigation directed toward extending the useful range of the electromagnetic spectrum

The lifetimes and fine structure of He(-) were studied using time-of-flight techniques and quenching by a static axial magnetic field. Using level-crossing spectroscopy the hyperfine constants A and B and the lifetime of the 3 2P3/2 state of Li-7 were measured. Polarization of the Ru 7S level was created as a first step in determining the hyperfine structure of the alkali excited S state. The parametric interaction between light and microwaves in optically pumped Rb-87 vapor were investigated. Measurements and analyses of transitions in formaldehyde and its isotopic species and in the lowest two excited vibrational states of H2CO were also made, as well as of transitions in furan, pyrrole, formic acid, and cyanoacetylene. The Hanle effect was studied in the NO molecule, and RF oscillators were developed with flat, wideband output to observe excited state hyperfine transitions at zero field. Data was generated on the time-dependent behavior of photon echoes in ruby. Stimulated Raman scattering was studied in atomic Tl vapor. A Q switched, temperature-tuned ruby laser was developed which operates between 6934 and 6938 A. The frequency shift due to resonant interaction between identical radiating atoms was calculated.

Hartmann, S. R.↗
NASA NTRS1988

Nitrogen geochemistry of a Cretaceous-Tertiary boundary site in New Zealand

Nitrogen in the basal layer of the K-T boundary clay at Woodside Creek, New Zealand, has an abundance of 1100 ppm, a 20-fold enrichment over Cretaceous and Tertiary values. The enrichment parallels that for Ir and elemental carbon (soot); all decrease over the next 6 mm of the boundary clay. The C/N ratio, assuming the nitrogen to be associated with organic rather than elemental carbon, is approximately 5 for the basal layer compared to 20 to 30 for the remainder of the boundary clay. The correlation between N and Ir abundances appears to persist above the boundary, implying that the N is intimately associated with the primary fallout and remained with it during the secondary redeposition processes that kept the Ir abundance relatively high into the lowermost Tertiary. Apparently the basal layer of the boundary clay represents the accumulation of a substantial quantity of N with an isotopic composition approximately 10 percent heavier than background delta value of N-15 values. If the boundary clay represents an altered impact glass from a meteorite impact than it probably denotes a time period of less than 1 year. Therefore, the changes in nitrogen geochemistry apparently occurred over a very short period of time. The high abundance of N and the correspondingly low C/N ratio may reflect enhanced preservation of organic material as a result of the rapid sweepout and burial of plankton by impact ejecta, with little or no bacterial degradation. It is conceivable that the shift in delta value of N-15 may represent an influx of nitrogen from a different source deposited contemporaneously with the impact ejecta. An interesting possibility is that it may be derived from nitrate, produced from the combustion of atmospheric nitrogen.

Gilmour, Iain↗
NASA NTRS1994

Stable water isotope behavior during the last glacial maximum: A general circulation model analysis

Global water isotope geochemisty during the last glacial maximum (LGM) is simulated with an 8 deg x 10 deg atmospheric general circulation model (GCM). The simulation results suggest that the spatial delta O-18/temperature relationships observed for the present day and LGM climates are very similar. Furthermore, the temporal delta O-18/temperature relationship is similar to the present-day spatial relationship in regions for which the LGM/present-day temperature change is significant. This helps justify the standard practice of applying the latter to the interpretation of paleodata, despite the possible influence of other factors, such as changes in the evaportive sources of precipitation or in the seasonality of precipitation. The model suggests, for example, that temperature shifts inferred from ice core data may differ from the true shifts by only about 30%.

Jouzel, Jean↗
NASA NTRS2005

Genesis Noble Gas Measurements

The original thrust of our Genesis funding was to extend and refine the noble gas analytical capabilities of this laboratory to improve the precision and accuracy of noble gas measurements in order to optimize the scientific return from the Genesis Mission. This process involved both instrumental improvement (supplemented by a SRLIDAP instrument grant) and refinement of technique. The Genesis landing mishap shifted our emphasis to the irregular aluminum heat shield material from the flat collector wafers. This has required redesign of our laser extraction cells to accommodate the longer focal lengths required for laser extraction from non-flat surfaces. Extraction of noble gases from solid aluminum surfaces, rather than thin coatings on transparent substrates has required refinement of controlled-depth laser ablation techniques. Both of these bring new problems, both with potentially higher blanks form larger laser cells and the larger quantities of evaporated aluminum which can coat the sapphire entrance ports. This is mainly a problem for the heavy noble gases where larger extraction areas are required, necessitating the new aluminum vapor containment techniques described below. With the Genesis Mission came three new multiple multiplier noble gas mass spectrometers to this laboratory, one built solely by us (Supergnome-M), one built in collaboration with Nu-Instruments (Noblesse), and one built in collaboration with GVI (Helix). All of these have multiple multiplier detection sections with the Nu-Instruments using a pair of electrostatic quad lenses for isotope spacing and the other two using mechanically adjustable positions for the electron multipliers. The Supergnome-M and Noblesse are installed and running. The GVI instrument was delivered a year late (in March 2005) and is yet to be installed by GVI. As with all new instruments there were some initial development issues, some of which are still outstanding. The most serious of these are performance issues with the miniature channel electron multipliers. The delayed installation of Helix by the GVI is partly due to failure of the initial batch of Burle channel multipliers to perform as expected. A number of the channel multipliers designed for Noblesse by Burle have also failed upon baking. Burle has now refined the design of these and we have installed two of the new multipliers and are assessing their performance. The remaining multipliers Will be upgraded to the new design from Burle once we confirm that the problem has been fixed.

Hohenberg, Charles M.↗
NASA NTRS2017

Variability and Quasi-Decadal Changes in the Methane Budget over the Period 2000-2012

Following the recent Global Carbon Project (GCP) synthesis of the decadal methane (CH4) budget over 2000- 2012, we analyse here the same dataset with a focus on quasi-decadal and inter-annual variability in CH4 emissions. The GCP dataset integrates results from top-down studies (exploiting atmospheric observations within an atmospheric inverse-modelling framework) and bottom-up models (including process-based models for estimating land surface emissions and atmospheric chemistry), inventories of anthropogenic emissions, and data-driven approaches. The annual global methane emissions from top-down studies, which by construction match the observed methane growth rate within their uncertainties, all show an increase in total methane emissions over the period 2000-2012, but this increase is not linear over the 13 years. Despite differences between individual studies, the mean emission anomaly of the top-down ensemble shows no significant trend in total methane emissions over the period 2000-2006, during the plateau of atmospheric methane mole fractions, and also over the period 2008-2012, during the renewed atmospheric methane increase. However, the top-down ensemble mean produces an emission shift between 2006 and 2008, leading to 22 [16-32] Tg CH4 yr(exp -1) higher methane emissions over the period 2008-2012 compared to 2002-2006. This emission increase mostly originated from the tropics, with a smaller contribution from mid-latitudes and no significant change from boreal regions. The regional contributions remain uncertain in top-down studies. Tropical South America and South and East Asia seem to contribute the most to the emission increase in the tropics. However, these two regions have only limited atmospheric measurements and remain therefore poorly constrained. The sectorial partitioning of this emission increase between the periods 2002-2006 and 2008-2012 differs from one atmospheric inversion study to another. However, all top-down studies suggest smaller changes in fossil fuel emissions (from oil, gas, and coal industries) compared to the mean of the bottom-up inventories included in this study. This difference is partly driven by a smaller emission change in China from the top-down studies compared to the estimate in the Emission Database for Global Atmospheric Research (EDGARv4.2) inventory, which should be revised to smaller values in a near future. We apply isotopic signatures to the emission changes estimated for individual studies based on five emission sectors and find that for six individual top-down studies (out of eight) the average isotopic signature of the emission changes is not consistent with the observed change in atmospheric 13CH4. However, the partitioning in emission change derived from the ensemble mean is consistent with this isotopic constraint. At the global scale, the top-down ensemble mean suggests that the dominant contribution to the resumed atmospheric CH4 growth after 2006 comes from microbial sources (more from agriculture and waste sectors than from natural wetlands), with an uncertain but smaller contribution from fossil CH4 emissions. In addition, a decrease in biomass burning emissions (in agreement with the biomass burning emission databases) makes the balance of sources consistent with atmospheric 13CH4 observations. In most of the top-down studies included here, OH concentrations are considered constant over the years (seasonal variations but without any inter-annual variability). As a result, the methane loss (in particular through OH oxidation) varies mainly through the change in methane concentrations and not its oxidants. For these reasons, changes in the methane loss could not be properly investigated in this study, although it may play a significant role in the recent atmospheric methane changes as briefly discussed at the end of the paper.

Saunois, Marielle↗