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Constraints on triple oxygen isotope kinetics

The general assumption that systems are in equilibrium is convenient, but imperfect. Instead, the partial or full expression of kinetic reaction steps may need to be determined. Using an isotope fractionation Monte-Carlo model under the harmonic approximation (Figure 1 envelopes), we find the range of kinetic isotope effects (i.e., resulting from unidirectional chemical reactions) contains and exceeds the range of accessible equilibrium isotope effects. For the 16O-17O-18O system, accessible kinetic isotope effects can yield Δ′17O variations as large 0.8‰ from a single kinetic fractionation step. Reactions that yield the largest deviations from equilibrium are those with the largest molecular mass difference between decomposition fragments, typically the two products, such as a gas and solid generated from the thermal decomposition of an initial solid. For example, previously published experiments on the thermal decomposition of calcite (CaCO3) and dehydroxylation of brucite (Mg(OH)2) are matched by density functional theory models of each kinetic isotope effect, thus revealing their origin in mass-dependent reaction. Beyond oxygen, our approach applies to any system with more than two isotopes.

Oxygen isotopes↗

Isotopic Enrichment of Boron in the Sputtering of Boron Nitride with Xenon Ions

An experimental study is described to measure the isotopic enrichment of boron. Xenon ions from 100 eV to 1.5 keV were used to sputter a boron nitride target. An ion gun was used to generate the ion beam. The ion current density at the target surface was approximately 30 microA/sq cm. Xenon ions impinged on the target surface at 50 deg angle to the surface normal. Since boron nitride is an insulator, a flood electron gun was used in our experiments to neutralize the positive charge buildup on the target surface. The sputtered secondary ions of boron were detected by a quadrupole mass spectrometer. The spectrometer entrance aperture was located perpendicular to the ion beam direction and 10 mm away from the target surface. The secondary ion flux was observed to be enriched in the heavy isotopes at lower ion energies. The proportion of heavy isotopes in the sputtered secondary ion flux was found to decrease with increasing primary ion energy from 100 to 350 eV. Beyond 350 eV, light isotopes were sputtered preferentially. The light isotope enrichment factor was observed to reach an asymptotic value of 1.27 at 1.5 keV. This trend is similar to that of the isotopic enrichment observed earlier when copper was sputtered with xenon ions in the same energy range.

Ray, P. K.↗

Low-Energy Sputtering Studies of Boron Nitride with Xenon Ions

Sputtering of boron nitride with xenon ions was investigated using secondary ion (SIMS) and secondary neutral (SNMS) mass spectrometry. The ions generated from the ion gun were incident on the target at an angle of 50' with respect to the surface'normal. The energy of ions ranged from 100 eV to 3 keV. A flood electron gun was used to neutralize the positive charge build-up on the target surface. The intensities of sputtered neutral and charged particles, including single atoms, molecules, and clusters, were measured as a function of ion energy. Positive SIMS spectra were dominated by the two boron isotopes whereas BN- and B- were the two major constituents of the negative SIMS spectra. Nitrogen could be detected only in the SNMS spectra. The intensity-energy curves of the sputtered particles were similar in shape. The knees in P-SIMS and SNMS intensity-energy curves appear at around I keV which is significantly higher that 100 to 200 eV energy range at which knees appear in the sputtering of medium and heavy elements by ions of argon and xenon. This difference in the position of the sputter yield knee between boron nitride and heavier targets is due to the reduced ion energy differences. The isotopic composition of secondary ions of boron were measured by bombarding boron nitride with xenon ions at energies ranging from 100 eV to 1.5 keV using a quadrupole mass spectrometer. An ion gun was used to generate the ion beam. A flood electron gun was used to neutralize the positive charge buildup on the target surface. The secondary ion flux was found to be enriched in heavy isotopes at lower incident ion energies. The heavy isotope enrichment was observed to decrease with increasing primary ion energy. Beyond 350 eV, light isotopes were sputtered preferentially with the enrichment increasing to an asymptotic value of 1.27 at 1.5 keV. The trend is similar to that of the isotopic enrichment observed earlier when copper was sputtered with xenon ions in the same energy range.

Ray, P. K.↗

Lead isotopic studies of lunar soils - Their bearing on the time scale of agglutinate formation

Fines (smaller than 75 microns) and bulk soil were studied to analyze loss of volatile lead; losses of the order of 10% to 30% radiogenic lead during the production of agglutinates are assessed. Lead isotope data from fine-agglutinate pairs are analyzed for information on the time scale of micrometeorite bombardment, from the chords generated by the data in concordia diagrams. Resulting mean lead loss ages were compared to spallogenic gas exposure ages for all samples. Labile parentless radiogenic Pb residing preferentially on or in the fines is viewed as possibly responsible for aberrant lead loss ages. Bulk soils plot above the concordia curve (in a field of excess radiogenic Pb) for all samples with anomalous ages.

Church, S. E.↗

Power System for Venus Surface Exploration

A radioisotope power and cooling system is designed to provide electrical power for a probe operating on the surface of Venus. Most foreseeable electronics devices and sensors cannot operate at the 450 C ambient surface temperature of Venus. Because the mission duration is substantially long and the use of thermal mass to maintain an operable temperature range is likely impractical, some type of active refrigeration may be required to keep electronic components at a temperature below ambient. The fundamental cooling parameters are the cold sink temperature, the hot sink temperature, and the amount of heat to be removed. In this instance, it is anticipated that electronics would have a nominal operating temperature of 300 C. Due to the highly thermal convective nature of the high-density (90 bar CO2) atmosphere, the hot sink temperature was assumed to be 50 C, which provided a 500 C temperature of the cooler's heat rejecter to the ambient atmosphere. The majority of the heat load on the cooler is from the high temperature ambient surface environment on Venus, with a small contribution of heat generation from electronics and sensors. Both thermoelectric (RTG) and dynamic power conversion systems were analyzed, based on use of a standard isotope (General-purpose heat source, or GPHS) brick. For the radioisotope Stirling power converter configuration designed, the Sage model predicts a thermodynamic power output capacity of 478.1 watts, which slightly exceeds the required 469.1 watts. The hot sink temperature is 1200 C, and the cold sink temperature is 500 C. The required heat input is 1740 watts. This gives a thermodynamic efficiency of 27.48 %. It is estimated that the mechanical efficiency of the power converter design is on the order of 85 %, based on experimental measurements taken from 500-watt power class, laboratory-tested Stirling engines. The overall efficiency is calculated to be 23.36 %. The mass of the power converter is estimated at approximately 21.6 kg. Additional information is included in the original extended abstract.

Landis, Geoffrey A.↗

Exploring the Atmosphere of Uranus with Small Next-generation Atmospheric Probe (SNAP)

In-situ atmospheric exploration of giant planets is a top priority of the planetary science community and NASA. The Galileo Probe a Jupiter made the first and only in-situ composition measurements of the atmosphere. Most importantly, the noble gas and isotopic ratio can be made only through in-situ measurements, and the Galileo Probe measurements must be followed up by similar measurements at Saturn, Uranus, and Neptune. In addition, abundances of condensable cloud-forming species are also needed to measure the vertical distribution of those molecules to provide ground-truths measurements for remote-sensing measurements. My talk will focus on the Small Next-generation Atmospheric Probe (SNAP) design developed in partnership by Hampton University and NASA Langley Research Center to enable delivery of multiple probes. Using SNAP as a reference design, I will also discuss key instrument trades and the state of the art in the atmospheric composition instruments.

Kunio Sayanagi↗

Volume Measurements of Laser-generated Pits for in Situ Geochronology Using KArLE (Potassium-Argon Laser Experiment)

KArLE (Potassium-­‐Argon Laser Experiment) has been developed for in situ planetary geochronology using the K - Ar (potassium-­‐argon) isotope system, where material ablated by LIBS (Laser-­‐Induced Breakdown Spectroscopy) is used to calculate isotope abundances. We are determining the accuracy and precision of volume measurements of these pits using stereo and laser microscope data to better understand the ablation process for isotope abundance calculations. If a characteristic volume can be determined with sufficient accuracy and precision for specific rock types, KArLE will prove to be a useful instrument for future planetary rover missions.

French, R. A.↗

CEM2k and LAQGSM Codes as Event-Generators for Space Radiation Shield and Cosmic Rays Propagation Applications

Space radiation shield applications and studies of cosmic ray propagation in the Galaxy require reliable cross sections to calculate spectra of secondary particles and yields of the isotopes produced in nuclear reactions induced both by particles and nuclei at energies from threshold to hundreds of GeV per nucleon. Since the data often exist in a very limited energy range or sometimes not at all, the only way to obtain an estimate of the production cross sections is to use theoretical models and codes. Recently, we have developed improved versions of the Cascade-Exciton Model (CEM) of nuclear reactions: the codes CEM97 and CEM2k for description of particle-nucleus reactions at energies up to about 5 GeV. In addition, we have developed a LANL version of the Quark-Gluon String Model (LAQGSM) to describe reactions induced both by particles and nuclei at energies up to hundreds of GeVhucleon. We have tested and benchmarked the CEM and LAQGSM codes against a large variety of experimental data and have compared their results with predictions by other currently available models and codes. Our benchmarks show that CEM and LAQGSM codes have predictive powers no worse than other currently used codes and describe many reactions better than other codes; therefore both our codes can be used as reliable event-generators for space radiation shield and cosmic ray propagation applications. The CEM2k code is being incorporated into the transport code MCNPX (and several other transport codes), and we plan to incorporate LAQGSM into MCNPX in the near future. Here, we present the current status of the CEM2k and LAQGSM codes, and show results and applications to studies of cosmic ray propagation in the Galaxy.

Mashnik, S. G.↗

Simulation of Helium-3 Extraction from Lunar Ilmenite

Knowledge of the trapping mechanisms and diffusion characteristics of solar-wind implanted isotopes in the minerals of the lunar regolith will enable the optimization of the processes to extract solar wind gases from regolith particles. Extraction parameters include the temperature and duration of extraction, particle size, and gas yield. Diffusion data will increase the efficiency and profitability of future mining ventures. This data will also assist in optimizing the evaluations of various potential mining sites based on remote sensing data. For instance, if magnesian ilmenite (Mg,Fel.,Ti03) is found to retain He better than stoichiometric ilmenite (FeTi03), remote sensing data for Mg could be considered in addition to Ti and maturity data. The context of the currently discussed work is the mining of helium-3 for potential use as a fuel for fusion energy generation. However, the potential resources deposited by the solar wind include hydrogen (and derived water), helium-4, nitrogen and carbon. Implantation experiments such as those performed for helium isotopes in ilmenite are important for the optimized extraction of these additional resources. These experiments can easily be reproduced for most elements or isotopes of interest.

Kuhlman, K. R.↗

Design of multihundredwatt DIPS for robotic space missions

Design of a dynamic isotope power system (DIPS) general purpose heat source (GPHS) and small free piston Stirling engine (FPSE) is being pursued as a potential lower cost alternative to radioisotope thermoelectric generators (RTG's). The design is targeted at the power needs of future unmanned deep space and planetary surface exploration missions ranging from scientific probes to SEI precursor missions. These are multihundredwatt missions. The incentive for any dynamic system is that it can save fuel which reduces cost and radiological hazard. However, unlike a conventional DIPS based on turbomachinery converions, the small Stirling DIPS can be advantageously scaled to multihundred watt unit size while preserving size and weight competitiveness with RTG's. Stirling conversion extends the range where dynamic systems are competitive to hundreds of watts (a power range not previously considered for dynamic systems). The challenge of course is to demonstrate reliability similar to RTG experience. Since the competative potential of FPSE as an isotope converter was first identified, work has focused on the feasibility of directly integrating GPHS with the Stirling heater head. Extensive thermal modeling of various radiatively coupled heat source/heater head geometries were performed using data furnished by the developers of FPSE and GPHS. The analysis indicates that, for the 1050 K heater head configurations considered, GPHS fuel clad temperatures remain within safe operating limits under all conditions including shutdown of one engine. Based on these results, preliminary characterizations of multihundred watt units were established.

Bents, D. J.↗

SEI power source alternatives for rovers and other multi-kWe distributed surface applications

To support the Space Exploration Initiative (SEI), a study was performed to investigate power system alternatives for the rover vehicles and servicers that were subsequently generated for each of these rovers and servicers, candidate power sources incorporating various power generation and energy storage technologies were identified. The technologies were those believed most appropriate to the SEI missions, and included solar, electrochemical, and isotope systems. The candidates were characterized with respect to system mass, deployed area, and volume. For each of the missions a preliminary selection was made. Results of this study depict the available power sources in light of mission requirements as they are currently defined.

Bents, David J.↗

SEI power source alternatives for rovers and other multi-kWe distributed surface applications

Results of the study performed to support the Space Exploration Initiative (SEI) which investigated power system alternatives for the rover vehicles and servicers that would be used for construction and operation of a lunar base is described. Using the mission requirements and power profiles that were subsequently generated for each of these rovers and servicers, candidate power sources incorporating various power generation and energy storage technologies were identified. The technologies were those believed most appropriate to the SEI missions, and included solar, electrochemical, and isotope systems. The candidates were characterized with respect to system mass, deployed area and volume. For each of the missions a preliminary selection was made. Results of this study depict the available power sources in light of the mission requirements as they are currently defined.

Bents, D. J.↗

The Generation of Lighting in the Solar Nebula

The process that melted and formed the chondrules, mm-sized glassy beads within meteorites, has not been conclusively identified. Origin by lightning in the solar nebula is consistent with many features of chondrules, but no viable model of lightning has yet been advanced. We present a model demonstrating how lightning could be generated in the solar nebula which differs from previous models in three important aspects. First, we identify a new', powerful charging mechanism that is based on the differences in contact potentials between particles of different composition, a form of triboelectric charging. In the presence of fine silicate grains and fine iron metal grains, large silicate particles (the chondrules) can acquire charges of +10(exp 5) e. Second, we assume that the chondrule precursor particles are selectively concentrated in clumps 1 - 100 km in size by the turbulent concentration mechanism described by Cuzzi et al. (1996). The concentration of these highly charged particles into clumps, in a background of negatively charged metal grains, is what generates the strong electric fields. Third, we make refinements in the estimates of the breakdown electric field and the ionization rate. We calculate that electric fields large enough to trigger breakdown easily could have existed over regions large enough (approx. 100km) to generate very large discharges of electrical energy (approx. 10(exp 16)erg). The discharges would have been sufficiently energetic and frequent to have formed the chondrules. We place constraints on the generation of lightning and conclude that it could not be generated if the abundance of Al-26 in chondrules was as high as the level in the CAls. This conclusion is consistent with isotopic analyses of chondrules. This possibly implies that Al-26 was non-uniformly distributed in the solar nebula or that the chondrules formed several Myr after the CAIs.

Cuzzi, Jeffrey↗

Molten Salt Lattice Confinement Fusion (LCF) Fast Fission Reactor for Lunar and Planetary Surface Power

Molten salt fission reactors (MSR) have been suggested for lunar and planetary surface power systems. They have the advantage of operating at high temperature, for efficient thermal-electrical conversion, low pressure, long-lived with high nuclear fuel burnup. MSR are often designed to breed fissile 233U from natural 232Th by neutron capture and  decay via: 232Th(n,)233Th(,)233Pa(,)233U Unfortunately, this process requires 233Pa isotope separation and segregation to decay to 233U. This requirement prevents additional neutron capture that interferes with 233U breeding. Instead, Wooley’s sub-critical, fast fission, molten salt reactor would use externally generated tokamak fusion neutrons1,2 to fission all actinides.We propose a simpler fusion-fast-fission sub-critical reactor that generates fast neutrons in situ from lattice confinement fusion (LCF) to fission fertile and fissile actinides. This hybrid reactor doesn't require enriched 235U fissile pins to initiate fis-sion reactions, nor 233Pa separation and segregation during operation. Like Wooley’s, this hybrid reactor “burns” natural uranium (238U) or thorium (232Th) which avoids uranium enrichment and additional fissile material launch safety and security costs. The LCF neutron source is initiated by bremsstrahlung photoneutrons (Fig. 1)3 or isotopic neutron sources in electron-screened lattices (Fig. 2)4,5. Alternatively, the electrolytic Pd-deuterium co-deposition6protocol fast fissions7 both 232Th and 238U. However, an aqueous electrolyte-based system, without pressurization similar to conventional pressurized water fission reactors, is incapable of high temperatures due to the boiling point of the electrolyte slightly over 100 C. Molten salts can be used instead as was demonstrated at the University of Hawaii8 using a variety of Ni and Pd cathodes in lithiated, hydrided and deuterated salts. These salts have melting points often exceeding 500C making them suitable to efficiently produce electrical power9 through either Advanced Stirling Genera-tors (< 100 kWe) or closed-Brayton Cycle (> 100 kWe). This hybrid reactor could power a wide range of lunar or Martian applications from unmanned in-struments, to charging vehicles and entire facilities such as human habitats or in situ resource utilization. The power conversion cycles are Carnot Cycle limited, but generally 30% efficient at best. However, waste heat on the moon or Mars is important to surviving either two-week lunar nights or Martian nights as well as providing process heat for mineral extraction and “living off the land”

Lawrence Forsley↗

Magnesian anorthosites from the western highlands of the Moon: Isotope geochemistry and petrogenesis

Breccias from the Apollo 14 landing site have provided a wealth of information on the genesis of the lunar highlands. Various pristine rock-types have been discovered in relative abundance including rare ferroan anorthosites and alkali-suite and magnesian-suite rocks. Mineral-chemical and radiogenic isotopic data are reported here for a newly discovered Mg-suite anorthosite from Apollo 14, sample 14303,347. Meyer et al. reported U-Pb zircon analyses of Mg-suite highlands rocks from the western limb of the Moon. We have compiled these ages and generated a weighted average age of 4211 = 6 Ma; some 200 Ma younger than ferroan anorthosites. Utilizing this age for Mg-anorthosite 14303,347, our data results in an initial epsilon(sub Nd) value of -1.0 and initial Sr-87/Sr-86 of 0.69915. Based on trace-element, isotopic, and mineral-chemical data, the western highlands Mg-suite is interpreted to be crustal precipitates of a picritic magma, which assimilated KREEPy trapped liquid from upper-mantle cumulates during its transport to the crust.

Snyder, Gregory A.↗

Constraints on Triple Oxygen Isotope Kinetics

Triple oxygen isotope methods (e.g., using δ 18 O, and Δ′ 17 O) have been used to classify meteorites, to constrain atmospheric chemistry, and to estimate primary productivity, among other uses. Such utility relies on the mass dependency of most chemical reactions: δ 17 O is proportional to δ 18 O by roughly a factor of 0.5. However, in detail, mass-dependency factors vary. While constraints on mass dependency are well established for equilibrium isotope effects, similar constraints for kinetic isotope effects are lacking. Using an ab initio Monte Carlo approach (see envelopes in Figure 1), we find the range of kinetic isotope effects (i.e., resulting from unidirectional chemical reactions) contains and exceeds the range of accessible equilibrium isotope effects for the 16 O 17 O 18 O system (Hayles and Killingsworth, 2022). Accessible kinetic isotope effects can yield Δ′ 17 O variations as large 0.8 ‰ from a single kinetic fractionation step. Reactions that yield the largest deviations from equilibrium are those with the largest molecular mass difference between decomposition fragments, typically the two products such as a gas and solid generated from the thermal decomposition of an initial solid. Comparison of DFT transition state model results against previously published experiments on the thermal decomposition of calcite (CaCO 3 ) (Miller et al., 2002) and dehydroxylation of brucite (Mg(OH) 2 ) (Clayton and Mayeda, 2009) show they are matched with mass-dependent kinetic isotope effects. This approach can be applied to any system with more than two isotopes.

Oxygen isotopes↗

Chemical composition of HAL, an isotopically-unusual Allende inclusion

Samples of hibonite, black rim, and portions of friable rim from an unusual Allende inclusion, named HAL, were analyzed by INAA and RNAA for 37 major, minor, and trace elements. An unusually low amount of Ce was found in HAL, although it otherwise was highly enriched in REE compared to C1 chondrites. HAL is also depleted in Sr, Ba, U, V, Ru, Os, and Ir relative to other refractory elements. It is concluded that the distribution of REE between hibonite and rims was established when hibonite and other refractory minerals were removed at slightly different temperatures from a hot, oxidizing gas in which they previously coexisted as separate grains. Possible locations for the chemical and mass dependent isotopic fractionation are considered to be in ejecta from the low temperature helium-burning zone of a supernova and in the locally oxidizing environment generated by evaporation of interstellar grains of near-chondritic chemical composition.

Davis, A. M.↗