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NASA NTRS2019

Multiple Reservoirs of Volatiles in the Moon Revealed by the Isotopic Composition of Chlorine in Lunar Basalts

The isotopes of chlorine (37Cl and 35Cl) are highly fractionated in lunar samples compared to most other Solar System materials. Recently, the chlorine isotope signatures of lunar rocks have been attributed to large-scale degassing processes that occurred during the existence of a magma ocean. In this study we investigated how well a suite of lunar basalts, most of which have not previously been analyzed, conform to previous models. The Cl isotope compositions (δ37Cl (‰) = [(37Cl/35Clsample/37Cl/35ClSMOC) − 1] × 1000, where SMOC refers to standard mean ocean chloride) recorded range from ∼+7 to +14‰ (Apollo 15), +10 to +19‰ (Apollo 12), +9 to +15‰ (70017), +4 to +8‰ (MIL 05035), and +15 to +22‰ (Kalahari 009). The Cl isotopic data from the present study support the mixing trends previously reported by Boyce et al. (2015) and Barnes et al. (2016), as the Cl isotopic composition of apatites are positively correlated with bulk-rock incompatible trace element abundances in the low-Ti basalts, inclusive of low-Ti and KREEP basalts. This trend has been interpreted as evidence that incompatible trace elements, including Cl, were concentrated in the urKREEP residual liquid of the lunar magma ocean, rather than the mantle cumulates, and that urKREEP Cl had a highly fractionated isotopic composition. The source regions for the basalts were thus created by variable mixing between the mantle (Cl-poor and relatively unfractionated) and urKREEP. The high-Ti basalts show much more variability in measured Cl isotope ratios and scatter around the trend formed by the low-Ti basalts. Most of the data for lunar meteorites also fits the mixing of volatiles in their sources, but Kalahari 009, which is highly depleted in incompatible trace elements, contains apatites with heavily fractionated Cl isotopic compositions. Given that Kalahari 009 is one of the oldest lunar basalts and ought to have been derived from very early-formed mantle cumulates, a heavy Cl isotopic signature is likely not related to its mantle source, but more likely to magmatic or secondary alteration processes, perhaps via impact-driven vapor metasomatism of the lunar crust.

Mccubbin, Francis M.↗

NASA NTRS2020

The Chlorine-Isotopic Composition of Lunar KREEP From Magnesian-Suite Troctolite 76535

We conducted in-situ Cl isotopic measurements of apatite within intercumulus regions and within a holocrystalline olivine-hosted melt inclusion in magnesian-suite troctolite 76535 from Apollo 17. These data were collected to place constraints on the Cl-isotopic composition of the last liquid to crystallize from the lunar magma ocean (i.e., urKREEP, named after its enrichments in incompatible lithophile trace elements like potassium, rare earth elements, and phosphorus). The apatite in the olivine-hosted melt inclusion and within the intercumulus regions of the sample yielded Cl-isotopic compositions of 28.3 ± 0.9 ‰ (2σ) and 30.3 ± 1.1 ‰ (2σ), respectively. The concordance of these values from both textural regimes we analyzed indicates that the Cl-isotopic composition of apatites in 76535 likely represents the Cl-isotopic composition of the KREEP-rich magnesian-suite magmas. Based on the age of 76535, these results imply that the KREEP reservoir attained a Cl-isotopic composition of 28–30 ‰ by at least 4.31 Ga, consistent with the onset of Cl-isotopic fractionation at the time of lunar magma ocean crystallization or shortly thereafter. Moreover, lunar samples that yield Cl-isotopic compositions higher than the value for KREEP are likely affected by secondary processes such as impacts and/or magmatic degassing. The presence of KREEP-rich olivine-hosted melt inclusions within one of the most pristine and ancient KREEP-rich rocks from the Moon provides a new opportunity to characterize the geochemistry of KREEP. In particular, a broader analysis of stable isotopic compositions of highly and moderately volatile elements could provide an unprecedented advancement in our characterization of the geochemical composition of the KREEP reservoir and of volatile-depletion processes during magma ocean crystallization, more broadly.

Francis M. McCubbin↗

NASA NTRS1985

Millimeter-scale variations of stable isotope abundances in carbonates from banded iron-formations in the Hamersley Group of Western Australia

Several diamond drill cores from formations within the Hamersley Group of Western Australia have been studied for evidence of short-range variations in the isotopic compositions of the carbonates. For a set of 32 adjacent microbands analyzed in a specimen from the Marra Mamba Iron Formation, carbon isotope compositions of individual microbands ranged from -2.8 to -19.8 per mil compared to PDB and oxygen isotope compositions ranged from 10.2 to 20.8 per mil compared to SMOW. A pattern of alternating abundances was present, with the average isotopic contrasts between adjacent microbands being 3.0 per mil for carbon and 3.1 per mil for oxygen. Similar results were obtained for a suite of 34 microbands (in four groups) from the Bruno's Band unit of the Mount Sylvia Formation. Difficulties were experienced in preparing samples of single microbands from the Dales Gorge Member of the Brockman Iron Formation, but overall isotopic compositions were in good agreement with values reported by previous authors. Chemical analyses showed that isotopically light carbon and oxygen were correlated with increased concentrations of iron. The preservation of these millimeter-scale variations in isotopic abundances is interpreted as inconsistent with a metamorphic origin for the isotopically light carbon in the BIF carbonates. A biological origin is favored for the correlated variations in 13C and Fe, and it is suggested that the 13C-depleted carbonates may derive either from fermentative metabolism or from anaerobic respiration. A model is presented in which these processes occur near the sediment-water interface and are coupled with an initial oxidative precipitation of the iron.

NASA Program Exobiology↗

NASA NTRSDate not supplied

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↗

DOE OSTI2025

Plutonium isotope ratio measurements by total evaporation-thermal ionization mass spectrometry (TE-TIMS): an evaluation of uncertainties using traceable standards from the New Brunswick Laboratory

The accuracy and precision of isotope amount ratio measurements using thermal ionization mass spectrometry (TIMS) instrumentation are described, and the measurement of Pu materials is emphasized. The mass fractionation observed for Am, Ga, Pu, and U for isotope amount ratio measurements using the total evaporation (TE) technique is compared with theoretical estimates to demonstrate the advantage of the TE methodology and to investigate systematic biases in the major isotope amount ratios of U and Pu certified reference material (CRM) standards from the U.S. provider of CRMs. The quality of the Pu isotopic data generated by TIMS instruments in an analytical laboratory is demonstrated by the application of the double ratio technique to estimate the 241 Pu half-life. Analytical data on traceable Pu CRMs from the New Brunswick Laboratory (NBL), generated as part of routine measurements supporting various programs, are used for this half-life estimation. Although the 241 Pu abundances in CRMs of 136, 137, 138, and 126-A are approximately 200–2000× smaller than those in the 241 Pu material used in the previous Institute for Reference Materials and Measurements (IRMM) evaluation of the 241 Pu half-life, the half-life value estimated in this work shows excellent agreement with the currently accepted value from the IRMM. This agreement also demonstrates the pedigree of the Pu isotopic standards from the NBL and the quality of the isotope amount ratio measurements using TIMS instrumentation. For both the major and minor Pu isotope amount ratios, this report describes the relative importance of the factors affecting the uncertainty of TIMS measurements, which are considered the gold standard in isotope ratio measurements (LA-UR-24-29199).

07 ISOTOPE AND RADIATION SOURCES↗

DOE OSTI2025

Detection of Isotopes in Urban Source Search Low-Count Gamma Spectra Using Hopfield Neural Networks

Source search campaigns involve measurements of background gamma-ray spectra with a mobile detector-spectrometer traveling along arbitrarily chosen trajectories over a wide screening area. Radiation counts are typically measured with a tellurium-doped sodium iodide [NaI(Tl)] scintillator detector-spectrometer in short acquisition intervals, usually 1 s. The objective is to detect orphan isotopes with half-lives shorter than those of the isotopes in the natural background. In principle, radioisotopes can be identified by their unique gamma emission spectrum. However, detecting orphan isotopes in search data is challenging because low counts measured in short acquisition intervals result in incomplete spectral lines. In this study, we investigate the performance of a Hopfield neural network (HNN) that implements an auto-associative memory for the detection of isotopes of interest in an urban search campaign. The HNN is trained on one example of gamma spectra with well-resolved spectral lines of each isotope of interest. During testing, the auto-associative memory implementation of the HNN processes low-count gamma spectra with partially complete isotopic lines by matching incoming measurements to the closest one of its memory-stored patterns. The testing database consisted of almost 10 000 1-s gamma spectra, including measurements of orphan isotopes 137 Cs, 241 Am, and 131 I, obtained during two urban search surveys with a NaI(Tl) detector. The performance of the HNN detection algorithm was evaluated using precision, recall, and F1 scores, and benchmarked with a multiple linear regression (MLR) identification algorithm. In conclusion, the test results demonstrate that HNN outperforms MLR in the detection of all the isotopes of interest.

Auto associative memory↗

DOE OSTI2026

Lead Isotope Fingerprinting of Nanoscale Mineral Particles via Single Particle Inductively Coupled Plasma Mass Spectrometry

Determining lead (Pb) isotopic ratios is of broad interest across chemical disciplines for source tracing and age determinations, but the technique is inherently limited when multiple sources of Pb are present in a single sample. Single particle methods offer a solution to directly resolve multiple distinct isotopic ratios within individual samples. In this study, single particle inductively coupled plasma-mass spectrometry (spICP-MS) was performed using time-of-flight (TOF) and multicollector (MC)-based platforms to measure the Pb isotopic composition of individual nanoscale particles. Distinct Pb isotope ratios were measured in particles from four powdered galena samples of different origins (average single-particle 206Pb/207Pb ratios ranging from 0.91 to 1.28) using both the TOF and the MC-based platforms. Differentiation of galena particles in a mixture (liberated grains and those hosted in a silicate matrix) was possible due to detecting their unique multielemental fingerprints. The differing behavior of the two galena samples during digestion was investigated; undigested galena particles trapped within silicate minerals were detected using spICP-MS, which has implications for Pb recovery in bulk-scale isotopic analysis. The multinuclide detection capability of the ICP-TOF-MS instrument allowed for the simultaneous detection of secondary constituent elements within the nanoparticles and the identification of multiple populations of isotopically distinct Pb-bearing particles in a copper ore sample, whereas the increased sensitivity of the MC instrument enabled quantification of 204Pb, allowing differentiation using multiple isotopic ratios. A single particle isotope ratio analysis module was developed within an open-source spICP-TOF-MS data processing platform, enabling its adoption across chemical disciplines.

Goodman, Aaron J. [University of Montreal, Quebec,↗

DOE OSTI2025

Photoselective isotope fractionation dynamics of N 2 with cosmo and atmospheric chemistry perspectives

Stable isotope ratio measurements provide valuable insights into a broad range of natural processes, from planetary atmospheres and climate to interstellar chemistry. Nitrogen, which has two stable isotopes, exhibits varying isotope ratios across the solar system. To model these observations, the isotope fraction as a function of energy is essential. At the Advanced Light Source (ALS), we measured the photodissociation of molecular nitrogen (N 2 ) with vacuum UV photons where a single photon is sufficiently energetic to dissociate the strong bond. The nitrogen atoms produced are scavenged with H 2 to form ammonia, whose isotopic makeup is determined. Blending the experiments with dynamical computations that include the shielding of light, we examine the isotopic composition and electronic atomic states produced. The measured photodissociation of N 2 at a natural isotopic composition with a frequency broad light beam exceptionally strongly favors the formation of the heavier nitrogen isotope, 15 N. Computations concur and suggest that the maximum in the quantum yield reflects significant variations in the specific electronic quantum states of the product N atoms that have quite different reactivities. Our quantum computations show that at similar energies, photodissociation of 14 N 14 N and 15 N 14 N can lead to different product channels. The computed dynamics include extensive state-selective spin–orbit and nonadiabatic couplings affecting the light absorption and dissociation pathways that proceed via the triplet manifold of states. Our results are relevant for future exploration missions, both in situ and sample-return and for other molecules such as O 2 and CO.

Komarova, Ksenia [Hebrew Univ. of Jerusalem (Israe↗

DOE OSTI2026

Iron isotope fractionation between solid and liquid metal in the Fe-P±Ni system: Experimental constraints and implications for meteorites

Iron meteorites record a range of Fe isotope compositions that hold valuable information regarding the evolution of their parent bodies. Interpreting this isotopic variability, however, requires experimental constraints on the equilibrium isotope fractionation between phases. It is thought that the cores of many iron meteorite parent bodies experienced fractional crystallization, during which crystallization of solid iron-nickel occurs from an increasingly non-metal-rich liquid alloy. Phosphorus is one component of this alloy, and this study provides the first constraints on Fe-isotope fractionation between solid and liquid alloys in the Fe-Ni-P system. Experiments comprising Fe and P show a clear enrichment in the light isotopes of Fe in the liquid phase, which increases with the amount of phosphorus. Nickel-bearing samples are offset from the trend defined by Ni-free experiments, which is accounted for by the change in the solid alloy phase from a body-centered cubic to face-centered cubic structure upon the addition of Ni. The increasing light isotope enrichment of the liquid with increasing P content suggests interstitial solution of P, which is known to lengthen Fe-Fe bonds in Fe-P liquids (Waseda and Shiraishi 1977). Results suggest a negligible effect of P on Fe isotope fractionation during planetesimal core crystallization. Iron isotopes may, however, prove useful for identifying the petrogenesis of schreibersite in pallasites and iron meteorites.

58 GEOSCIENCES↗

NASA NTRS1988

Impact-induced devolatilization and hydrogen isotopic fractionation of serpentine: Implications for planetary accretion

Impact-induced devolatilization of porous serpentine was investigated using two independent experimental methods, the gas recovery and the solid recovery method, each yielding nearly identical results. For shock pressures near incipient devolatilization, the hydrogen isotopic composition of the evolved H2O is very close to that of the starting material. For shock pressures at which up to 12 percent impact-induced devolatilization occurs, the bulk evolved gas is significantly lower in deuterium than the starting material. There is also significant reduction of H2O to H2 in gases recovered at these higher shock pressures, probably caused by reaction of evolved H2O with the metal gas recovery fixture. Gaseous H2O-H2 isotopic fractionation suggests high temperature isotopic equilibrium between the gaseous species, indicating initiation of devolatilization at sites of greater than average energy deposition. Bulk gas-residual solid isotopic fractionations indicate nonequilibrium, kinetic control of gas-solid isotopic ratios. Impact-induced hydrogen isotopic fractionation of hydrous silicates during accretion can strongly affect the long-term planetary isotopic ratios of planetary bodies, leaving the interiors enriched in deuterium. Depending on the model used for extrapolation of the isotopic fractionation to devolatilization fractions greater than those investigated experimentally can result from this process.

Tyburczy, James A.↗

NASA NTRS1987

Mechanisms and observations for isotope fractionation of molecular species in planetary atmospheres

Chemcial and physical processes which may give rise to isotope fractionation of molecular species in the atmospheres of both earth and other planets are reviewed, along with observations of isotopically substituted molecules in planetary atmospheres. Mechanisms for production of isotope fractionation considered include atmospheric escape and the effect of isotope substitution on equilibrium constants (including those of phase changes), photolysis rates, and chemical reaction rates. The isotopes considered for compounds in the terrestrial atmosphere include D, T, C-13, C-14, N-15, O-18, and S-34. Compounds for which data about isotopic composition in the terrestrial atmosphere are summarized include CO, CO2, O3, N2O, NH3, SO2, H2S, H2O, H, H2, and CH4. Planetary atmospheres discussed include those of Venus, Mars, Jupiter, Saturn, Uranus, and Titan; isotopes reviewed are D, C-13, N-15, and O-18. Suggestions for additional research in the area of isotopically substituted molecules in atmospheres are offered.

Kaye, Jack A.↗

NASA NTRS1989

Isotopic microanalysis of returned comet nucleus samples

If isotopic measurements of interplanetary dust particles (IDPs) and primitive meteorites can serve as a guide to the isotopic analysis of returned comet nucleus material, an essential requirement will be the capability for microanalysis. The reason is that in both types of extraterrestrial samples large isotopic heterogeneities on a small spatial scale have become apparent once it was possible to measure isotopes in small samples. In the discovery of large isotopic anomalies the ion microprobe has played a significant role because of its high spatial resolution for isotopic ratio measurements. The largest isotopic anomalies in C, N, O, Mg, Si, Ca and Ti found to date were measured by ion microprobe mass spectrometry. The most striking examples are D/H measurements in IDPs and isotopic measurements of C, N and Si in SiC from the CM chondrites Murray and Murchison.

Zinner, Ernst↗

NASA NTRS1993

Factors that control the stable carbon isotopic composition of methane produced in an anoxic marine sediment

The carbon isotopic composition of methane produced in anoxic marine sediment is controlled by four factors: (1) the pathway of methane formation, (2) the isotopic composition of the methanogenic precursors, (3) the isotope fractionation factors for methane production, and (4) the isotope fractionation associated with methane oxidation. The importance of each factor was evaluated by monitoring stable carbon isotope ratios in methane produced by a sediment microcosm. Methane did not accumulate during the initial 42-day period when sediment contained sulfate, indicating little methane production from 'noncompetitive' substrates. Following sulfate depletion, methane accumulation proceeded in three distinct phases. First, CO2 reduction was the dominant methanogenic pathway and the isotopic composition of the methane produced ranged from -80 to -94 per thousand. The acetate concentration increased during this phase, suggesting that acetoclastic methanogenic bacteria were unable to keep pace with acetate production. Second, acetate fermentation became the dominant methanogenic pathway as bacteria responded to elevated acetate concentrations. The methane produced during this phase was progressively enriched in C-13, reaching a maximum delta(C-13) value of -42 per thousand. Third, the acetate pool experienced a precipitous decline from greater than 5 mM to less than 20 micro-M and methane production was again dominated by CO2 reduction. The delta(C-13) of methane produced during this final phase ranged from -46 to -58 per thousand. Methane oxidation concurrent with methane production was detected throughout the period of methane accumulation, at rates equivalent to 1 to 8 percent of the gross methane production rate. Thus methane oxidation was too slow to have significantly modified the isotopic signature of methane. A comparison of microcosm and field data suggests that similar microbial interactions may control seasonal variability in the isotopic composition of methane emitted from undisturbed Cape Lookout Bight sediment.

Alperin, M. J.↗

NASA NTRS1997

Interchange for Joint Research Entitled: Measurement of Stable Nitrogen and Sulfur Isotopes

Viking measurements of the Martian atmosphere indicate a value of N-15/N-14 which is markedly greater than that found in Earth's atmosphere. These isotopic measurements provide a powerful diagnostic tool which may be used to derive valuable information regarding the past history of Mars and they have been used to place important constraints on the evolution of Mars' atmosphere. Initial partial pressures of nitrogen, outgassing rates, and integrated deposition of nitrogen into minerals have been calculated from this important atmospheric data (McElroy et al., 1976 and 1977; Fox and Dalgarno, 1983). The greater precision obtained in laser spectrometer isotopic measurements compared to the Viking data will greatly improve these calculated values. It has also been proposed that the N-15/N-14 value in Mars' atmosphere has increased monotonically over time (McElroy et al., 1977; Fox and Dalgarno, 1983; Wallis, 1989) owing to preferential escape of atmospheric 14N to space. Nitrogen isotopic ratios might be used to identify relatively ancient crustal rocks (R. Mancinelli, personal communication), and perhaps determine relative aces of surface samples. As a first step in successfully measuring nitrogen isotopes optically we have demonstrated the measurement of 15NI14N to a precision of 0.1% (See Figures 1-4) using a tunable diode laser and an available gas (N-,O) with spectral lines in the 2188 cm-1 region. The sample and reference gas cells contained gases of identical isotopic composition so that the 15NI14N absorption ratio determined from the sample cell, when divided by the 15NI14N absorption ratio determined from the reference cell, should yield an ideal value of unity. The average measured value of this "ratio of ratios" was 0.9983 with a standard deviation (20 values) of 0.0010. This corresponds to a precision of 0.1% (1 per mil) for nitrogen isotopes, a value sufficiently precise to provide important isotopic data of interest to exobiologists. The precision presently attainable in gases is sufficient to permit the instrument to be used in the measurement of isotopic ratios of interest to exobiologists as well as geologists and planetary scientists.

Becker, Joseph F.↗

NASA NTRS1998

Water Isotopes in Precipitation: Data/Model Comparison for Present-Day and Past Climates

Variations of HDO and H2O-18 concentrations are observed in precipitation both on a geographical and on a temporal basis. These variations, resulting from successive isotopic fractionation processes at each phase change of water during its atmospheric cycle, are well documented through the IAEA/WMO network and other sources. Isotope concentrations are, in middle and high latitudes, linearly related to the annual mean temperature at the precipitation site. Paleoclimatologists have used this relationship to infer paleotemperatures from isotope paleodata extractable from ice cores, deep groundwater and other such sources. For this application to be valid, however, the spatial relationship must also hold in time at a given location as the location undergoes a series of climatic changes. Progress in water isotope modeling aimed at examining and evaluating this assumption has been recently reviewed with a focus on polar regions and, more specifically, on Greenland. This article was largely based on the results obtained using the isotopic version of the NASA/GISS Atmospheric General Circulation Model (AGCM) fitted with isotope tracer diagnostics. We extend this review in comparing the results of two different isotopic AGCMs (NASA/GISS and ECHAM) and in examining, with a more global perspective, the validity of the above assumption, i.e. the equivalence of the spatial and temporal isotope-temperature relationship. We also examine recent progress made in modeling the relationship between the conditions prevailing in moisture source regions for precipitation and the deuterium-excess of that precipitation.

Jouzel, J.↗

NASA NTRS1999

Interchange for Joint Research Entitled: Miniature Laser Spectrometer for Stable Isotope Measurements

As a first step in successfully measuring carbon isotopes optically we have previously demonstrated the measurement of C-13/C-12 to a precision of 0.1% using a tunable diode laser and CO2 spectral lines in the 2300/cm spectral region. This precision of 0.1% (1 per mil) for carbon isotopes is a value sufficiently precise to provide important isotopic data of interest to astrobiologists. The precision presently attainable in gases is sufficient to permit our instrument to be used in the measurement of isotopic ratios of interest to astrobiologists as well as geologists and planetary scientists. A small stable isotope laser spectrometer with a 10 cm path gas cell was designed and constructed. The cell was integrated with a liquid nitrogen cooled tunable diode laser and indium antimonide detector for evaluation. Using the small gas cell, preliminary measurements of 13C/12C in CO2 were made employing single-beam sequential acquisitions of the required spectral data. The results indicate an accuracy of 0.1% which is sufficiently high to make meaningful measurements of martian samples. In addition, improvements in the spectrometer gas handling system have been made to markedly reduce C-13/C-12 isotopic fractionation during sample gas cell loading which we expect will lead to further improvements in precision and accuracy. An important part of making isotopic ratio measurements in solid samples using diode lasers is the conversion of the elements of interest to molecules that have absorption spectra in the mid-ir spectral range accessible by tunable diode lasers. In this project we have investigated the necessary sample preparation procedures to extract carbon, an element of astrobiological importance, from model soil compounds and to convert it to CO2, a molecule with appropriate optical absorption characteristics for reliable laser spectrometer isotopic ratio measurements of 13C/12C. We have considered calcium carbonate as a model for a component of the martian regolith, and we have formulated a simple heating protocol for extracting carbon in the form of CO2.

Becker, J. F.↗

NASA NTRS1995

Isotopic Measurements of Organic Sulfonates From The Murchison Meteorite

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.

Cooper, G. W.↗

NASA NTRS2006

Compound-specific Isotope Analysis of Cyanobacterial Pure cultures and Microbial Mats: Effects of Photorespiration?

Microbial mats are considered modern homologs of Precambrian stromatolites. The carbon isotopic compositions of organic matter and biomarker lipids provide clues to the depositional environments of ancient mat ecosystems. As the source of primary carbon fixation for over two billion years, an understanding of cyanobacterial lipid biosynthesis, associated isotopic discriminations, and the influence of physiological factors on growth and isotope expression is essential to help us compare modern microbial ecosystems to their ancient counterparts. Here, we report on the effects of photorespiration (PR) on the isotopic composition of cyanobacteria and biomarker lipids, and on potential PR effects associated with the composition of various microbial mats. The high light, high O2 and limiting CO2 conditions often present at the surface of microbial mats are known to support PR in cyanobacteria. The oxygenase function of ribulose bisphosphate carboxylase/oxygenase can result in photoexcretion of glycolate and subsequent degration by heterotrophic bacteria. We have found evidence which supports an isotopic depletion (increased apparent E) scaled to O2 level associated with growth of Phormidium luridum at low CO2 concentrations (less than 0.04%). Similar to previous studies, isotopic differences between biomass and lipid biomarkers, and between lipid classes were positively correlated with overall fractionation, and should provide a means of estimating the influence of PR on overall isotopic composition of microbial mats. Several examples of microbial mats growing in the hydrothermal waters of Yellowstone National Park and the hypersaline marine evaporation ponds at Guerrero Negro, Baja Sur Mexico will be compared with a view to PR as a possible explanation of the relatively heavy C-isotope composition of hypersaline mats.

Jahnke, L. L.↗