Stable isotope mass fragmentography - Identification and hydrogen-deuterium exchange studies of eight Murchison meteorite amino acids
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Intramolecular carbon, hydrogen, and sulfur isotope measurements have been made on a homologous series of organic sulfonates discovered in the Murchison meteorite. Mass independent sulfur isotope fractionations were observed along with D/H ratios clearly larger than terrestrial. The sulfur fractionations may be produced chemically and due to molecular symmetry factors. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low temperature astrophysical environment consistent with that of molecular clouds. The source of the sulfonate precursors may have been the reactive interstellar molecule, CS. Low temperature CS reactions also produce other sulfur containing compounds as well as a solid phase. Isotopic measurements on bulk phosphonates were also made.
Ammonia poses a challenge in effluent gas streams due to its corrosive nature. However, in fusion settings tritiated ammonia can be formed, leading to both tritium loss in inventory and the generation of reactive species. Therefore, identifying pathways in which both tritium can be recovered, and the ammonia can be easily handled would be beneficial. One such way to do so would be to combine two useful techniques: ammonia sequestration and hydrogen exchange (ND 3 →NH 3 ). However, materials that can both adsorb ammonia and subsequently perform reactions on ammonia have not been well explored. Here, in this work, we present the development of ion-exchanged A-type zeolites to be utilized as a support material for platinum catalysts. In this way, the zeolite can adsorb ammonia and the platinum catalyst can facilitate hydrogen exchange allowing for bifunctional reactivity of the material to be achieved. A variety of elements were explored for their effect on A-type zeolites and resulted in an isotopic difference in the adsorption of ND 3 and NH 3 , noting the use of deuterium as a surrogate for tritium. Several platinum-impregnated zeolites were able to remove ND 3 from the gas stream, indicating that utilizing these materials in isotope recovery processes would improve accountability of these valuable hydrogen isotopes.
Organic sulfonates and phosphonates have been extracted from the Murchison meteorite for stable isotope measurements. Preliminary stable isotope measurements of individual alkyl sulfonates, R-SO3H (R=C(sub n)H(sub 2n+l)), are shown. These compounds were found in aqueous extracts of Murchison. Both groups show trends similar to other homologous series of organic compounds indigenous to Murchison. Molecular abundances decrease with increasing carbon number, and all possible isomers at each carbon number (through C-4) are present. Carbon isotope measurements of the sulfonates show a decrease in the C-13/C-12 ratio with increasing carbon number. The overall objectives of this project are to obtain dime element carbon, hydrogen, and sulfur - intramolecular isotopic analyses of individual sulfonates, and isotopic measurement of carbon and hydrogen of the phosphonates as a group. The Murchison meteorite is the best characterized carbonaceous chondrite with respect to organic chemistry. The finding of organic sulfonates and phosphonates in Murchison is of interest because they are the first well-characterized series of sulfur and phosphorus containing organic compounds found in meteorites. Also, meteorites, comets, and interplanetary dust particles may have been involved in chemical evolution on the early Earth. Because of the critical role of organic phosphorus and sulfur in all living systems, it is particularly interesting to see examples of abiotic syntheses of these classes of compounds. The study of the isotopic composition of the sulfonates and phosphonates can yield insight into their possible interstellar origin as well as their mechanisms of synthesis in the early solar system. Previous isotopic analyses of other classes of organic compounds indigenous to meteorites, e.g., amino acids, carboxylic acids, and hydrocarbons indicate the possibility that interstellar molecules were incorporated into meteorite parent bodies. In these compounds the ratios of heavy to light isotopes of hydrogen (D/H), carbon (C-13/C-12), and nitrogen (N-15/N-14), are anomalous relative to bulk terrestrial and meteoritic values. In some cases, the D/H ratios approach those observed for molecules in interstellar clouds.
The internal energy, pressure, and compressibility of ground-state, spin-aligned atomic hydrogen, deuterium, and tritium are calculated assuming that all pair interactions occur via the atomic triplet (spin-aligned) potential. The conditions required to obtain atomic hydrogen and its isotopes in bulk are discussed; such a development would be of value in propulsion systems because of the light mass and energetic recombination of atomic hydrogen. Results show that atomic triplet hydrogen and deuterium remain gaseous at 0 K, and that tritium forms a liquid with a binding energy of approximately -0.75 K per atom at a molar volume of 130 cu cm per mole. The pair distribution function for these systems is calculated, and the predicted superfluid behavior of atomic triplet hydrogen and tritium is briefly discussed.
Solar activity has been correlated to climatic fluctuations and has been postulated as a major factor in quasi-periodic global climatic change. However, correlations are not explanations of physical mechanisms and do not couple cause with effect. A mechanism for a chronometer for solar output variability is proposed based on relations between properties of thermonuclear fusion, nuclear magnetic moment, and nuclear magnetic resonance. A fundamental oscillation of a nucleus with a net nuclear magnetic moment (NMM) is the precession of its axis of rotation when subjected to a magnetic field. Nuclear magnetic resonance (NMR) is the preferred frequency of precession for a nucleus of a particular isotope when placed in a magnetic field of specific intensity. The NMM for those isotopes involved in the proton-proton (p-p) chain pathway for solar fusion varies from strong positive to strong negative. Individual fusion events, for hydrogen and helium isotopes which release varying amounts of energy, may be controlled by NMR frequencies. The pulses of energy from fusion events occurring at NMR frequencies in the solar interior may be transformed into pressure or gravity waves that emerge as gravity or acoustic waves at the surface. Dictated by spherical harmonics, certain wavelengths may be reinforced and reenter the solar interior to modulate the fusion process. Qualitative analysis of solar and climatic data support the interaction of the three basic components of the chronometer, magnetic activity, oscillation frequency, and solar energy output.
A description is given of an experiment which was designed to measure the spectra and composition of cosmic-ray hydrogen and helium isotopes in the interval 120-280 MeV per nucleon to compare with the recent values observed at low energies and also with the only earlier measurement in this high-energy regime. The results presented were obtained during a high-altitude balloon flight from Thompson, Manitoba, in 1973 August. This flight occurred during the period in which the presence of the anomalous component in the helium spectrum became apparent, and provides the opportunity of determining whether this component extends to higher energies than those studied by satellite experiments. The results place an upper limit on the flux of 'anomalous' He-4 (which appeared at low energy in 1972) of at most 15% in the energy range of this experiment, and combined with the low-energy observations of the Chicago group, show an energy dependence of the average ratio of the helium isotopes in the modulated cosmic rays which is difficult to reconcile with current modulation models.
In this study, we discovered a turbulence transition in a large helical device. The turbulence level and turbulence-driven energy transport decrease to a specific transition density and increase above it. The ruling turbulences below and above the transition density were ion-temperature gradient (ITG) and resistive-interchange (RI) turbulences, consistent with the predictions of gyrokinetic theory and two-fluid MHD model, respectively. Isotope experiments on hydrogen (H) and deuterium (D) clarified the role of transitions. In the ITG regime, turbulence levels and energy transport were comparable in the H and D plasmas. In contrast, in the RI regime, they were clearly suppressed in the D plasma. The results provide crucial knowledge for understanding isotope effects and future optimization of stellarator and heliotron devices. Published by the American Physical Society 2024
The charge, energy spectra, and isotopic composition of hydrogen through nitrogen have been studied with the GSFC/UNH cosmic ray experiments on board the Pioneer 10 and 11 spacecraft. Good charge and mass resolution have been obtained by utilizing three parameter analysis (i.e., two measurements of delta E and a measurement of the residual kinetic energy of stopping particles). This method allows isotopic resolution for the High Energy Telescope (HET) which operates over a typical energy range of 30-56-MeV/nuc for He. The observations will be over solar quiet times from September 1976-September 1977. The resolution, methods of analysis, spectra, and isotopic composition will be presented and discussed where the statistical significance of H to C isotopes is meaningful.
Present and future climatic trends are expected to markedly alter water fluxes and stores in the hydrologic cycle. In addition, water demand continues to grow due to increased human use and a growing population. Sustainably managing water resources requires a thorough understanding of water storage and flow in natural, agricultural, and urban ecosystems. Measurements of stable isotopes of water (hydrogen and oxygen) in the water cycle (atmosphere, soils, plants, surface water, and groundwater) can provide information on the transport pathways, sourcing, dynamics, ages, and storage pools of water that is difficult to obtain with other techniques. However, the potential of these techniques for practical questions has not been fully exploited yet. Here, we outline the benefits and limitations of potential applications of stable isotope methods useful to water managers, farmers, and other stakeholders. We also describe several case studies demonstrating how stable isotopes of water can support water management decision-making. Finally, we propose a workflow that guides users through a sequence of decisions required to apply stable isotope methods to examples of water management issues. We call for ongoing dialogue and a stronger connection between water management stakeholders and water stable isotope practitioners to identify the most pressing issues and develop best-practice guidelines to apply these techniques.
We have used a combination of pico-to-nano temporal/spatial scale computational physics and chemistry modeling of plasma–material interfaces in the tokamak fusion plasma edges to unravel the evolving characteristics, not readily accessible by empirical means, of lithium-, oxygen-, and hydrogen-containing materials of plasma-facing components under irradiation by hydrogen and its isotopes. In the present calculation, amorphous lithium compound surfaces containing oxygen, Li 2 O, and LiOH were irradiated by 1-100 eV particles at incident angles on the surface ranging from perpendicular to almost grazing angles. Consequential surface processes, reflection, retention, and sputtering were studied at “the same footing” and compared to earlier results from amorphous Li and LiH surfaces. In conclusion, the critical role of charging dynamics of lithium, oxygen, and hydrogen atoms in the surface chemistry during hydrogen-fuel irradiation was found to drive the kinetics and dynamics of these surfaces in unexpected ways that ultimately could have profound effects on fusion plasma confinement behavior and surface erosion.
A simple exponential-potential model of molecular collisions leads to a two-parameter analytic expression for rates of collisionally induced vibrational-translation (VT) energy exchange that has been shown to be accurate over variations of orders of magnitude as a function of temperature in a variety of systems. This includes excellent agreement with reported experimental and theoretical results for the fundamental self-relaxation rate of molecular hydrogen H2(v = 1) + H2 yields H2(v = 0) + H2. The analytic rate successfully follows the five-orders-of-magnitude change in experimental values for the temperature range 50-2000 K. This approach is now applied to isotope effects in the vibrational relaxation rates of excited HD and D2 in collision with H2: HD(v = 1)+H2 yields HD(v = 0)+H2 and D2(v = 1)+H2 yields D2(v = 0)+H2. The simplicity of the analytic expression for the thermal rate lends itself to convenient application in modeling the evolving vibrational populations of molecular hydrogen in shocked astrophysical environments.
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.
The data collected in the present work extend the measured phase diagram for palladium hydride and palladium deuteride to a region that has been sparsely reported in open literature. Absorption isotherms were measured using a 2.5-g bed of palladium powder at temperatures between 130 K and 393 K and pressures less than 1.3 x 10 5 Pa. Such low-pressure and low-temperature measurements are useful for characterizing palladium beds used for tritium pumping and storage. For tritium storage, pressures are kept below a few millibar for safety reasons. Low temperatures increase the tritium storage capacity of palladium. The measured absorption isotherms show the well-documented, two-phase behavior for this system: two solubility regions and a mixed, hydride-forming region. The isotherms show that an increased quantity of hydride is formed at lower temperatures, as marked by an increase in the hydride-forming region. This region exceeds hydrogen to metal ratios of 0.75 for T ≤ 273 K. Equilibrium pressures in the mixed region decrease with decreasing temperatures until a critical temperature is reached for each isotope. Below these critical temperatures, the rate of pressure decrease with decreasing temperature is significantly reduced. This change in trend suggests hydrogen isotopes are adsorbed onto the palladium surface, rather than forming a hydride. Using the equilibrium pressures recorded at temperatures between 236 K and 393 K for protium and between 211 K and 354 K for deuterium, the van’t Hoff constants were calculated to be A = –36 ± 1 kJ/mol and B = 88 ± 3 J/K for protium and A = -32 ± 2 kJ/mol and B = 88 ± 9 J/K for deuterium. As a result, these constants agree favorably with literature in the range where the temperatures of the measured isotherms overlap.
Measurements of stable hydrogen, carbon, and nitrogen isotopic ratios (delta D, delta C-13, delta N-15) of organic compounds can reveal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may point towards the most likely of these proposed pathways. The technique of gas chromatography coupled with mass spectrometry and isotope ratio mass spectrometry provides compound-specific structural and isotopic information from a single splitless injection, enhancing the amount of information gained from small amounts of precious samples such as carbonaceous chondrites. We have applied this technique to measure the compound-specific C, N, and H isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites. We are using these measurements to evaluate predictions of expected isotopic enrichments from potential formation pathways and environments, leading to a better understanding of the origin of these compounds.
Developing a Fusion Pilot Plant (FPP) design that minimizes risks due to tritium in-process inventory (IPI) is an important concern for the operation of commercial devices. This becomes even more of concern since an FPP will be breeding more tritium than is burned in the reactor for sustainability. The IPI is the tritium moving through the system that is not in the storage and delivery subsystem. Here a process model that solves time-dependent differential equations based on processing times was used to investigate the reduction of the IPI of a potential fuel cycle design. The impact of new and more efficient technologies such as direct internal recycling (DIR), metal foil pumps, continuous pumping, improved isotope separation, and hydrogen separating continuous pumps on IPI was investigated by adjusting subsystem processing times and material flow streams. It was shown that any of the insertions of DIR studied in this paper caused a reduction in the total IPI of the system and proved to be the optimal way to reduce the IPI in the system. Fuel cycle modifications near the torus, such as a coupled DIR and improved pumping systems, produced the largest reductions in tritium inventory.
Increasing robustness of the ITER diagnostic residual gas analyzer (DRGA) is critical for the potential control of plasma heating and fuel-cycle processing. Robustness is a requirement for a diagnostic to have a control function. The DRGA is a multisensor diagnostic system capable of resolving isotopic compositions of hydrogen and helium as well as other heavier elements and compounds. The divertor-specific DRGA system is intended to measure the composition of gases in the ITER subdivertor region and midplane. Its analysis station will be located in a port cell at the divertor level. From there, it will sample a slip stream of gas from the cryogenic pump duct. It will then exhaust into a shared roughing line where helium or other light gas impurities, some potentially from other diagnostic systems, are likely to be present. In order to provide reliable measurements, the DRGA must be robust in areas such as plasma optical emission source geometry for a compact design, mitigation of back-streaming from light gases and resilience to the ITER port cell environment, and radiation hardening of the DRGA electronics. By incorporating robustness into the design, areas of plasma heating and fuel-cycle control may be explored with the DRGA for ITER and next-generation fusion devices.