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Chlorine Isotopes: As a Possible Tracer of Fluid/Bio-Activities on Mars and a Progress Report on Chlorine Isotope Analysis by TIMs

Significantly large mass fractionations between chlorine isotopes (Cl-35, Cl-37) have been reported for terrestrial materials including both geological samples and laboratory materials. Also, the chlorine isotopic composition can be used as a tracer for early solar system processes. Moreover, chlorine is ubiquitous on the Martian surface. Typical chlorine abundances in Gusev soils are approx.0.5 %. The global surface average chlorine abundance also is approx.0.5 %. Striking variations among outcrop rocks at Meridiani were reported with some chlorine abundances as high as approx.2%. Characterizing conditions under which chlorine isotopic fractionation may occur is clearly of interest to planetary science. Thus, we have initiated development of a chlorine isotopic analysis technique using TIMS at NASA-JSC. We present here a progress report on the current status of development at JSC and discuss the possible application of chlorine isotopic analysis to Martian meteorites in a search for fluid- and possibly biological activity on Mars.

Nakamura, N.

FE and MG Isotopic Analyses of Isotopically Unusual Presolar Silicate Grains

Interstellar and circumstellar silicate grains are thought to be Mg-rich and Fe-poor, based on astronomical observations and equilibrium condensation models of silicate dust formation in stellar outflows. On the other hand, presolar silicates isolated from meteorites have surprisingly high Fe contents and few Mg-rich grains are observed. The high Fe contents in meteoritic presolar silicates may indicate they formed by a non-equilibrium condensation process. Alternatively, the Fe in the stardust grains could have been acquired during parent body alteration. The origin of Fe in presolar silicates may be deduced from its isotopic composition. Thus far, Fe isotopic measurements of presolar silicates are limited to the Fe-54/Fe-56 ratios of 14 grains. Only two slight anomalies (albeit solar within error) were observed. However, these measurements suffered from contamination of Fe from the adjacent meteorite matrix, which diluted any isotopic anomalies. We have isolated four presolar silicates having unusual O isotopic compositions by focused ion beam (FIB) milling and obtained their undiluted Mg and Fe isotopic compositions. These compositions help to identify the grains stellar sources and to determine the source of Fe in the grains.

Nguyen, A. N.

Carbon Isotope Measurements of Experimentally-Derived Hydrothermal Mineral-Catalyzed Organic Products by Pyrolysis-Isotope Ratio Mass Spectrometry

We report results of experiments to measure the C isotope composition of mineral catalyzed organic compounds derived from high temperature and high pressure synthesis. These experiments make use of an innovative pyrolysis technique designed to extract and measure C isotopes. To date, our experiments have focused on the pyrolysis and C isotope ratio measurements of low-molecular weight intermediary hydrocarbons (organic acids and alcohols) and serve as a proof of concept for making C and H isotope measurements on more complicated mixtures of solid-phase hydrocarbons and intermediary products produced during high temperature and high pressure synthesis on mineral-catalyzed surfaces. The impetus for this work stems from recently reported observations of methane detected within the Martian atmosphere [1-4], coupled with evidence showing extensive water-rock interaction during Martian history [5-7]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization reactions [8,9]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [10-12]. Further, recent experiments by Fu et al. [13] focus on examining detailed C isotope measurements of hydrocarbons produced by surface-catalyzed mineral reactions. Work described in this paper details the experimental techniques used to measure intermediary organic reaction products (alcohols and organic acids).

Socki, Richard A.

Hydrogen Isotopic Composition of Apatite in Northwest Africa 7034: A Record of the "Intermediate" H-Isotopic Reservoir in the Martian Crust?

Northwest Africa (NWA) 7034 and its pairings comprise a regolith breccia with a basaltic bulk composition [1] that yields a better match than any other martian meteorite to visible-infrared reflectance spectra of the martian surface measured from orbit [2]. The composition of the fine-grained matrix within NWA 7034 bears a striking resemblance to the major element composition estimated for the martian crust, with several exceptions. The NWA 7034 matrix is depleted in Fe, Ti, and Cr and enriched in Al, Na, and P [3]. The differences in Al and Fe are the most substantial, but the Fe content of NWA 7034 matrix falls within the range reported for the southern highlands crust [6]. It was previously suggested by [4] that NWA 7034 was sourced from the southern highlands based on the ancient 4.4 Ga ages recorded in NWA 7034/7533 zircons [4, 5]. In addition, the NWA 7034 matrix material is enriched in incompatible trace elements by a factor of 1.2-1.5 [7] relative to estimates of the bulk martian crust. The La/Yb ratio of the bulk martian crust is estimated to be approximately 3 [7], and the La/Yb of the NWA 7034 matrix materials ranges from approximately 3.9 to 4.4 [3, 8], indicating a higher degree of LREE enrichment in the NWA 7034 matrix materials. This elevated La/Yb ratio and enrichment in incompatible lithophile trace elements is consistent with NWA 7034 representing a more geochemically enriched crustal terrain than is represented by the bulk martian crust, which would be expected if NWA 7034 represents the bulk crust from the southern highlands. Given the similarities between NWA 7034 and the martian crust, NWA 7034 may represent an important sample for constraining the composition of the martian crust, particularly the ancient highlands. In the present study, we seek to constrain the H isotopic composition of the martian crust using Cl-rich apatite in NWA 7034. Usui et al., [9] recently proposed that a H isotopic reservoir exists within the martian crust that has a H-isotopic composition that is intermediate (δD of 1000-2000per mille) between an isotopically light mantle (Delta D is less than 275per mille [10]) and an isotopically heavy atmosphere (δD of 2500-6100per mille [11, 12]). Apatites in NWA 7034 occur in a number of lithologic domains, however apatites across all lithologic domains have been affected by a Pb-loss event at about 1.5 Ga before present [5], so they are unlikely to have retained a primary composition and are more likely to have equilibrated with fluids within the martian crust that may or may not have exchanged with the martian atmosphere. Equilibration of apatite with crustal fluids is further supported by the chlorine-rich compositions exhibited by apatites in NWA 7034 in comparison to apatites from other martian meteorites (Figure 1; [13]). Cl is more hydrophilic than F, which promotes formation of Cl-rich apatite compositions in fluid-rich systems [e.g., 14, 15-17].

McCubbin, F. M.

Utilizing Stable Isotopes and Isotopic Anomalies to Study Early Solar System Formation Processes

Chondritic meteorites contain a diversity of particle components, i.e., chondrules and calcium-, aluminum-rich refractory inclusions (CAIs), that have survived since the formation of the Solar System. The chemical and isotopic compositions of these materials provide a record of the conditions present in the protoplanetary disk where they formed and can aid our understanding of the processes and reservoirs in which solids formed in the solar nebula, an important step leading to the accretion of planetesimals. Isotopic anomalies associated with nucleosynthetic processes are observed in these discrete materials, and can be compared to astronomical observations and astrophysical formation models of stars and more recently proplyds. The existence and size of these isotopic anomalies are typically thought to reflect a significant state of isotopic heterogeneity in the earliest Solar System, likely left over from molecular cloud heterogeneities on the grain scale, but some could also be due to late stellar injection. The homogenization of these isotopic anomalies towards planetary values can be used to track the efficiency and timescales of disk wide mixing,

Simon, Justin

Nitrogen isotopes in drive tube 79002/79001 - Regolith history and nitrogen isotopic evolution in the solar wind

Variations in abundance and isotopic composition of nitrogen in 79002/79001 drive tube samples result from mixing of two soil components: one mature, N-rich, and isotopically light, resembling breccia material in the core, and the other immature, N-poor, and isotopically heavy. That these materials are common to soil at each stratigraphic level in the core suggests widespread distribution in the local regolith. Preservation of mixing correlations involving nitrogen isotopic compositions and cosmogenic N-15 concentrations suggests relatively recent mixing, perhaps in association with emplacement of the core stratigraphy. Characteristics of nitrogen release from the endmember materials, relationships between their nitrogen contents and maturity, and contrasts in their cosmogenic N-15 contents are consistent with models involving secular increase of the N-15/N-14 ratio of the solar wind.

Stone, J.

Acceleration of uranium beam to record power of 10.4 kW and observation of new isotopes at Facility for Rare Isotope Beams

The Facility for Rare Isotope Beams (FRIB) is a major nuclear physics facility for research with fast, stopped, and reaccelerated beams that was successfully commissioned in May 2022. A key capability of FRIB is the production of an acceleration of the uranium beam, but this capability requires the facility to work at the design limits of the lowest charge-to-mass ratio and the highest power density on the beam intercepting devices. This paper presents techniques for overcoming the significant challenges in accelerating the uranium beam, culminating in the demonstration of 10.4 kW on target, and the discovery of three new isotopes. The high-power uranium beam enabled us to produce and identify G 88 a , A 93 s , and S 96 e , within the first 24 h of operation. The successful uranium operation at FRIB sets a new record for accelerated uranium beam power above 10 kW and opens a new avenue of research with rare isotopes. Published by the American Physical Society 2024

43 PARTICLE ACCELERATORS

A non-mass-dependent oxygen isotope effect in the production of ozone from molecular oxygen - The role of molecular symmetry in isotope chemistry

It was previously reported that the reaction products from the synthesis of ozone in an electric discharge through molecular oxygen display a nonmass-dependent (NoMaDic) oxygen isotope effect. In this paper, a detailed characterization of the isotope effect, including the effect of molecular oxygen pressure, and the presence of a chemically inert third body (helium), is reported. The NoMaDic effect is due to an isotopically selective stabilization of the O3 formation reaction intermediate, possibly resulting from the ability of the different isotopomers to exhibit different molecular symmetries.

Heidenreich, J. E., III

Nitrogen isotopic analyses by isotope-ratio-monitoring gas chromatography/mass spectrometry

Amino acids containing natural-abundance levels of 15N were derivatized and analyzed isotopically using a technique in which individual compounds are separated by gas chromatography, combusted on-line, and the product stream sent directly to an isotope-ratio mass spectrometer. For samples of N2 gas, standard deviations of ratio measurement were better than 0.1% (Units for delta are parts per thousand or per million (%).) for samples larger than 400 pmol and better than 0.5% for samples larger than 25 pmol (0.1% 15N is equivalent to 0.00004 atom % 15N). Results duplicated those of conventional, batchwise analyses to within 0.05%. For combustion of organic compounds yielding CO2/N2 ratios between 14 and 28, in particular for N-acetyl n-propyl derivatives of amino acids, delta values were within 0.25% of results obtained using conventional techniques and standard deviations were better than 0.35%. Pooled data for measurements of all amino acids produced an accuracy and precision of 0.04 and 0.23%, respectively, when 2 nmol of each amino acid was injected on column and 20% of the stream of combustion products was delivered to the mass spectrometer.

Non-NASA Center

Isotopically pure magnesium isotope-24 is prepared from magnesium-24 oxide

Apparatus is used to prepare isotopically pure magnesium isotope-24, suitable for use in neutron scattering and polarization experiments. The apparatus permits thermal reduction of magnesium-24 oxide with aluminum and calcium oxide, and subsequent vaporization of the product metal in vacuum. It uses a resistance-heated furnace tube and cap assembly.

Chellew, N. R.

Isotopic stack - measurement of heavy cosmic ray isotopes

Heavy cosmic ray nuclei with nuclear charge, Z, equal to or greater than 3 are to be measured using an isotopic stack consisting of passive visual track detectors which remain sensitive throughout the entire mission. The scientific data are stored in latent tracks which are produced by heavy ions and which can be revealed in the investigator's laboratory after recovery. During the mission, only housekeeping data have to be collected. The exposure onboard Spacelab 1 allows the study of the chemical composition and energy spectrum of articles which have energies in the range 20 to 100 million electron volts per atomic mass unit, as well as the isotopic composition of heavy galactic cosmic rays with energies in the range 100 to 1000 million electron volts per atomic mass unit.

Beaujean, R.

Isotopic equilibration between dissolved and suspended particulate lead in the Atlantic Ocean - Evidence from Pb-210 and stable Pb isotopes

Vertical profiles of, on one hand, the stable Pb isotopic composition, and on the other, the ratio of total Pb to Pb-210 in suspended particles, are noted to closely track contemporaneous depth variations in these ratios for dissolved Pb throughout the upper 2 km of the Sargasso Sea near Bermuda. A simple flux model suggests that the effect of deep ocean scavenging processes on the flux and isotopic composition of Pb sinking on large particles was minor throughout the preanthropogenic, and most of the anthropogenic era: but it has become more important as surface inputs decrease to preleaded gasoline levels, perhaps exceeding the contribution of surface-derived Pb flux in the next decade.

Sherrell, Robert M.

High purity isotopically enriched Ge-70 and Ge-74 single crystals - Isotope separation, growth, and properties

Ge-70 and Ge-74 isotopes were successfully separated from natural Ge, and were zone purified. Several highly enriched, high purity Ge-70 and Ge-74 single crystals were grown by the vertical Bridgman method. The growth system was designed for reliable growth of low dislocation density, high purity Ge single crystals of about 4 g weight. A Ge-70 and a Ge-74 crystal were selected for complete characterization. In spite of the large surface-to-volume ratio of these ingots, both Ge-70 and Ge-74 crystals contain low electrically active chemical net-impurity concentrations of about 2 x 10 exp 12/cu cm, which is 2 orders of magnitude better than that of Ge-74 crystals previously grown by two different groups. Isotopic enrichment of the Ge-70 and the Ge-74 crystals is 96.3 percent and 96.8 percent, respectively. The residual donors and acceptors present in both crystals were identified as phosphorus and copper, respectively. In addition, less than 10 exp 11/cu cm Ga, Al, and In were found in the Ge-70 crystal.

Itoh, Kohei

Carbon isotopic analysis of atmospheric methane by isotope-ratio-monitoring gas chromatography-mass spectrometry

Less than 15 min are required for the determination of delta C(sub PDB)-13 with a precision of 0.2 ppt(1 sigma, single measurement) in 5-mL samples of air containing CH4 at natural levels (1.7 ppm). An analytical system including a sample-introduction unit incorporating a preparative gas chromatograph (GC) column for separation of CH4 from N2, O2, and Ar is described. The 15-min procedure includes time for operation of that system, high-resolution chromatographic separation of the CH4, on-line combustion and purification of the products, and isotopic calibration. Analyses of standards demonstrate that systematic errors are absent and that there is no dependence of observed values of delta on sample size. For samples containing 100 ppm or more CH4, preconcentration is not required and the analysis time is less than 5 min. The system utilizes a commercially available, high-sensitivity isotope-ratio mass spectrometer. For optimal conditions of smaple handling and combustion, performance of the system is within a factor of 2 of the shot-noise limit. The potential exists therefore for analysis of samples as small as 15 pmol CH4 with a standard deviation of less than 1 ppt.

Merritt, Dawn A.

Oxygen Isotopes in AMMS and IDPS: Universality of Oxygen Isotope Systematics Of Crystalline Silicates in Comets

It has been suggested that the major source of crystalline silicates in comets is CR chondrule-like materials along with minor sources including O, R, CH-CB chondrite chondrule-like materials based on the comparisons of oxygen isotope systematics between cometary silicates and chondrules from various types of primitive chondrites [1-3]. However, cometary silicates used for these studies are from only two comets: Wild2 and a parent comet of U2-20GCA. It is uncertain that the oxygen isotope systematics represent that of crystalline silicates in all comets.

D Nakashima

Isotope-ratio-monitoring gas chromatography-mass spectrometry: methods for isotopic calibration

In trial analyses of a series of n-alkanes, precise determinations of 13C contents were based on isotopic standards introduced by five different techniques and results were compared. Specifically, organic-compound standards were coinjected with the analytes and carried through chromatography and combustion with them; or CO2 was supplied from a conventional inlet and mixed with the analyte in the ion source, or CO2 was supplied from an auxiliary mixing volume and transmitted to the source without interruption of the analyte stream. Additionally, two techniques were investigated in which the analyte stream was diverted and CO2 standards were placed on a near-zero background. All methods provided accurate results. Where applicable, methods not involving interruption of the analyte stream provided the highest performance (sigma = 0.00006 at.% 13C or 0.06% for 250 pmol C as CO2 reaching the ion source), but great care was required. Techniques involving diversion of the analyte stream were immune to interference from coeluting sample components and still provided high precision (0.0001 < or = sigma < or = 0.0002 at.% or 0.1 < or = sigma < or = 0.2%).

NASA Discipline Exobiology