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At least 199 records · Page 11

Development of Analytical Protocols For Organics and Isotopes Analysis on the 2009 MARS Science Laboratory.

The Mars Science Laboratory, under development for launch in 2009, is designed explore and quantitatively asses a local region on Mars as a potential habitat for present or past life. Its ambitious goals are to (1) assess the past or present biological potential of the target environment, (2) to characterize the geology and geochemistry at the MSL landing site, and (3) to investigate planetary processes that influence habitability. The planned capabilities of the rover payload will enable a comprehensive search for organic molecules, a determination of definitive mineralogy of sampled rocks and fines, chemical and isotopic analysis of both atmospheric and solid samples, and precision isotope measurements of several volatile elements. A range of contact and remote surface and subsurface survey tools will establish context for these measurements and will facilitate sample identification and selection. The Sample Analysis at Mars (SAM) suite of MSL addresses several of the mission's core measurement goals. It includes a gas chromatograph, a mass spectrometer, and a tunable laser spectrometer. These instruments will be designed to analyze either atmospheric samples or gases extracted from solid phase samples such as rocks and fines. We will describe the range of measurement protocols under development and study by the SAM engineering and science teams for use on the surface of Mars.

Mahaffy, P. R.↗

Radiation Chemistry of Solid Acetone in the Interstellar Medium - A New Dimension to an Old Problem

A laboratory investigation of acetone, an interstellar and cometary molecule, has produced new results concerning its decomposition in a radiation environment. Mid-infrared spectroscopy has been used to follow amorphous acetone's destruction by ionizing radiation (1 MeV protons) at 20 K. Radiation products identified are the CH4, CO, and CO2 usually made in such experiments, along with ketene, allene, and the acetonyl radical, all identified here for the first time in irradiated solid acetone. Evidence for the reduction product 2-propanol was suggestive, but a firm identification could not be made either for it or for the C2 hydrocarbons (i.e., C2H6, C2H4, C2H2). The acetyl radical was not observed as a radiation product. Isotopically labeled reagents were used to demonstrate ketene formation and to emphasize that multiple approaches are needed for robust assignments of infrared spectral features of irradiated icy solids. Results from a supporting radiation experiment with isotopically labeled acetic acid are described. Comparisons are made to a previous study of acetone's stability in extraterrestrial radiation environments, and caution is urged in measuring and interpreting CO abundances in irradiated icy solids.

cometary molecule↗

Radiation Chemistry of Solid Acetone in the Interstellar Medium - A New Dimension to an Old Problem

A laboratory investigation of acetone, an interstellar and cometary molecule, has produced new results concerning its decomposition in a radiation environment. Mid-infrared spectroscopy has been used to follow amorphous acetone’s destruction by ionizing radiation (1 MeV protons) at 20 K. Radiation products identified are the CH4, CO, and CO2 usually made in such experiments, along with ketene, allene, and the acetonyl radical, all identified here for the first time in irradiated solid acetone. Evidence for the reduction product 2-propanol was suggestive, but a firm identification could not be made either for it or for the C2 hydrocarbons (i.e., C2H6, C2H4, C2H2). The acetyl radical was not observed as a radiation product. Isotopically labeled reagents were used to demonstrate ketene formation and to emphasize that multiple approaches are needed for robust assignments of infrared spectral features of irradiated icy solids. Results from a supporting radiation experiment with isotopically labeled acetic acid are described. Comparisons are made to a previous study of acetone’s stability in extraterrestrial radiation environments, and caution is urged in measuring and interpreting CO abundances in irradiated icy solids.

R. L. Hudson↗

Search for Presolar Materials and Isotopically Anomalous Diffuse Insoluble Organic Matter in Samples From Asteroid 101955 Bennu

Carbonaceous asteroids allow us to study the original materials that formed the planets in the protoplanetary disk. They contain organic matter and (sub-)micrometer-size dust grains, called presolar grains, that condensed in the circumstellar envelopes of evolved stars and the ejecta of stellar explosions, such as novae and supernovae, before the formation of our Solar System. The isotopically anomalous organics are thought to have formed in the interstellar medium and the early Solar System. Whereas presolar grains provide insight into the building blocks of our Solar System, studying organics can help us understand the origin of life on Earth. These organics might have contributed to ingredients that helped life emerge. The return of samples from asteroid 101955 Bennu by NASA’s Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer (OSIRIS-REx) mission gives us a new opportunity to elucidate the formation mechanism(s) and evolution of organics, as well as the abundance and distribution presolar grains in carbonaceous asteroids. Here, we report on our ongoing work to characterize the isotopic and chemical compositions, microstructure, distribution, and abundance of insoluble organic matter (IOM) and presolar grains in Bennu samples. This work supports hypotheses 2 and 3 of the OSIRIS-REx Sample Analysis Plan.

P. Haenecour↗

A Complex History of Silicate Differentiation of Mars from Nd and Hf Isotopes in Crustal Breccia NWA 7034

Resolving the possible mantle and crustal sources for shergottite meteorites is crucial for understanding the formation and early differentiation of Mars. Orbiter and rover characterization of the martian surface reveal that the major element composition of most of its surface does not match the shergottites (McSween et al., 2009)leaving the relationship between them poorly understood. The identification of the meteorite NWA 7034 and its pairs as a Mars surface rock (Cartwright et al., 2014)provides access to a representative sample of Mars' crust (Agee et al., 2013;Humayun et al., 2013). Utilizing the short-lived Sm-146 - Nd-142, and long-lived Sm-142 - Nd-142 and Lu-176 - Hf-176 chronometers, which are sensitive to silicate differentiation, we analyzed three fragments of NWA 7034. The very negative mean isotopic compositions for this breccia, μNd-142(sub JNdi-1)=−45 +/-5(2SD), εNd-143(sub CHUR)=−16.7 +/-0.4(2SD) and εHf176(sub CHUR)=−61 +/-9(2SD) point to an ancient origin for this martian crust. However, modeling of the data shows that the crust sampled by NWA 7034 possesses a Hf/Nd ratio and coupled εNd-143 - μNd-142 model age that are incompatible with this crustal reservoir being an end-member that generated the shergottite source mixing array. In addition, this crust is not juvenile, despite its rare earth element profile, but has had a multistage formation history. Therefore, early crustal extraction alone was not responsible for the creation of the reservoirs that produced the shergottites. Instead mantle reservoirs formed via other early differentiation processes such as in a Mars magma ocean must be responsible for the trace element and isotopic signatures present in shergottites.

Rosalind M. G. Armytage↗

Composition and metabolism of microbial communities in soil pores

Delineation of microbial habitats within the soil matrix and characterization of their environments and metabolic processes are crucial to understand soil functioning, yet their experimental identification remains persistently limited. We combined single- and triple-energy X-ray computed microtomography with pore specific allocation of 13 C labeled glucose and subsequent stable isotope probing to demonstrate how long-term disparities in vegetation history modify spatial distribution patterns of soil pore and particulate organic matter drivers of microbial habitats, and to probe bacterial communities populating such habitats. Here we show striking differences between large (30-150 µm Ø) and small (4-10 µm Ø) soil pores in (i) microbial diversity, composition, and life-strategies, (ii) responses to added substrate, (iii) metabolic pathways, and (iv) the processing and fate of labile C. We propose a microbial habitat classification concept based on biogeochemical mechanisms and localization of soil processes and also suggests interventions to mitigate the environmental consequences of agricultural management.

59 BASIC BIOLOGICAL SCIENCES↗

Cosmic ray experimental observations

The current experimental situation in cosmic ray studies is discussed, with special emphasis on the development of new detector systems. Topics covered are the techniques for particle identification, energy measurements, gas Cerenkov counters, magnet spectrometers, ionization spectrometers, track detectors, nuclear emulsions, multiparameter analysis using arrays of detectors, the Goddard ionization spectrometer, charge spectra, relative abundances, isotope composition, antinuclei in cosmic rays, electrons, the measurement of cosmic ray arrival directions, and the prehistory of cosmic rays.

Balasubrahmanyan, V. K.↗

Identification of HgO/x/ species by matrix isolation spectroscopy

The condensation of Hg atoms in an ozone-doped argon matrix gas with irradiation from a medium-pressure mercury arc lamp at 10 K resulted in the formation of several trapped HgO(x) species. Tentative identification of HgO has been made from absorption bands appearing in the visible and IR regions of the spectrum based on (O-16)2 and (O-18)2 isotope studies. The following spectroscopic constants were obtained: nu(00) = 14634 cm, nu(1) = 548 cm, and nu(11) = 676 cm. Some qualitative evidence was obtained for the existence of HgO2.

Butler, R.↗

A silicon surface barrier telescope for solar particles identification

From the results three conclusions can be made: (1) the detector system described and tested is capable of good charge resolution from He to Al although beyond Ne the statistic is very poor; (2) in the high gain mode, isotopic resolution has been achieved for Li-6/Li-7 Be-7/Be-9; (3) the much higher yield of He over He and of Be-9 over Be-10 in these types of nuclear reactions prevents obtaining experimental evidence of those isotopes, although it is believed that, at least He-3/He-4 can be resolved under other more favorable conditions (i.e., solar He-3-rich events).

Sequeiros, J.↗

SNC Meteorites, Organic Matter and a New Look at Viking

Recently, evidence has begun to grow supporting the possibility that the Viking GC-MS would not have detected certain carboxylate salts that could have been present as metastable oxidation products of high molecular weight organic species. Additionally, despite the instrument's high sensitivity, the possibility had remained that very low levels of organic matter, below the instrument's detection limit, could have been present. In fact, a recent study indicates that the degradation products of several million microorganisms per gram of soil on Mars would not have been detected by the Viking GC-MS. Since the strength of the GC-MS findings was considered enough to dismiss the biology packet, particularly the LR results, any subsequent evidence suggesting that organic molecules may in fact be present on the Martian surface necessitates a re-evaluation of the Viking LR data. In addition to an advanced mass spectrometer to look for isotopic signatures of biogenic processes, future lander missions will include the ability to detect methane produced by methanogenic bacteria, as well as techniques based on biotechnology. Meanwhile, the identification of Mars samples already present on Earth in the form of the SNC meteorites has provided us with the ability to study samples of the Martian upper crust a decade or more in advance of any planned sample return missions. While contamination issues are of serious concern, the presence of indigenous organic matter in the form of polycyclic aromatic hydrocarbons has been detected in the Martian meteorites ALH84001 and Nakhla, while there is circumstantial evidence for carbonaceous material in Chassigny. The radiochronological ages of these meteorites are 4.5 Ga, 1.3 Ga, and 165 Ma respectively representing a span of time in Earth history from the earliest single-celled organisms to the present day. Given this perspective on organic material, a biological interpretation to the Viking LR results can no longer be ruled out. In the LR experiment, a solution containing C-14 labeled organic compounds was injected into soil samples. The detection of radioactivity in the overhead space would indicate that one or more of the substrates had been chemically converted into a carbon-containing gas. To serve as a control, some samples were heated enough to destroy most known terrestrial microbes so that an indication for life would be a positive response from unheated samples and a negative response from heated samples. On Mars, the LR results had met minimum criteria for a biological interpretation but due to the GC-MS results, the LR responses were later attributed to putative soil inorganic oxidants. Since the time of Viking, studies have been carried out with the objective of determining an oxidant or combination of oxidants that might exist on Mars and have produced the observed kinetics of the LR response. To date, no such agent has been found that produces all aspects of the LR results on Mars. While the above considerations in no way imply the existence of life forms at the two Viking landing sites, inorganic and biological explanations for the Viking LR data should now be considered equally plausible until more complete studies of the Martian surface are carried out. Therefore, in light of the SNC meteorites data and their implications for the possibility of organic matter near or on the Martian surface the Viking biology experiments should thus be seen, not as failures for their inability to provide unambiguous evidence for or against Martian life, but as a foundation for the development of future life-detection instruments. Additional information is contained in the original extended abstract.

Warmflash, David M.↗

The Atmospheres of Titan and Saturn in the Infrared from Cassini: The Interplay Between Observation and Laboratory Studies

The Composite Infrared Spectrometer (CIRS) aboard the Cassini spacecraft has been recording spectra of Saturn and Titan since its arrival in the Saturn system in 2004. CIRS, a Fourier transform spectrometer, observes the thermal infrared spectrum of both atmospheres from 10 to 1500/cm with resolutions up to 0.5/cm (Flasar et al. 2004). From these data CIRS provides global coverage of the molecular composition of the stratosphere and troposphere, as well as maps of temperature and winds. From such studies CIRS helps reveal the chemistry and evolutionary history of Saturn and Titan and their relationships to other Solar System bodies. The Cassini mission is continuing until 2017, permitting CIRS to search for atmospheric changes during more than a Saturnian season. By combining with results from Voyager (1980, 1981) the baseline becomes more than one Saturnian year (Coustenis et al. 2011). CIRS spectroscopy of the atmospheres of Saturn and Titan has raised a variety of questions that require new laboratory studies. A complete understanding of the CIRS high-resolution atmospheric spectra cannot be fully achieved without new or improved line positions and intensities for some trace molecules (e.g., Nixon et al. 2009). Isotopic variants of some of the more abundant species often need improved line parameters in order to derive isotopic ratios (e.g., Coustenis et al. 2008 and Fletcher et a!. 2009). Isotopic ratios contain information about the history of an atmosphere if experimental fractionation rates are available (Jennings et al. 2009). Some aerosol and haze features continue to defy identification and will not be explained without better knowledge of how these materials are formed and until we obtain their laboratory spectra. The interaction between CIRS investigations and laboratory research has been productive and has already led to new discoveries.

Jennings, D. E.↗

D-Band EPR and ENDOR Spectroscopy of 15 N-Labeled Photosystem I

For billions of years, nature has optimized the photosynthetic machinery that converts light energy into chemical energy. Key primary reactions of photosynthesis occur in large membrane protein-cofactor complexes. The light-induced sequential electron transfer reactions occur through a chain of donor/acceptor cofactors embedded in the protein matrix resulting in a long-lived transmembrane charge-separated state. EPR is the method of choice to study electron transfer and the interaction of protein environment with redox-active cofactors. However, the spectra of organic cofactor radicals typically are not fully resolved and severely overlap at conventional X-band EPR. Even at Q-band EPR, this overlap is present and often a serious problem. As a result, there is a large variation of the reported EPR data and limited understanding of electronic structures of several redox-active cofactors. These serious problems can often be overcome by the excellent spectral resolution provided by high-frequency EPR (HF EPR). In this work, we study the electronic structure of the primary electron donor P 700 and the secondary electron acceptor A 1 of Photosystem I (PSI) using 130 GHz (D-band) EPR and Electron-Nuclear-Double-Resonance (ENDOR) spectroscopy. PSI was isotopically labeled with 15 N (I = $\frac{1/2}$) to avoid quadrupolar interactions in the most abundant nitrogen isotope 14 N (I = 1) and simplify the ENDOR spectra. ENDOR spectroscopy is central for determining the hyperfine coupling of nitrogen atoms of the two chlorophyll molecules comprising oxidized P 700 and the involvement of protein nitrogen atoms with reduced A 1 . While HF ENDOR of A 1 - allows identification of two nitrogen atoms, HF ENDOR of P 700 + still does not permit unique assignment of the recorded hyperfine couplings.

15N↗

Identification of Primitive Unequilibrated Ordinary Chondrites from Four Antarctic Dense Collections Areas (EET, GRO, LEW, and MET)

Unequilibrated ordinary chondrites (UOC) typically contain metal [1], primitive chondrules [2], pre-solar grains [3], organics [4], nebular materials in matrix [5], and isotopic records of early solar system processes [6], and are thus scientifically valuable samples that provide important information about the early solar system. UOCs from dense collection areas (DCA) like in the Transantarctic Mtns. pose several specific challenges. First, they are commonly part of large pairing groups for which preliminary studies are followed up by detailed studies that reveal differences among the pairs (e.g., [7,8]). Second, subsequent visits to the DCA identify and recover new members of the pairing group. Thus over time, the pairing groups must be re-assessed as new information becomes available for existing and new members of the larger pairing groups. Given the suggestion that many samples in these groups could be more primitive than L3.4 (e.g., [7]), we have undertaken a survey of 103 chondrites. Here we report olivine analyses from Type II (FeO-rich) chondrules with a goal of identifying primitive (<L3.20) UOCs using the Cr in olivine approach [9]. In the process of the detailed work, we identified 22 samples of petrologic grade 3.2 or lower that were previously unrecognized. Pairing relations of L3.x chondrites in these 3 areas are accordingly re-assessed.

chondrite↗

Direct reactions with the AT-TPC

Direct reactions are crucial tools for accessing properties of the atomic nucleus. Fundamental and exotic phenomena such as collective modes, pairing, weakbinding effects and evolution of single-particles energies can be investigated in peripheral collisions between a heavy nucleus and a light target. The necessity of using inverse kinematics to reveal how these structural properties change with isospin imbalance renders direct reactions a challenging technique when using the missing mass method. In this scenario, Active Target Time Projection Chambers (AT-TPC) have demonstrated an outstanding performance in enabling these types of reactions even under conditions of very low beam intensities. The AT-TPC of the Facility for Rare Isotope Beams (FRIB) is a next generation multipurpose Active Target. When operated inside a solenoidal magnet, direct reactions benefit from the measurement of the magnetic rigidity that enables particle identification and the determination of the excitation energy with high resolution without the need of auxiliary detectors. Additionally, the AT-TPC can be coupled to a magnetic spectrometer improving even further its spectroscopic investigation capability. In this contribution, we discuss inelastic scattering and transfer reaction data obtained via the AT-TPC and compare them to theory. In particular, we present the results for the 14 C(p,p′) and 12 Be (p,d) 11 Be reactions. For 14 C, we compare the experimental excitation energy of the first 1 – excited state with coupled-cluster calculationsbased on nuclear interactions from chiral effective field theory and with available shell-model predictions. For 12 Be, we determine the theoretical spectroscopic factors of the 12 Be (p,d) 11 Be transfer reaction in the shell modeland compare them to the experimental excitation spectrum from a qualitative standpoint.

active target↗

Mass spectrometric analysis of organic compounds, water and volatile constituents in the atmosphere and surface of Mars - The Viking Mars Lander.

An experiment centering around a mass spectrometer is described, which is aimed at the identification of organic substances present in the top 10 cm of the surface of Mars and an analysis of the atmosphere for major and minor constituents as well as isotopic abundances. In addition, an indication of the abundance of water in the surface and some information concerning the mineralogy can be obtained by monitoring the gases produced upon heating the soil sample. The organic material will simply be expelled by heating to 150, 300, and 500 C into the carrier gas stream of a gas chromatograph interfaced to the mass spectrometer or by slowly heating the sample in direct communication with the spectrometer. It is planned to analyze a total of up to nine soil samples in order to study diurnal and seasonal variations. The system is designed to give useful data even for minor constituents if the total of organics should be as low as 5 ppm. The spectrometer covers the mass range of 12-200 with adequate resolution.

Anderson, D. M.↗

Heavy carbon in individual oxide grains from the Murchison meteorite

The carbon isotopic composition of individual oxide grains from Murchison HF-HCl acid residue CFOc has been measured in the ion microprobe. Many grains contain carbon with large C-13 excesses ranging to 7000 per mil. In most cases the carbon is present as micron-sized subgrains. The association of silicon with the anomalous carbon points towards SiC as carrier. If this tentative identification is correct, then the SIC grains most likely originated in the circumstellar atmospheres of red giants. Oxide grains in which the O-18/O-16 ratio has also been measured show variable O-16 excesses which are not correlated with the C-13 excesses. This indicates that the sources of the anomalous carbon and oxygen isotopic compositions of the oxide grains are unrelated.

Zinner, Ernst↗

Scientific returns from a program of space missions to comets

A program of cometary missions is proposed. The nature and size of interstellar dust, its origin and evolution; identification of new interstellar molecules; clarification of interstellar chemistry; accretion of grains into protosolar cometesimals; role of a T Tauri wind in the dissipation of the protosolar nebula; record of isotopic anomalies, better preserved in comets than in meteorites; cosmogenic and radiogenic dating of comets; cosmochronology and mineralogy of meteorites, as compared with that of cometary samples; origin of the earth's biosphere, and the origin of life are topics discussed in relation to comet exploration.

Delsemme, A. H.↗

Carbon in comet dust

The association of Halley particle results with data from existing meteoritic materials that can be analyzed in the laboratory is discussed. Comet samples must exist in present collections of meteoritic materials and the Halley results provide clues for identifying them. Although it is not presently possible to positively identify cometary meteorites or cometary interplanetary dust (IDP) samples, it is possible to determine which materials are similar to Halley dust and which ones are distinctly unlike Halley. The properties of these existing Halley-compatible samples provide insight into the possible properties of cometary material. Positive identification of meteoritic comet samples or direct samples returned from a comet nucleus would of course revolutionize our ability to study carbonaceous matter in comets. Modern analytical techniques are very powerful and it is possible to perform elemental, chemical, mineralogical and even limited isotopic analysis on micron-size particles. There is an important synergism between the laboratory studies of collected samples and astronomical data from comets and interstellar grains. To fully interpret results there must be convincing methods for associating a particular class or classes of meteoritic material with comets. Ultimately this will be done by direct comet sample return such as the Rosetta mission under development by ESA. At the present time the only links that can be made involve comparison with sample properties and measurable properties of comets. Unfortunately there is at present no known unique property of cometary dust that allows its absolute identification in the laboratory. The results from Halley encounters and observation do provide much new information on cometary grains. The Halley grain compositions, density, size distribution and scattering properties all provide a basis for future investigations. Other Halley properties such as the presence of polyoxymethylene and the 3.4um emission feature could play key roles for making convincing links in the future.

Brownlee, D. E.↗