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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2002

A Deuterium NMR Study of Bent-Core Liquid Crystals: Synthesis and Characterization of Deuterium-Labeled Oxadiazole-Containing Liquid Crystals - 1

We have synthesized two deuterated boomerang-shaped liquid crystals based on 2,5-bis(4-hydroxyphenyl)-1,3,4-oxadiazole (ODBP). Deuterium was introduced in the rigid 2,5-diphenyl-1,3,4-oxadiazole core and in the aromatic ring of the terminal 4-dodecyloxyphenyl moiety using standard acid catalyzed deuterium exchange conditions. Both compounds, ([4,4'(1,3,4-oxadiazole-2,5-diyl-d4)] di-4-dodecyloxybenzoate: ODBP-d4-Ph-O-C12) and ([4,4'(1,3,4-oxadiazole-2,5-diyl)] di-4-dodecyloxy-benzoate-d4; ODBP-Ph-d4-O-C12) were investigated by nuclear magnetic resonance, optical microscopy and differential scanning calorimetry. The optical textures and thermal behavior of both compounds were found to be identical to the non-deuterated analog [4,4(1,3,4-oxadiazole-2,5-diyl)] di-4-dodecyloxybenzoate (ODBP-Ph-O-C12) which we reported earlier. These compounds exhibit behavior indicative of a biaxial nematic liquid crystal phase, which we hope to confirm using deuterium NMR spectroscopy in the next phase of this study.

Dingemans, Theo J.↗
NASA NTRS2000

Deuterium enrichment of polycyclic aromatic hydrocarbons by photochemically induced exchange with deuterium-rich cosmic ices

The polycyclic aromatic hydrocarbon (PAH) coronene (C24H12) frozen in D2O ice in a ratio of less than 1 part in 500 rapidly exchanges its hydrogen atoms with the deuterium in the ice at interstellar temperatures and pressures when exposed to ultraviolet radiation. Exchange occurs via three different chemical processes: D atom addition, D atom exchange at oxidized edge sites, and D atom exchange at aromatic edge sites. Observed exchange rates for coronene (C24H12)-D2O and d12-coronene (C24D12)-H2O isotopic substitution experiments show that PAHs in interstellar ices could easily attain the D/H levels observed in meteorites. These results may have important consequences for the abundance of deuterium observed in aromatic materials in the interstellar medium and in meteorites. These exchange mechanisms produce deuteration in characteristic molecular locations on the PAHs that may distinguish them from previously postulated processes for D enrichment of PAHs.

NASA Center ARC↗
NASA NTRS2022

A Primordial Atmospheric Origin of Hydrospheric Deuterium Enrichment on Mars

The deuterium-to-hydrogen (D/H or 2H/1H) ratio of Martian atmospheric water (~6× standard mean ocean water, SMOW) is higher than that of known sources, requiring planetary enrichment. A recent measurement by NASA’s Mars Science Laboratory rover Curiosity of Hesperian-era (>3 Ga) clays yields a D/H ratio ~3×SMOW, demonstrating that most of the enrichment occurs early in Mars’s history, reinforcing the conclusions of Martian meteorite studies. As on Venus, Mars’s D/H enrichment is widely thought to reflect preferential loss to space of 1H (protium) relative to 2H (deuterium), but both the cause and the global environmental context of large and early hydrogen losses remain to be determined. Here, we apply a recent model of primordial atmosphere evolution to Mars, link the magma ocean of the accretion epoch with a subsequent water-ocean epoch, and calculate the behavior of deuterium for comparison with the observed record. In contrast to earlier works that consider Martian D/H fractionation in atmospheres in which hydrogen reservoirs are present exclusively as H2O or H2, here we consider 2-component (H2O-H2) outgassed atmospheres in which both condensed (H2O) and escaping (H2) components – and their interaction – are explicitly calculated. We find that a a ≈2-3× hydrospheric deuterium-enrichment is produced rapidly if the Martian magma ocean is chemically reducing at last equilibration with the primordial atmosphere, making H2 and CO the initially dominant species, with minor abundances of H2O and CO2. Reducing gases – in particular H2 – can cause substantial greenhouse warming and prevent a water ocean from freezing immediately after the magma ocean epoch. We find that greenhouse warming due to plausible H2 inventories (pH2=1-102 bars) yields surface temperatures high enough (Ts=290-560 K) to stabilize a water ocean and produce an early hydrological cycle through which surface water can be circulated. Moreover, the pressure-temperature conditions are high enough to produce ocean-atmosphere H2O-H2 isotopic equilibrium through gas-phase deuterium exchange such that surface H2O strongly concentrates deuterium relative to H2, which preferentially takes up protium and escapes from the primordial atmosphere. The efficient physical separation of deuterium-rich (H2O) and deuterium-poor (H2) species via condensation permits equilibrium isotopic partitioning and early atmospheric escape to be recorded in modern crustal reservoirs. The proposed scenario of primordial H2-CO-rich outgassing and escape suggests significant durations (>Myr) of chemical conditions on the Martian surface conducive to prebiotic chemistry immediately following magma ocean crystallization.

Mars↗
NASA NTRS1997

Deuterium Enrichment of Amino and Hydroxy Acids Found in the Murchison Meteorite: Constraints on Parent Body Conditions

The alpha-amino and alpha-hydroxy acids found in the Murchison carbonaceous chondrite are deuterium enriched. These compounds are thought to have originated from common deuterium enriched carbonyl precursors, by way of a Strecker synthesis which took place in a solution of HCN, NH3, and carbonyl compounds during the period of aqueous alteration of the meteorite parent body. However, the hydroxy acids found on Murchison are less deuterium enriched than the amino acids. With the objective of determining if the discrepancy in deuterium enrichment between the amino acids and the hydroxy acids found on Murchison is consistent with their formation in a Strecker synthesis, we have measured the deuterium content of alpha-amino and alpha-hydroxy acids produced in solutions of deuterated carbonyl compounds, KCN and NH4Cl, and also in mixtures of such solutions and Allende dust at 263 K and 295 K. Retention of the isotopic signature of the starting carbonyl by both alpha amino acids and alpha hydroxy acids is more dependent upon temperature, concentration and pH than upon the presence of meteorite dust in the solution. The constraints these observations place on Murchison parent body conditions will be discussed.

Lerner, Narcinda R.↗
NASA NTRS2013

Modeling Insights into Deuterium Excess as an Indicator of Water Vapor Source Conditions

Deuterium excess (d) is interpreted in conventional paleoclimate reconstructions as a tracer of oceanic source region conditions, such as temperature, where precipitation originates. Previous studies have adopted co-isotopic approaches to estimate past changes in both site and oceanic source temperatures for ice core sites using empirical relationships derived from conceptual distillation models, particularly Mixed Cloud Isotopic Models (MCIMs). However, the relationship between d and oceanic surface conditions remains unclear in past contexts. We investigate this climate-isotope relationship for sites in Greenland and Antarctica using multiple simulations of the water isotope-enabled Goddard Institute for Space Studies (GISS) ModelE-R general circulation model and apply a novel suite of model vapor source distribution (VSD) tracers to assess d as a proxy for source temperature variability under a range of climatic conditions. Simulated average source temperatures determined by the VSDs are compared to synthetic source temperature estimates calculated using MCIM equations linking d to source region conditions. We show that although deuterium excess is generally a faithful tracer of source temperatures as estimated by the MCIM approach, large discrepancies in the isotope-climate relationship occur around Greenland during the Last Glacial Maximum simulation, when precipitation seasonality and moisture source regions were notably different from present. This identified sensitivity in d as a source temperature proxy suggests that quantitative climate reconstructions from deuterium excess should be treated with caution for some sites when boundary conditions are significantly different from the present day. Also, the exclusion of the influence of humidity and other evaporative source changes in MCIM regressions may be a limitation of quantifying source temperature fluctuations from deuterium excess in some instances.

simulation↗
NASA NTRS1973

Possible detection of interstellar deuterium

The abundance of deuterium relative to hydrogen is an important parameter in constructing models of the early expansion of the universe in Big-Bang cosmologies. Calculations by Wagoner et al. (1967) and by Wagoner (1973) show that the deuterium abundance would be very sensitive to the density of baryons in the fireball and hence to the present mean mass density of the universe. Reeves et al. (1973) use data on the abundance of deuterium in the solar system to deduce a ratio of n sub D/n sub H = 1.8 plus or minus 0.8 x 10 to the minus 5 power, and note that other authors have pointed out that processing of matter in stars slowly reduces the deuterium abundance in the galaxy.

Cesarsky, D. A.↗
NASA NTRS1990

The effects of deuterium on static posture control

A significant operational problem impacting upon the Space Shuttle program involves the astronaut's ability to safely egress from the Orbiter during an emergency situation. Following space flight, astronauts display significant movement problems. One variable which may contribute to increased movement ataxia is deuterium (D2O). Deuterium is present in low levels within the Orbiter's water supply but may accumulate to significant physiological levels during lengthy missions. Deuterium was linked to a number of negative physiological responses, including motion sickness, decreased metabolism, and slowing of neural conduction velocity. The effects of D2O on static postural control in response to a range of dosage levels were investigated. Nine sugjects were divided into three groups of three subjects each. The groups were divided into a low, medium, and a high D2O dosage group. The subjects static posture was assessed with the use of the EquiTest systems, a commercially available postural control evaluation system featuring movable force plates and a visual surround that can be servoed to the subject's sway. In addition to the force plate information, data about the degree of subject sway about the hips and shoulders was obtained. Additionally, surface electromyographic (EMG) data from the selected lower limb muscles were collected along with saliva samples used to determine the amount of deuterium enrichment following D2O ingestion. Two baseline testing sessions were performed using the EquiTest testing protocol prior to ingestion of the D2O. Thirty minutes after dosing, subjects again performed the tests. Two more post-dosing tests were run with an interest interval of one hour. Preliminary data anlaysis indicates that only subjects in the igh dose group displayed any significant static postural problems. Future analyses of the sway and EMG is expected to reveal significant variations in the subject's postural control strategy following D2O dosing. While functionally significant static postural problems were not commonly observed, subjects in both the medium and high dosage groups displayed significant, and in some cases, severe voluntary movement problems.

Layne, Charles S.↗
NASA NTRS1992

Calculations of ion-molecule deuterium fractionation reactions involving HD

Gas-phase chemical models of deuterium fractionation in dense interstellar clouds utilize a small number of exothermic reactions to achieve fractionation. Although HD is a major repository of deuterium, it appears not to exchange deuterium with many molecular ions. Useful semiquantitative reasons have been given for the unusual lack of reactivity of exothermic ion-HD deuterium exchange systems, but quantum chemical studies are needed to understand these ideas in more detail and to determine if the lack of reactivity pertains at very low temperatures not studied in the laboratory, or whether tunneling can drive the reactions. Accordingly, the potential energy surfaces of three representative ion-molecule exchange reactions involving protonated ions and HD have been investigated with ab initio quantum chemical techniques. Our results generally confirm the semiquantitative picture as to which reactions are likely to occur and show that tunneling at low temperatures is unlikely to alter this picture.

Maluendes, Sergio A.↗
NASA NTRS1977

Deuterium and hydrogen in the local interstellar medium

Densities of neutral hydrogen and deuterium are found from observation with the Copernicus satellite of the Ly-alpha line toward two nearby stars. The hydrogen density is 0.03 + or - 0.01 per cu cm toward Alpha Aur (Capella) and 0.20 + or - 0.05 per cu cm in the direction of Alpha Cen A, values indicating that the nearby (less than 14 pc) interstellar medium is inhomogeneous and can be of low density in certain directions. The ratios of deuterium to hydrogen - 3.9 (+5.7, -1.7) by 10 to the -5th power and 0.24 (+0.12, -0.07) by 10 to the -5th power for Alpha Aur and Alpha Cen A, respectively - suggest that variations in the deuterium abundance may exist.

Dupree, A. K.↗
NASA NTRS1984

Observations of interstellar hydrogen and deuterium toward Alpha Centauri A

A composite profile is presented of the Ly-alpha emission line of Alpha Cen A, obtained from 10 individual spectra with the high-resolution spectrograph aboard the International Ultraviolet Explorer (IUE) satellite. There is excellent overall agreement with two previous Copernicus observations. Interstellar deuterium is detected, and a lower limit is set on the deuterium to hydrogen ratio of nDI/nHI greater than 8 x 10 to the -6th. In addition, the deuterium bulk velocity appears blueshifted by 8 + or - 2 km/s with respect to interstellar hydrogen, suggesting a nonuniform medium along the line of sight.

Landsman, W. B.↗
NASA NTRS1986

A possible deuterium anomaly: Implications of the CH3D/CH4 mixing ratios in the atmospheres of Jupiter, Saturn, and Uranus

Observations of CH3D in the atmospheres of the outer planets provide a test of the theory of deuterium fractionation equilibrium in the formation and evolution of these planets. Recent measurements of the CH3D/CH4 mixing ratios made for Saturn and Uranus are presented and intercompared with current values of Jupiter, illustrating large differences between the planets. Their implied D/H ratios are compared to D/H ratios derived from measurements of HD/H2; and, in the cases of Jupiter and Saturn, they may be incompatible. Implications of these comparisons are discussed in terms of the deuterium fractionation chemistry and possible enrichments of deuterium in the core ices of the planets.

Lutz, Barry L.↗
NASA NTRS1987

Deuterium in the daytime thermosphere

Ion concentration measurements for H(+) and D(+) from the magnetic ion mass spectrometer on the Atmosphere Explorer C satellite are used, in conjunction with other atmospheric data, to determine the concentrations of H and D in the nonpolar daytime thermosphere. The ratio of the observed D(+) to H(+) concentrations has essentially the same height dependence in the 300 to 800-km region as expected for their neutral counterparts, even in the presence of ion temperature gradients and probable large vertical ion fluxes. Rapid charge exchange with atomic oxygen ensures that D/H is about equal to D(+)/H(+) at the lower altitudes where the derived D to H concentration ratio is a factor of about 6 larger than its sea level value, for an exospheric temperature of 930 K. This relative enhancement of deuterium arises from the fact that hydrogen more readily escapes the earth, and a large vertical gradient in the H concentration relative to its diffusive equilibrium value is necessary to drive this upward flux through the lower thermosphere. If these planetary losses of hydrogen are much greater than those associated with evaporative escape, as is the current view, then correspondingly larger deuterium loss rates are also likely in order that the thermospheric D/H ratio not increase well above the observed value. The absolute winter daytime concentration of deuterium at 300 km is found to be 210 + or - 50 atoms/cu cm.

Breig, E. L.↗
NASA NTRS1998

Deuterium Enrichment of PAHs by VUV Irradiation of Interstellar Ices

Laboratory results demonstrate that polycyclic aromatic hydrocarbons (PAHs) rapidly exchange their hydrogen atoms with those of nearby molecules when they are frozen into low-temperature ices and exposed to vacuum ultraviolet radiation. As a result, PAHs quickly become deuterium-enriched when VUV irradiated in D-containing ices. This mechanism has important consequences for several astrophysical issues owing to the ubiquitous nature of PAHs in the interstellar medium. For example, this process may explain the deuterium enrichments found in PAHs in meteorites and interplanetary dust particles. These results also provide general predictions about the molecular siting of the deuterium on aromatic materials in meteorites if this process produced a significant fraction of their D-enrichment.

Bernstein, Max P.↗
NASA NTRS2019

Permeation Rate Equations for Hydrogen and Deuterium in a Palladium-Silver Alloy

Mass transfer of a gas through a selective, solid membrane is an effective method for separation of desired species. This selective permeability is evident in the flow of hydrogen and the isotope deuterium through palladium-silver metal alloy media. In this study, based upon Sieverts’s law and the Arrhenius diffusion equation, an empirical correlation was developed to determine the steady-state permeation rate R, dependence on media temperature T, gas supply pressure p(sub S), and gas backpressure p(sub B) on the lower pressure side. Because of an extensive range of experimental conditions and complete reporting of raw data, the research by Ackerman and Koskinas was used as a source for data allowing empirical equation fitting. Unfortunately, those authors reported best-fit equations that poorly represented their own results. To improve the modeling of the original data and demonstrate the quality of the measurements, the current study develops improved hydrogen and deuterium permeation rate equations: P = 4.22×10(exp −6) A[exp(−704/T)](sq. root p(sub S) − sq. root p(sub B))/t for hydrogen P = 2.12×10(exp −6) A[exp(−468/T )](sq. root p(sub S) − sq. root p(sub B))/t for deuterium for values of cross-sectional area A (sq.cm), medium thickness t (cm), pressure p (psia), and temperature T (Kelvin), giving a permeation rate in mole/minute. These equations model permeation rate data more closely than do several other existing literature sources.

Smith, Phillip J.↗
NASA NTRS2022

Deuterium Isotope Fractionation of Polycyclic Aromatic Hydrocarbons in Meteorites as an Indicator of Interstellar/Protosolar Processing History

The stable isotope composition of soluble and insoluble organic compounds in carbonaceous chondrites can be used to determine the provenance of organic molecules in space. Deuterium enrichment in meteoritic organics could be a residual signal of synthetic reactions occurring in the cold interstellar medium or an indicator of hydrothermal parent-body reactions. δD values have been measured in grains and bulk samples for a wide range of meteorites; however, these reservoirs are highly variable and may have experienced fractionation during thermal and/or aqueous alteration. Among the plethora of organic compounds in meteorites are polycyclic aromatic hydrocarbons (PAHs), which are stable and abundant in carbonaceous chondrites, and their δD ratio may preserve evidence about their formation environment as well as the influence of parent-body processes. This study tests hypotheses about the potential links between PAHs-deuteration concentrations and their formation conditions by examining the δD ratio of PAHs in three CM carbonaceous chondrites representing an aqueous alteration gradient. We use deuterium enrichments in soluble 2–5-ring PAHs as an indicator of either photon-driven deuteration due to unimolecular photodissociation in warm regions of space, gas-phase ion–molecule reactions in cold interstellar regions of space, or UV photolysis in ices. We also test hypothesized reaction pathways during parent-body processing that differ between partially and fully aromatized PAHs. New methodological approaches were developed to extract small, volatile PAHs without fractionation. Our results suggest that meteoritic PAHs could have formed through reactions in cold regions, with possible overprinting of deuterium enrichment during aqueous parent-body alteration, but the data could not rule out PAH alteration in icy mantles as well.

H V Graham↗