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At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
NASA NTRS1991

Oxygen isotope studies of ordinary chondrites

Several stages in the evolution of ordinary chondritic meteorites are recorded in the oxygen isotopic composition of the meteorites and their separable components (chondrules, fragments, clasts, and matrix). The whole-rock isotopic compositions reflect the iron-group of the meteorite (H, L, or LL). Isotopic uniformity of H3 to H6 and L3 to L6 are consistent with closed-system metamorphism within each parent body. LL3 chondrites differ slightly from LL4 to LL6, implying a small degree of open-system aqueous alteration and carbon reduction. On the scale of individual chondrules, the meteorites are isotopically heterogeneous, allowing recognition of the solar-nebular processes of chondrule formation. Chondrules for all classes of ordinary chondrites are derived from a common population, which was separate from the population of chondrules in carbonaceous or enstatite chondrites. Chondrules define an isotopic mixing line dominated by exchange between (O - 16)-rich and (O - 16)-poor reservoirs. The oxygen isotopic compositions of chondrites serve as 'fingerprints' for identification of genetic association with other meteorite types (achondrites and iron) and for recognition of source materials in meteoritic breccias.

Clayton, Robert N.↗
NASA NTRS1993

Iron and nickel isotopic mass fractionation in deep-sea spherules

Magnetite-wuestite spherules collected from deep-sea sediments are thought to have originally been Fe-Ni metal particles at the top of the atmosphere that were oxidized and melted during entry into the earth's atmosphere. Some likely sources for the metal particles are Fe-Ni interplanetary dust particles (IDP's) and metal or sulfide from stony IDP's that separated after melting. Davis et al. reported that four of these spherules are enriched in the heavy isotopes of iron, with enrichments of 8-23%/amu. We have developed a technique for analysis of both iron and nickel isotopes on the same ion microprobe spot and have applied this technique to a number of deep-sea spherules in order to better understand the processes leading to isotopic mass fractionation. Eight spherules show iron and nickel isotopic mass fractionation, with iron and nickel enriched in the heavy isotopes by 10-19%/amu and 4-32%/amu, respectively. If the mass fractionations are due to Rayleigh fractionation during evaporation, these spherules lost 76-94% of their original mass. We have analyzed the four magnetite-wuestite spherules for which iron isotopic data were reported by Davis et al. as well as four new spherules.

Davis, Andrew M.↗
NASA NTRS1994

Light stable isotope analysis of meteorites by ion microprobe

The main goal was to develop the necessary secondary ion mass spectrometer (SIMS) techniques to use a Cameca ims-4f ion microprobe to measure light stable isotope ratios (H, C, O and S) in situ and in non-conducting mineral phases. The intended application of these techniques was the analysis of meteorite samples, although the techniques that have been developed are equally applicable to the investigation of terrestrial samples. The first year established techniques for the analysis of O isotope ratios (delta O-18 and delta O-17) in conducting mineral phases and the measurement of S isotope ratios (delta S-34) in a variety of sulphide phases. In addition, a technique was developed to measure delta S-34 values in sulphates, which are insulators. Other research undertaken in the first year resulted in SIMS techniques for the measurement of wide variety of trace elements in carbonate minerals, with the aim of understanding the nature of alteration fluids in carbonaceous chondrites. In the second year we developed techniques for analyzing O isotope ratios in nonconducting mineral phases. These methods are potentially applicable to the measurement of other light stable isotopes such as H, C and S in insulators. Also, we have further explored the analytical techniques used for the analysis of S isotopes in sulphides by analyzing troilite in a number of L and H ordinary chondrites. This was done to see if there was any systematic differences with petrological type.

Mcsween, Harry Y., Jr.↗
NASA NTRS1994

Chronology of chrondrule and CAI formation: Mg-Al isotopic evidence

Details of the chondrule and Ca-Al-rich inclusion (CAI) formation during the earliest history of the solar system are imperfectly known. Because CAI's are more 'refractory' than ferromagnesian chondrules and have the lowest recorded initial Sr-87/Sr-86 ratios of any solar system materials, the expectation is that CAI's formed earlier than chondrules. But it is not known, for example, if CAI formation had stopped by the time chondrule formation began. Conventional (absolute) age-dating techniques cannot adequately resolve small age differences (less than 10(exp 6) years) between objects of such antiquity. One approach has been to look at systematic differences in the daughter products of short-lived radionuclides such as Al-26 and I-129. Unfortunately, neither system appears to be 'well-behaved.' One possible reason for this circumstance is that later secondary events have partially reset the isotopic systems, but a viable alternative continues to be large-scale (nebular) heterogeneity in initial isotopic abundances, which would of course render the systems nearly useless as chronometers. In the past two years the nature of this problem has been redefined somewhat. Examination of the Al-Mg isotopic database for all CAI's suggests that the vast majority of inclusions originally had the same initial Al-26/Al-27 abundance ratio, and that the ill-behaved isotopic systematics now observed are the results of later partial reequilibration due to thermal processing. Isotopic heterogeneities did exist in the nebula, as demonstrated by the existence of so-called FUN inclusions in CV3 chondrites and isotopically anomalous hibonite grains in CM2 chondrites, which had little or no live Al-26 at the time of their formation. But, among the population of CV3 inclusions at least, FUN inclusions appear to have been a relatively minor nebular component.

Macpherson, G. J.↗
NASA NTRS1998

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.↗
NASA NTRS1996

Pyroxene Homogenization and the Isotopic Systematics of Eucrites

The original Mg-Fe zoning of eucritic pyroxenes has in nearly all cases been partly homogenized, an observation that has been combined with other petrographic and compositional criteria to establish a scale of thermal "metamorphism" for eucrites. To evaluate hypotheses explaining development of conditions on the HED parent body (Vesta?) leading to pyroxene homogenization against their chronological implications, it is necessary to know whether pyroxene metamorphism was recorded in the isotopic systems. However, identifying the effects of the thermal metamorphism with specific effects in the isotopic systems has been difficult, due in part to a lack of correlated isotopic and mineralogical studies of the same eucrites. Furthermore, isotopic studies often place high demands on analytical capabilities, resulting in slow growth of the isotopic database. Additionally, some isotopic systems would not respond in a direct and sensitive way to pyroxene homogenization. Nevertheless, sufficient data exist to generalize some observations, and to identify directions of potentially fruitful investigations.

Nyquist, L. E.↗
NASA NTRS2004

Oxygen Isotopes in Early Solar System Materials: A Perspective Based on Microbeam Analyses of Chondrules from CV Carbonaceous Chondrites

Some of the biggest challenges to understanding the early history of the solar system include determining the distribution of oxygen isotopes amongst materials that existed in the solar nebula, and interpreting the processes that might have resulted in the observed isotopic distributions. Oxygen isotope ratios in any individual mineral grain from a chondritic meteorite may be the cumulative product of a variety of processes, including stellar nucleosynthetic events, gas/solid interactions in the molecular cloud, mixing of independent isotopic reservoirs in the nebula, mass-independent processing in the nebula, and mass-dependent fractionation effects in various environments. It is not possible to unravel this complex isotopic record unless the distribution of oxygen isotope ratios in chondritic materials is fully understood.

Jones, R. H.↗
NASA NTRS2004

More on Ru Endemic Isotope Anomalies in Meteorites

We reported last year on endemic isotope anomalies for Ru in iron meteorites, pallasites, ordinary chondrites, and on a whole-rock sample of Allende. We have extended the Ru measurements to more meteorites, to refractory Ca-Al-rich inclusions (CAI) from Allende, and to a whole rock sample of Murchison (CM2). In a companion abstract we report on new measurements for the Mo isotopes, in some of the same samples. There has been a renewed interest in searching for isotope anomalies in this nuclide region, as Ru and Mo include many isotopes from r-, s-, and p-process nucleosynhesis. Furthermore, the Ru and Mo p-process isotopes show atypically high abundances, which have been hard to explain through the standard nucleosynthetic processes. Effects are possible in Ru-98 and Ru-99 from Tc-98 (with a poorly known t(sub 1/2)=4.2 to 10Ma) and from Tc-99 (t(sub 1/2)=0.21Ma). Natural Tc is now extinct on Earth due to the short half-lives, but may have been present in the early solar system. Both radiogenic and general isotope anomalies are important in understanding the processes for the formation of the early solar system. The current emphasis on Ru and Mo is also the result of the development of Negative-ion Thermal Ionization Mass Spectrometry and of Multiple-Collector, Inductively-Coupled-Mass-Spectrometry. We have also developed specific chemical siparation techniques for Ru, which eliminated mass interference effects.

Papanastassiou, D. A.↗
NASA NTRS2003

The Stable Isotope Fractionation of Abiotic Reactions: A Benchmark in the Detection of Life

One very important tool in the analysis of biogenic, and potentially biogenic, samples is the study of their stable isotope distributions. The isotope distribution of a sample depends on the process(es) that created it. One important application of the analysis of C & N stable isotope ratios has been in the determination of whether organic matter in a sample is of biological origin or was produced abiotically. For example, the delta C-13 of organic material found embedded in phosphate grains was cited as a critical part of the evidence for life in 3.8 billion year old samples. The importance of such analysis in establishing biogenicity was highlighted again by the role this issue played in the recent debate over the validity of what had been accepted as the Earth s earliest microfossils. These kinds of analysis imply a comparison with the fractionation that one would have seen if the organic material had been produced by alternative, abiotic, pathways. Could abiotic reactions account for the same level of fractionation? Additionally, since the fractionation can vary between different abiotic reactions, understanding their fractionations can be important in distinguishing what reactions may have been significant in the formation of different abiological samples (such as extraterrestrial samples). There is however, a scarcity of data on the fractionation of carbon and nitrogen by abiotic reactions. In order to interpret properly what the stable isotope ratios of samples tell us about their biotic or abiotic nature, more needs to be known about how abiotic reactions fractionate C and N. Carbon isotope fractionations have been studied for a few abiotic processes. These studies presumed the presence of a reducing atmosphere, focusing on reactions involving spark discharge, W photolysis of reducing gas mixtures, and cyanide polymerization in the presence of ammonia. They did find that the initial products showed a depletion in I3C with values in the range of a few per mil to as low as -60 % (potentially comparable to that which accompanies the biosynthesis of organic matter). We need to understand what kind of fractionations are observed with reactions under the non-reducing or mildly reducing conditions now thought to be present on the early Earth. While nitrogen is receiving increased attention as a tool for these kinds of analyses, almost nothing is known about the isotope fractionation that one would expect for abiotic sources of fixed/reduced nitrogen. This project will measure the fixation from a series of abiotic reactions that may have been present on the early Earth (and other terrestrial planets) and produced organic material that could have ended up in the rock record. The work will look at a number of reactions, under a non- reducing, or mildly reducing, atmosphere, covering sources of prebiotic organic C & N from shock heating, to photochemistry, to hydrothermal reactions. Some reactions that we plan to study are; Shock heating of a non-reducing atmosphere to produce CO and NO (in collaboration with Chris McKay), formation of formaldehyde (and related compounds) from COY the formation of ammonia from nitrogen oxides (ultimately from NO) by ferrous iron reduction, and the hydrothermal synthesis of compounds including the hydrocarboxylation/hydrocarbonylation reaction (in collaboration with George Cody), reactions of oxalate to form hydrocarbons and other oxygenated compounds and the formation of lipids from oxalic/formic acid (in collaboration with Tom McCollom), and reactions of carbon monoxide & carbon dioxide with N2, ammonia or nitritehitrate to form hydrogen cyanide, nitriles, ammonia/amines and nitrous

Summers, David P.↗
NASA NTRS2003

Stable carbon isotope fractionation by sulfate-reducing bacteria

Biogeochemical transformations occurring in the anoxic zones of stratified sedimentary microbial communities can profoundly influence the isotopic and organic signatures preserved in the fossil record. Accordingly, we have determined carbon isotope discrimination that is associated with both heterotrophic and lithotrophic growth of pure cultures of sulfate-reducing bacteria (SRB). For heterotrophic-growth experiments, substrate consumption was monitored to completion. Sealed vessels containing SRB cultures were harvested at different time intervals, and delta(13)C values were determined for gaseous CO(2), organic substrates, and products such as biomass. For three of the four SRB, carbon isotope effects between the substrates, acetate or lactate and CO(2), and the cell biomass were small, ranging from 0 to 2 per thousand. However, for Desulfotomaculum acetoxidans, the carbon incorporated into biomass was isotopically heavier than the available substrates by 8 to 9 per thousand. SRB grown lithoautotrophically consumed less than 3% of the available CO(2) and exhibited substantial discrimination (calculated as isotope fractionation factors [alpha]), as follows: for Desulfobacterium autotrophicum, alpha values ranged from 1.0100 to 1.0123; for Desulfobacter hydrogenophilus, the alpha value was 0.0138, and for Desulfotomaculum acetoxidans, the alpha value was 1.0310. Mixotrophic growth of Desulfovibrio desulfuricans on acetate and CO(2) resulted in biomass with a delta(13)C composition intermediate to that of the substrates. The extent of fractionation depended on which enzymatic pathways were used, the direction in which the pathways operated, and the growth rate, but fractionation was not dependent on the growth phase. To the extent that environmental conditions affect the availability of organic substrates (e.g., acetate) and reducing power (e.g., H(2)), ecological forces can also influence carbon isotope discrimination by SRB.

Deltaproteobacteria/growth & development/metabolis↗
NASA NTRS2001

Mercury Abundances and Isotopic Compositions in the Murchison (CM) and Allende (CV)Carbonaceous Chondrites

The abundance and isotopic composition of Hg was determined in bulk samples of both the Murchison (CM) and Allende (CV) carbonaceous chondrites using single- and multi-collector inductively coupled plasma mass spectrometry (ICP-MS). The bulk abundances of Hg are 294 6 15 ng/g in Murchison and 30.0 6 1.5 ng/g in Allende. These values are within the range of previous measurements of bulk Hg abundances by neutron activation analysis (NAA). Prior studies suggested that both meteorites contain isotopically anomalous Hg, with d l 96/202Hg values for the anomalous, thermal-release components from bulk samples ranging from 2260 %o to 1440 9/00 in Murchison and from 2620 9/00 to 1540 9/00 in Allende (Jovanovic and Reed, 1976a; 1976b; Kumar and Goel, 1992). Our multi-collector ICP-MS measurements suggest that the relative abundances of all seven stable Hg isotopes in both meteorites are identical to terrestrial values within 0.2 to 0.5 9/00m. On-line thermal-release experiments were performed by coupling a programmable oven with the singlecollector ICP-MS. Powdered aliquots of each meteorite were linearly heated from room temperature to 900 C over twenty-five minutes under an Ar atmosphere to measure the isotopic composition of Hg released fiom the meteorites as a h c t i o n of temperature. In separate experiments, the release profiles of S and Se were determined simultaneously with Hg to constrain the Hg distribution within the meteorites and to evaluate the possibility of Se interferences in previous NAA studies. The Hg-release patterns differ between Allende and Murchison. The Hg-release profile for Allende contains two distinct peaks, at 225" and 343"C, whereas the profile for Murchison has only one peak, at 344 C. No isotopically anomalous Hg was detected in the thermal-release experiments at a precision level of 5 to 30 9/00, depending on the isotope ratio. In both meteorites the Hg peak at ;340"C correlates with a peak in the S-release profile. This correlation suggests that Hg is associated with S-bearing phases and, thus, that HgS is a major Hg-bearing phase in both meteorites. The Hg peak at 225 C for Allende is similar to release patterns of physically adsorbed Hg on silicate and metal grains.

Lauretta, D. S.↗
NASA NTRS2004

Measurement of the Abundance of Radioactive Be-10 and Other Light Isotopes in Cosmic Radiation Up to 2 GeV /Nucleon with the Balloon-Borne Instrument Isomax

The Isotope Magnet Experiment (ISOMAX), a balloon-borne superconducting magnet spectrometer, was designed to measure the isotopic composition of the light isotopes (3 les than or = Z less than or = 8) of cosmic radiation up to 4 GeV/nucleon with a mass resolution of better than 0.25 amu by using the velocity versus rigidity technique. To achieve this stringent mass resolution, ISOMAX was composed of three major detector systems: a magnetic rigidity spectrometer with a precision drift chamber tracker in conjunction with a three-layer time-of-flight system, and two silica-aerogel Cerenkov counters for velocity determination. A special emphasis of the ISOMAX program was the accurate measurement of radioactive Be-10 with respect to its stable neighbor isotope Be-9, which provides important constraints on the age of cosmic rays in the Galaxy. ISOMAX had its first balloon flight on 1998 August 4-5 from Lynn Lake, Manitoba, Canada. Thirteen hours of data were recorded during this flight at a residual atmosphere of less than 5 g/sq cm. The isotopic ratio at the top of the atmosphere for Be-10/Be-9 was measured to be 0.195 +/- 0.036 (statistical) +/- 0.039 (systematic) between 0.26 and 1.03 GeV/nucleon and 0.317 +/- 0.109(statistical) +/- 0.042(systematic) between 1.13 and 2.03 GeV/nucleon. This is the first measurement of its kind above l GeV/nucleon. ISOMAX results tend to be higher than predictions from current propagation models. In addition to the beryllium results, we report the isotopic ratios of neighboring lithium and boron in the energy range of the time-of-flight system (up to approx. 1 GeV/nucleon). The lithium and boron ratios agree well with existing data and model predictions at similar energies.

Hams, T.↗
NASA NTRS2007

Isotopic Measurements in CAIs with the Nanosims: Implications to the understanding of the Formation process of Ca, Al-Rich Inclusions

Ca, Al-rich Inclusions (CAIs) preserve evidence of thermal events that they experienced during their formation in the early solar system. Most CAIs from CV and CO chondrites are characterized by large variations in O-isotopic compositions of primary minerals, with spinel, hibonite, and pyroxene being more O-16-rich than melilite and anorthite, with delta 17, O-18 = approx. -40%o (DELTA O-17 = delta O-17 - 0.52 x delta O-18 = approx. - 20%o ). These anomalous compositions cannot be accounted for by standard mass dependent fractionation and diffusive process of those minerals. It requires the presence of an anomalous oxygen reservoir of nucleosynthetic origin or mass independent fractionations before the formation of CAIs in the early solar system. The CAMECA NanoSIMS is a new generation ion microprobe that offers high sensitivity isotopic measurements with sub 100 nm spatial resolution. The NanoSIMS has significantly improved abilities in the study of presolar grains in various kind of meteorites and the decay products of extinct nuclides in ancient solar system matter. This instrument promises significant improvements over other conventional ion probes in the precision isotopic characterization of sub-micron scales. We report the results of our first O isotopic measurements of various CAI minerals from EK1-6-3 and 7R19-1(a) utilizing the JSC NanoSIMS 50L ion microprobe. We evaluate the measurement conditions, the instrumental mass fractionation factor (IMF) for O isotopic measurement and the accuracy of the isotopic ratio through the analysis of a San Carlos olivine standard and CAI sample of 7R19-1(a).

Ito, M.↗
NASA NTRS2007

Coupled Nd-142, Nd-143 and Hf-176 Isotopic Data from 3.6-3.9 Ga Rocks: New Constraints on the Timing of Early Terrestrial Chemical Reservoirs

Increasingly precise data from a range of isotopic decay schemes, including now extinct parent isotopes, from samples of the Earth, Mars, Moon and meteorites are rapidly revising our views of early planetary differentiation. Recognising Nd-142 isotopic variations in terrestrial rocks (which can only arise from events occurring during the lifetime of now extinct Sm-146 [t(sub 1/2)=103 myr]) has been an on-going quest starting with Harper and Jacobsen. The significance of Nd-142 variations is that they unequivocally reflect early silicate differentiation processes operating in the first 500 myr of Earth history, the key time period between accretion and the beginning of the rock record. The recent establishment of the existence of Nd-142 variations in ancient Earth materials has opened a new range of questions including, how widespread is the evidence of early differentiation, how do Nd-142 compositions vary with time, rock type and geographic setting, and, combined with other types of isotopic and geochemical data, what can Nd-142 isotopic variations reveal about the timing and mechanisms of early terrestrial differentiation? To explore these questions we are determining high precision Nd-142, Nd-143 and Hf-176 isotopic compositions from the oldest well preserved (3.63- 3.87 Ga), rock suites from the extensive early Archean terranes of southwest Greenland and western Australia.

Bennett, Vickie C.↗
NASA NTRS2008

Oxygen Isotope Systematics of Chondrules from the Least Equilibrated H Chondrite

Oxygen isotope compositions of bulk chondrules and their mineral separates in type 3 ordinary chondrites (UOC) show several % variability in the oxygen three isotope diagram with slope of approx.0.7 [1]. In contrast, ion microprobe analyses of olivine and pyroxene phenocrysts in ferromagnesian chondrules from LL 3.0-3.1 chondrites show mass dependent isotopic fractionation as large as 5% among type I (FeO-poor) chondrules, while type II (FeO-rich) chondrules show a narrow range (less than or equal to 1%) of compositions [2]. The .Delta(exp 17)O (=delta(exp 17)O-0.52xdelta(exp 18)O) values of olivine and pyroxene in these chondrules show a peak at approx.0.7% that are systematically lower than those of bulk chondrule analyses as well as the bulk LL chondrites [2]. Further analyses of glass in Semarkona chondrules show .17O values as high as +5% with highly fractionated d18O (max +18%), implying O-16-poor glass in chondrules were altered as a result of hydration in the parent body at low temperature [3]. Thus, chondrules in LL3.0-3.1 chondrites do not provide any direct evidence of oxygen isotope exchange between solid precursor and O-16-depleted gas during chondrule melting events. To compare the difference and/or similarity between chondrules from LL and H chondrites, we initiated systematic investigations of oxygen isotopes in chondrules from Yamato 793408 (H3.2), one of the least equilibrated H chondrite [4]. In our preliminary study of 4 chondrules, we reported distinct oxygen isotope ratios from dusty olivine and refractory forsterite (RF) grains compared to their host chondrules and confirmed their relict origins [5].

Kita, N. T.↗
NASA NTRS2006

Isotopic Dependence of GCR Fluence behind Shielding

In this paper we consider the effects of the isotopic composition of the primary galactic cosmic rays (GCR), nuclear fragmentation cross-sections, and isotopic-grid on the solution to transport models used for shielding studies. Satellite measurements are used to describe the isotopic composition of the GCR. For the nuclear interaction data-base and transport solution, we use the quantum multiple-scattering theory of nuclear fragmentation (QMSFRG) and high-charge and energy (HZETRN) transport code, respectively. The QMSFRG model is shown to accurately describe existing fragmentation data including proper description of the odd-even effects as function of the iso-spin dependence on the projectile nucleus. The principle finding of this study is that large errors (+/-100%) will occur in the mass-fluence spectra when comparing transport models that use a complete isotopic-grid (approx.170 ions) to ones that use a reduced isotopic-grid, for example the 59 ion-grid used in the HZETRN code in the past, however less significant errors (<+/-20%) occur in the elemental-fluence spectra. Because a complete isotopic-grid is readily handled on small computer workstations and is needed for several applications studying GCR propagation and scattering, it is recommended that they be used for future GCR studies.

Cucinotta, Francis A.↗
NASA NTRS2010

Evaluating the Historical Importance of Impact Induced Hydrothermal Systems on Mars Using the Stable Isotopic Composition of Martian Water

The importance of impact events during the early history of Mars is obvious through a simple examination of the character of the martian surface. This ancient, heavily cratered terrain has been shown to be associated with extensive phyllosilicate deposits. This geologic link could suggest that the extensive phyllosilicate-forming alteration may have occurred during early martian history through impact-induced hydrothermal alteration. However, examination of the oxygen isotopic composition of water on Mars suggests that the extensive phyllosilicate deposits were formed primarily through low temperature (<30 C) interactions, and that high temperature weathering in impact-induced hydrothermal systems have not been a dominant process on Mars. The average oxygen isotopic composition of water on Earth is dictated by the nature of water-rock interactions. If these interactions occur at higher temperatures then the water will contain a higher proportion of 18O, while lower temperature interactions will result in water with a lower proportion of 18O. Water on Earth today contains a higher proportion of 18O because of plate tectonics and hydrothermal interaction at mid-ocean ridges. The oxygen isotopic composition of water on early earth, however, may have been quite different, containing a smaller proportion of 18O suggesting much less hydrothermal interaction. Because there are not yet any direct measurements of the oxygen isotopic composition of water on Mars, it needs to be inferred through examination of carbonates preserved in martian meteorites and the isotopic composition of atmospheric CO2. This can be done because the oxygen incorporated into carbonates and CO2 is easily exchanged with liquid water if it is present. Independently, both measurements provide an estimate for the (Sigma)18O of water on Mars to be near -16%. This composition is consistent with low temperature weathering of the silicate crust, and indicates that impact hydrothermal systems did not play an important role in the early alteration of the planet. However, our understanding of impact-induced hydrothermal systems remains unclear. If most of the water mobilized by an impact event remained at relatively low temperatures (<30deg), low-temperature interactions could predominate in these environments. These conditions would be consistent with the isotopic constraints suggested in this study.

Niles, Paul B.↗
NASA NTRS2010

Experimental Study of Abiotic Organic Synthesis at High Temperature and Pressure Conditions: Carbon Isotope and Mineral Surface Characterizations

Abiotic organic synthesis processes have been proposed as potential mechanisms for methane generation in subseafloor hydrothermal systems on Earth, and on other planets. To better understand the detailed reaction pathways and carbon isotope fractionations in this process under a wide range of physical and chemical conditions, hydrothermal experiments at high temperature (750 C) and pressure (0.55 GPa) were performed using piston cylinder apparatus. Formic acid was used as the source of CO2 and H2, and magnetite was the mineral catalyst. The chemical and carbon isotopic compositions of dissolved organic products were determined by GC-C-MS-IRMS, while organic intermediaries on the mineral catalyst were characterized by Pyrolysis-GC-MS. Among experimental products, dissolved CO2 was the dominant carbon species with a relative abundance of 88 mol%. Dissolved CH4 and C2H6 were also identified with a mole ratio of CH4 over C2H6 of 15:1. No dissolved CO was detected in the experiment, which might be attributable to the loss of H2 through the Au capsule used in the experiments at high temperature and pressure conditions and corresponding conversion of CO to CO2 by the water-gas shift reaction. Carbon isotope results showed that the 13C values of CH4 and C2H6 were -50.3% and -39.3% (V-PDB), respectively. CO2 derived from decarboxylation of formic acid had a (sigma)C-13 value of -19.2%, which was 3.2% heavier than its source, formic acid. The (sigma)C-13 difference between CO2 and CH4 was 31.1%, which was higher than the value of 9.4% calculated from theoretical isotopic equilibrium predictions at experimental conditions, suggesting the presence of a kinetic isotope effect. This number was also higher than the values (4.6 to 27.1%) observed in similar experiments previously performed at 400 C and 50 MPa with longer reaction times. CH4 is 11.0% less enriched in C-13 than C2H6. Alcohols were observed as carbon compounds on magnetite surfaces by Pyrolysis-GC-MS, which confirms the hypothesis regarding the reaction pathways of hydrothermal abiotic organic synthesis proposed by Fu et al. (2007, 2008). In this proposed pathway, hydroxymethylene (-CHOH) groups serve as organic intermediaries on mineral surfaces while dissolved H2 serves as a chain terminator/breaker to generate short chain hydrocarbons and oxygenated compounds. This pathway is different from the carbide polymerization theory of Fischer- Tropsch-type (FTT) synthesis in a gas phase. The observed increase of (sigma)C-13 values of C1 and C2 alkanes with carbon number in our hydrothermal experiments can be readily interpreted by hydroxymethylene pathway, and might be used to differentiate between hydroxymethylene and carbide polymerization pathways. Carbon isotope analysis of alcohols on mineral catalyst surfaces is under way to provide further constraints on formation of organic compounds by FTT in hydrothermal systems.

Fu, Qi↗