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At least 955 records · Page 53

Geochemical, Biological, and Clumped Isotopologue Evidence for Substantial Microbial Methane Production Under Carbon Limitation in Serpentinites of the Samail Ophiolite, Oman

In hyperalkaline (pH > 10) fluids that have participated in low-temperature (<150°C) serpentinization reactions, the dominant form of C is often methane (CH 4 ), but the origin of this CH 4 is uncertain. To assess CH 4 origin in serpentinite aquifers within the Samail Ophiolite, Oman, we determined fluid chemical compositions, analyzed taxonomic profiles of fluid-hosted microbial communities, and measured isotopic compositions of hydrocarbon gases. We found that 16S rRNA gene sequences affiliated with methanogens were widespread in the aquifer. We measured clumped isotopologue ( 13 CH 3 D and 12 CH 2 D 2 ) relative abundances less than equilibrium, consistent with substantial microbial CH 4 production. Furthermore, we observed an inverse relationship between dissolved inorganic C concentrations and δ 13 C CH 4 across fluids bearing microbiological evidence of methanogenic activity, suggesting that the apparent C isotope effect of microbial methanogenesis is modulated by C availability. An additional source of CH 4 is evidenced by the presence of CH 4 -bearing fluid inclusions in the Samail Ophiolite and our measurement of high δ 13 C values of ethane and propane, which are similar to those reported in studies of CH 4 -rich inclusions in rocks from the oceanic lithosphere. In addition, we observed 16S rRNA gene sequences affiliated with aerobic methanotrophs and, in lower abundance, anaerobic methanotrophs, indicating that microbial consumption of CH 4 in the ophiolite may further enrich CH 4 in 13 C. We conclude that substantial microbial CH 4 is produced under varying degrees of C limitation and mixes with abiotic CH 4 released from fluid inclusions. This study lends insight into the functioning of microbial ecosystems supported by water/rock reactions.

58 GEOSCIENCES↗

Galactic cosmic ray composition

An assessment is given of the galactic cosmic ray source (GCRS) elemental composition and its correlation with first ionization potential. The isotopic composition of heavy nuclei; spallation cross sections; energy spectra of primary nuclei; electrons; positrons; local galactic reference abundances; comparison of solar energetic particles and solar coronal compositions; the hydrogen; lead; nitrogen; helium; and germanium deficiency problems; and the excess of elements are among the topics covered.

Meyer, J. P.↗

The nu-process

As the core of a massive star collapses to form a neutron star, the flux of neutrinos in the overlying shells of heavy elements becomes so great that, despite the small cross section, substantial nuclear transmutation is induced. Neutrinos excite heavy elements and even helium to particle unbound levels. The evaporation of a single neutron or proton, and the back reaction of these nucleons on other species present, significantly alters the outcome of traditional nucleosynthesis calculations leading to a new process: nu-nucleosynthesis. Modifications to traditional hydrostatic and explosive varieties of helium, carbon, neon, oxygen, and silicon burning are considered. The results show that a large number of rare isotopes, including many of the odd-Z nuclei from boron through copper, owe much of their present abundance in nature to this process.

Woosley, S. E.↗

Large Isotope Spectrometer for Astromag

The Large Isotope Spectrometer for Astromag (LISA) is an experiment designed to measure the isotopic composition and energy spectra of cosmic rays for elements extending from beryllium through zinc. The overall objectives of this investigation are to study the origin and evolution of galactic matter; the acceleration, transport, and time scales of cosmic rays in the galaxy; and search for heavy antinuclei in the cosmic radiation. To achieve these objectives, the LISA experiment will make the first identifications of individual heavy cosmic ray isotopes in the energy range from about 2.5 to 4 GeV/n where relativistic time dilation effects enhance the abundances of radioactive clocks and where the effects of solar modulation and cross-section variations are minimized. It will extend high resolution measurements of individual element abundances and their energy spectra to energies of nearly 1 TeV/n, and has the potential for discovering heavy anti-nuclei which could not have been formed except in extragalactic sources.

Binns, W. R.↗

Martian carbon dioxide: Clues from isotopes in SNC meteorites

Attempts to unravel the origin and evolution of the atmosphere and hydrosphere on Mars from isotopic data have been hampered by the impreciseness of the measurements made by the Viking Lander and by Earth-based telescopes. The SNC meteorites which are possibly pieces of the Martian surface offer a unique opportunity to obtain more precise estimates of the planet's volatile inventory and isotopic composition. Recently, we reported results on oxygen isotopes of water extracted by pyrolysis from samples of Shergotty, Zagami, Nakhla, Chassigny, Lafayette, and EETA-79001. Now we describe complementary results on the stable isotopic composition of carbon dioxide extracted simultaneously from those same samples. We will also report on C-14 abundances obtained by accelerator mass spectrometry (AMS) for some of these CO2 samples.

Karlsson, H. R.↗

Experimental and Analytical Studies of Solar System Chemistry

The cosmochemistry research funded by this grant resulted in the publications given in the attached Publication List. The research focused in three areas: (1) Experimental studies of trace element partitioning. (2) Studies of the minor element chemistry and O isotopic compositions of MgAlO4 spinels from Ca-Al-Rich Inclusions in carbonaceous chondrite meteorites, and (3) The abundances and chemical fractionations of Th and U in chondritic meteorites.

Burnett, Donald S.↗

Elemental Abundance Variations Observed in Solar Energetic Particle Events During Solar Cycle 23

We report on observations of the abundances of elements from Helium to Nickel in over 50 different solar energetic particle events using the Solar Isotope Spectrometer (SIS) on-board the Advanced Composition Explorer (ACE) spacecraft. It had originally been expected that the energy spectra of different elements would show spectral roll-overs at energies related to the Q/M ratio of each element. Due to the partial stripping of Fe and essentially complete stripping of O, it was expected that the Fe/O ratio would be observed to decrease with increasing energy. While many events show this pattern, others have Fe/O which is constant with energy, while for yet others Fe/O actually increases with energy. Events having constant Fe/O could simply have their spectral breaks outside of the observed energy range. However, events which show increasing Fe/O cannot be explained within the framework of spectral breaks. Possible explanations include injection of remnant heavy ions from earlier impulsive events, hybrid Events consisting of a combination of flare-accelerated and shock-accelerated particles from a single solar event, and some new physical process in shock acceleration. We will report on efforts to distinguish these possible explanations.

vonRosenvinge, T. T.↗

Peering Through a Martian Veil: ALHA84001 Sm-Nd Age Revisited

The ancient Martian orthopyroxenite ALH84001experienced a complex history of impact and aqueous alteration events. Here we summarize Sm-147-Nd-143 and Sm-146-Nd-142 analyses performed at JSC. Further, using REE data, we model the REE abundance pattern of the basaltic magma parental to ALH84001 cumulus orthopyroxene. We find the Sm-146-Nd-142 isotopic data to be consistent with isotopic evolution in material having the modeled Sm/Nd ratio from a time very close to the planet's formation to igneous crystallization of ALH84001 as inferred from the Sm-Nd studies.

Nyquist, Laurence E.↗

Documenting Antarctic Alteration of Eucrites

When meteorites were discovered in Antarctica, it was anticipated that terrestrial alteration would be at a minimum because of their deepfreeze storage where chemical reaction rates would be low. However, early compositional and petrologic studies established the presence of terrestrial alteration phases (e.g., [1, 2]). These were especially prevalent in chondrites because metal and troilite are most susceptible to terrestrial alteration [3]. Howardites, eucrites and diogenites (HEDs) are less prone to alteration because they have low abundances of metal and troilite. Nevertheless, investigations of HED meteorites document a wide array of mineralogical, compositional and isotopic effects of terrestrial alteration (e.g., [4-8]). Studies of the mineralogical effects of alteration [4] were done with old scanning electron microscope (SEM) technology which could only image small regions at a time. The micro-context of alteration phases was revealed, but larger-scale context was difficult to establish. Here we demonstrate the utility of wholethin-section X-ray mapping of eucrites by modern SEMs to document large-scale distributions of alteration materials which serve to evaluate sample freshness, highlight regions for detail study, and facilitate testing a hypothesis for alteration of eucrites [8]

Mittlefehldt, D. W.↗

Distribution of the pre-solar component in Allende and other carbonaceous chondrites

Detailed analyses of separated phases of several Allende Ca-Al-rich inclusions are reported which reveal a consistent pattern of large O-16 enrichments in spinel, pyroxene, and sometimes olivine, and small O-16 enrichments in melilite, feldspathoids, and grossular. The heterogeneous distribution of the O-16 excesses, together with their enhancement in minerals believed to be early solar nebular condensates, suggests the existence of pre-solar carriers of the isotopic anomaly, probably grains or molecules with oxygen which was nearly pure O-16. Pre-solar grains of corundum or spinel, and pre-solar molecules of SiO are considered possibilities. Excess O-16, relative to terrestrial abundances, has been found in all samples of C2, C3 (the Allende is this kind), and C4 carbonaceous chondrites which have been analyzed. No direct correlation has yet been observed between the oxygen anomalies and isotope anomalies in neon, magnesium, or xenon.

Clayton, R. N.↗

A New Look at Aubrites: Investigating 3D Modal Mineralogy with X-Ray Computed Tomography

The aubrites (approximately 30 known meteorites) are a unique group of differentiated meteorites that formed on asteroids with oxygen fugacities (ƒO2) from approximately 2 to approximately 6 log units below the iron-wustite buffer. At these highly reduced conditions, elements deviate from the geochemical behavior exhibited at terrestrial ƒO2, forming FeO-poor silicates and exotic sulfides. While previous studies have described the petrology and 2D modal abundances of aubrites, this work investigates the 3D modal mineralogies of silicate, metal, and sulfide phases in aubrite samples, which are then compared to the available 2D data. In addition to 3D modal mineralogies, we have examined the geochemistry of fourteen aubrites, including mineral major-element compositions, bulk-rock compositions, and oxygen isotopic compositions to understand their formation and evolution at extreme ƒO2 conditions. We utilize X-ray computed tomography (XCT) to non-destructively analyze the distribution and abundances of mineral phases in aubrites and locate composite clasts of sulfide grains for future analytical study. In order to better constrain elemental behavior under reduced conditions, we specifically target minerals phases that comprise moderately volatile elements (i.e. oldhamite [CaS], caswellsilverite [NaCrS2] and djerfisherite [K6Na(Fe,Cu,Ni)25S26Cl]) as it has been shown that their geochemical behavior changes as a function of ƒO2. Currently, we have produced 3D scans of the Norton County aubrite. The results of the XCT data have allowed for the determination of the abundances of silicate groundmass (i.e., enstatite, forsterite, albite, and diopside), light (based on electron density) sulfides (i.e. alabandite [MnS] and daubréelite [FeCr2S4]), heavy (based on electron density) sulfides (i.e., troilite [FeS]), and Fe,Ni metal by segmenting a density histogram in Volume Graphics Studio software. XCT scans of additional aubrites are underway. By combining the 3D representation of the exotic phases found in aubrites with existing 2D characterizations, we are able to better determine modal abundances. By integrating 3D and 2D modal abundances and geochemistry, we can ultimately better constrain aubrite petrogenesis and elemental partitioning under reduced conditions. Furthermore, application of this new 3D approach offers the opportunity to identify and select clasts for future study prior to cutting the sample, which will minimize sample loss of this precious material.

Wilbur, Zoe↗

Amino Acid Chemistry as a Link Between Small Solar System Bodies and Carbonaceous Chondrites

Establishing chemical links between meteorites and small solar system bodies, such as comets and asteroids, provides a tool for investigating the processes that occurred during the formation of the solar system. Carbonaceous meteorites are of particular interest, since they may have seeded the early Earth with a variety of prebiotic organic compounds including amino acids, purines and pyrimidines, which are thought to be necessary for the origin of life. Here we report the results of high-performance liquid chromatography (HPLC) based amino acid analyses of the acid-hydrolyzed hot water extracts from pristine interior pieces of the CI carbonaceous chondrites Orgueil and Ivuna and the CM meteorites Murchison and Murray. We found that the CI meteorites Orgueil and Ivuna contained high abundances of beta-alanine and glycine, while only traces of other amino acids like alanine, alpha-amino-n-butryic acid (ABA) and alpha-aminoisobutyric acid (AIB) were detected in these meteorites. Carbon isotopic measurements of beta-alanine and glycine in Orgueil by gas chromatography combustion-isotope ratio mass spectrometry clearly indicate an extraterrestrial origin of these amino acids. The amino acid composition of Orgueil and Ivuna was strikingly different from the CM chondrites Murchison and Murray. The most notable difference was the high relative abundance of B-alanine in Orgueil and Ivuna compared to Murchison and Murray. Furthermore, AIB, which is one of the most abundant amino acids found in Murchison and Murray, was present in only trace amounts in Orgueil and Ivuna. Our amino acid data strongly suggest that the CI meteorites Orgueil and Ivuna came from a different type of parent body than the CM meteorites Murchison and Murray, possibly from an extinct comet. It is generally thought that carbonaceous meteorites are fragments of larger asteroidal bodies delivered via near Earth objects (NEO). Orbital and dynamic studies suggest that both fragments of main belt asteroids and comets replenish the NEO population, therefore extinct comets may contribute up to half of all NEO's. A comparison of an amino acid analysis of a returned NEO sample to CI and CM carbonaceous chondrites would help establish a link between small solar system bodies and meteorites. Based on our amino acid measurements of CI and CM chondrites, amino acid chemistry can be included as an additional set of criteria to constrain the nature of meteorite parent bodies.

Glavin, Daniel P.↗

The isotopes of H and He in solar cosmic rays

The isotopic composition of H and He in solar cosmic rays was studied with the solar galactic cosmic ray experiment on the Orbiting Geophysical Observatory, OGO-6. Averaging over 20 days of data from seven flare events during 1969, the ratios He-3/-He-4 = 0.10 + or - 0.02, D/H (76) .0003 and T/H (76) .0001 in the 4 to 5 MeV/nucleon energy range were obtained. In addition, large variations were found in the relative abundance of He-3 from event of event, with a maximum ratio of He-3/He-4 = 0.26 + or - 0.08 observed on October 14 and 15, 1969. The relative abundance of He-3 and D during this event does not seem to be consistent with existing calculations of the nuclear interaction orgin of these isotopes.

Garrard, T. L.↗

Discreditation of Bobdownsite and the Establishment of Criteria for the Identification of Minerals with Essential Monofluorophosphate (PO3F2-)

Bobdownsite, IMA number 2008-037, was approved as a new mineral by the Commission on New Minerals, Nomenclature and Classification (CNMNC) as the fluorine endmember of the mineral whitlockite. The type locality of bobdownsite is in Big Fish River, Yukon Canada, and bobdownsite was reported to be the first naturally occurring mineral with essential monofluorophosphate (PO3F2-). The type specimen of bobdownsite has been reinvestigated by electron probe microanalysis (EPMA), and our data indicate that fluorine abundances are below detection in the mineral. In addition, we conducted detailed analysis of bobdownsite from the type locality by gas chromatography isotope ratio mass spectrometry, Raman spectroscopy, EPMA, and NMR spectroscopy. These data were compared with previously published data on synthetic monofluorophosphate salts. Collectively, these data indicate that bobdownsite is indistinguishable from whitlockite with a composition along the whitlockite-merrillite solid solution. Bobdownsite is therefore discredited as a valid mineral species. An additional mineral, krásnoite, has been purported to have monofluorophosphate components in its structure, but reexamination of those data indicate that F- in krásnoite forms bonds with Al, similar to OH- bonded to Al in perhamite. Consequently, krásnoite also lacks monofluorophosphate groups, and there are currently no valid mineral species with monofluorophosphate in their structure. We recommend that any future reports of new minerals that contain essential monofluorophosphate anions be vetted by abundance measurements of fluorine, vibrational spectroscopy (both Raman and FTIR), and where paramagnetic components are permissibly low, NMR spectroscopy. Furthermore, we emphasize the importance of using synthetic compounds containing monofluorophosphate anions as a point of comparison in the identification of minerals with essential monofluorophosphate. Structural data that yield satisfactory P-F bond lengths determined by X-ray crystallography, coupled with direct chemical analyses of fluorine in a material do not constitute sufficient evidence alone to identify a new mineral with essential monofluorophosphate anions.

McCubbin, Francis M.↗

Probing Light-Dependent Regulation of the Calvin Cycle Using a Multi-Omics Approach

Photoautotrophic microorganisms are increasingly explored for the conversion of atmospheric carbon dioxide into biomass and valuable products. The Calvin-Benson-Bassham (CBB) cycle is the primary metabolic pathway for net CO 2 fixation within oxygenic photosynthetic organisms. The cyanobacteria, Synechocystissp. PCC 6803, is a model organism for the study of photosynthesis and a platform for many metabolic engineering efforts. The CBB cycle is regulated by complex mechanisms including enzymatic abundance, intracellular metabolite concentrations, energetic cofactors and post-translational enzymatic modifications that depend on the external conditions such as the intensity and quality of light. However, the extent to which each of these mechanisms play a role under different light intensities remains unclear. In this work, we conducted non-targeted proteomics in tandem with isotopically non-stationary metabolic flux analysis (INST-MFA) at four different light intensities to determine the extent to which fluxes within the CBB cycle are controlled by enzymatic abundance. The correlation between specific enzyme abundances and their corresponding reaction fluxes is examined, revealing several enzymes with uncorrelated enzyme abundance and their corresponding flux, suggesting flux regulation by mechanisms other than enzyme abundance. Additionally, the kinetics of 13 C labeling of CBB cycle intermediates and estimated inactive pool sizes varied significantly as a function of light intensity suggesting the presence of metabolite channeling, an additional method of flux regulation. These results highlight the importance of the diverse methods of regulation of CBB enzyme activity as a function of light intensity, and highlights the importance of considering these effects in future kinetic models.

54 ENVIRONMENTAL SCIENCES↗

FE-60 and the evolution of eucrites

We have recently presented evidence for the existence of live Fe-60 in the early solar system. This evidence comes from observations of 2.4 to 50 epsilon unit (1 part in 10(exp 4)) relative excesses of Ni-60 measured in samples from the eucrite Chervony Kut (CK). These isotopic excesses have been produced by the decay of the short-lived radionuclide Fe-60 (T(sub 1/2) = 1.5 Ma). Because CK originates from a planetesimal which was totally molten and its high Fe/Ni ratio is due to a planet-wide Fe-Ni fractionation during metal-silicate segregation, the presence of the Fe-60 decay product indicates the large scale abundance of Fe-60 in the early solar system and its presence during differentiation of this planetesimal. The observed variable Ni-60 excesses in different bulk samples and mineral separates from CK can only be understood if some Fe-60 was still alive at the time when basaltic magma had solidified on the eucrite parent body. The lack of a correlation between Ni-60 and the respective Fe/Ni ratios in different mineral fractions from CK indicates a metamorphic remobilization of Ni after essentially all Fe-60 has decayed. However, Ni-60 from three bulk samples from different locations within the meteorite appears to correlate reasonably well with the respective Fe/Ni ratios. If we regard this correlation as an isochron then its slope yields a Fe-60/Fe-56 ratio f (3.9 +/- 0.6) x 10(exp -9) and an initial Ni-60 of 3.2 plus or minus 0.9 epsilon units at the time of crystallization of CK. Estimates based on these values and a approximately 10 Ma time interval between CK solidification and formation of the earliest condensates in the solar system followed by rapid accretion of planetary bodies indicate that the decay of Fe-60 could produce sufficient heat to melt these planetesimals. If Al-26 was present on a planetary scale as Fe-60 and at abundances close to values observed in Allende inclusions then melting of small early formed planets is inevitable. As an attempt to further explore the Fe-60/Ni-60 isotope system as an early solar system chronometer we studied another noncumulate eucrite, Juvinas (JUV) (sample USNM 1051), which belongs to the same subgroup as CK.

Shukolyukov, A.↗

Formation and Processing of Amorphous Silicates in Primitive Carbonaceous Chondrites and Cometary Dust

Chondritic-porous interplanetary dust particles (CP IDPs) exhibit strongly heterogeneous and unequilibrated mineralogy at sub-micron scales, are enriched in carbon, nitrogen and volatile trace elements, and contain abundant presolar materials [1-4]. These observations suggest that CP IDPs have largely escaped the thermal processing and water-rock interactions that have severely modified or destroyed the original mineralogy of primitive meteorites. CP IDPs are believed to represent direct samples of the building blocks of the Solar System - a complex mixture of nebular and presolar materials largely unperturbed by secondary processing. The chemical and isotopic properties of CP IDPs and their atmospheric entry velocities are also consistent with cometary origins. GEMS (glass with embedded metal and sulfides) grains are a major silicate component of CP IDPs. GEMS grains are < 0.5 microns in diameter objects that consist of numerous 10 to 50 nm-sized Fe-Ni metal and Fe-Ni sulfide grains dispersed in a Mg-Si-Al-Fe amorphous silicate matrix [2, 5]. Based on their chemistry and isotopic compositions, most GEMS appear to be non-equilibrium condensates from the early solar nebula [2]. If GEMS grains are a common nebular product, then they should also be abundant in the matrices of the most physically primitive chondritic meteorites. Although amorphous silicates are common in the most primitive meteorites [6-9], their relationship to GEMS grains and the extent to which their compositions and microstructure have been affected by parent body processing (oxidation and aqueous alteration) is poorly constrained. Here we compare and contrast the chemical, microstructural and isotopic properties of amorphous silicates in primitive carbonaceous chondrites to GEMS grains in IDPs.

Keller, Lindsay P.↗