Experimental and Analytical Studies of Solar System Chemistry

NASA Technical Reports Server (NTRS)

Burnett, Donald S.

2003-01-01

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.

High pressure cosmochemistry applied to major planetary interiors: Experimental studies. [phase diagram for the ammonia water system

NASA Technical Reports Server (NTRS)

Nicol, M. F.; Johnson, M.; Schwake, A.

1983-01-01

Progress is reported in the development of the P-T-X diagram for 0 less than or = X less than or = 0.50 and in the development of techniques for measuring adiabats of phases of NH3-H2O. The partial phase diagram is presented, investigations of the compositions of ammonia ices are described, and methods for obtaining the infrared spectra of ices are discussed.

Stellar Explosions: Hydrodynamics and Nucleosynthesis

NASA Astrophysics Data System (ADS)

Jose, Jordi

2016-01-01

Stars are the main factories of element production in the universe through a suite of complex and intertwined physical processes. Such stellar alchemy is driven by multiple nuclear interactions that through eons have transformed the pristine, metal-poor ashes leftover by the Big Bang into a cosmos with 100 distinct chemical species. The products of stellar nucleosynthesis frequently get mixed inside stars by convective transport or through hydrodynamic instabilities, and a fraction of them is eventually ejected into the interstellar medium, thus polluting the cosmos with gas and dust. The study of the physics of the stars and their role as nucleosynthesis factories owes much to cross-fertilization of different, somehow disconnected fields, ranging from observational astronomy, computational astrophysics, and cosmochemistry to experimental and theoretical nuclear physics. Few books have simultaneously addressed the multidisciplinary nature of this field in an engaging way suitable for students and young scientists. Providing the required multidisciplinary background in a coherent way has been the driving force for Stellar Explosions: Hydrodynamics and Nucleosynthesis. Written by a specialist in stellar astrophysics, this book presents a rigorous but accessible treatment of the physics of stellar explosions from a multidisciplinary perspective at the crossroads of computational astrophysics, observational astronomy, cosmochemistry, and nuclear physics. Basic concepts from all these different fields are applied to the study of classical and recurrent novae, type I and II supernovae, X-ray bursts and superbursts, and stellar mergers. The book shows how a multidisciplinary approach has been instrumental in our understanding of nucleosynthesis in stars, particularly during explosive events.

Stellar Explosions: Hydrodynamics and Nucleosynthesis

NASA Astrophysics Data System (ADS)

José, Jordi

2015-12-01

Stars are the main factories of element production in the universe through a suite of complex and intertwined physical processes. Such stellar alchemy is driven by multiple nuclear interactions that through eons have transformed the pristine, metal-poor ashes leftover by the Big Bang into a cosmos with 100 distinct chemical species. The products of stellar nucleosynthesis frequently get mixed inside stars by convective transport or through hydrodynamic instabilities, and a fraction of them is eventually ejected into the interstellar medium, thus polluting the cosmos with gas and dust. The study of the physics of the stars and their role as nucleosynthesis factories owes much to cross-fertilization of different, somehow disconnected fields, ranging from observational astronomy, computational astrophysics, and cosmochemistry to experimental and theoretical nuclear physics. Few books have simultaneously addressed the multidisciplinary nature of this field in an engaging way suitable for students and young scientists. Providing the required multidisciplinary background in a coherent way has been the driving force for Stellar Explosions: Hydrodynamics and Nucleosynthesis. Written by a specialist in stellar astrophysics, this book presents a rigorous but accessible treatment of the physics of stellar explosions from a multidisciplinary perspective at the crossroads of computational astrophysics, observational astronomy, cosmochemistry, and nuclear physics. Basic concepts from all these different fields are applied to the study of classical and recurrent novae, type I and II supernovae, X-ray bursts and superbursts, and stellar mergers. The book shows how a multidisciplinary approach has been instrumental in our understanding of nucleosynthesis in stars, particularly during explosive events.

Isotopic studies of planetary and nuclear materials: A scientific tribute to Ian Douglass Hutcheon (1947-2015)

NASA Astrophysics Data System (ADS)

Huss, Gary R.

2017-03-01

This issue of Geochimica et Cosmochimica Acta is a scientific tribute to Dr. Ian D. Hutcheon (Fig. 1), who passed away on March 26th, 2015. Ian was a pioneer in the fields of isotope cosmochemistry and nuclear forensics, a friend and colleague to many of us, and an effective and dedicated mentor to young scientists. His scientific interests were wide-ranging and are reflected in the papers in this issue. Many of the authors worked closely with him over the years.

Radial Breathing Modes in Cosmochemistry and Meteoritics

NASA Technical Reports Server (NTRS)

Wilson, T.L.; Wilson, K.B.

2009-01-01

One area of continuing interest in cosmochemistry and meteoritics (C&M) is the identification of the nature of Q-phase, although some researchers in C&M are not reporting relevant portions of Raman spectral data. Q is the unidentified carrier of noble gases in carbonaceous chondrites (CCs). Being carbonaceous, the focus has been on any number of Q-candidates arising from the sp2 hybridization of carbon (C). These all derive from various forms of graphene, a monolayer of C atoms packed into a two-dimensional (2D) hexagonal honeycomb lattice that is the basic building block for graphitic materials of all other dimensions for sp2 allotropes of C. As a basic lattice, 2D graphene can be curled into fullerenes (0D), wrapped into carbon nanotubes or CNTs (1D), and stacked into graphite (3D). These take such additional forms as scroll-like carbon whiskers, carbon fibers, carbon onions, GPCs (graphite polyhedral crystals) [6], and GICs (graphite intercalation compounds). Although all of these have been observed in meteoritics, the issue is which can explain the Q-abundances. In brief, one or more of the 0D-3D sp2 hybridization forms of C is Q. For some Q-candidates, the radial breathing modes (RBMs) are the most important Raman active vibrational modes that exist, and bear a direct relevance to solving this puzzle. Typically in C&M they are ignored when present. Their importance is addressed here as smoking-gun signatures for certain Q-candidates and are very relevant to the ultimate identification of Q.

Condensation from Cluster-IDP Enriched Vapor Inside the Snow Line: Implications for Mercury, Asteroids, and Enstatite Chondrites

NASA Technical Reports Server (NTRS)

Ebel, D. S.; Alexander, C. M. OD.

2005-01-01

Enstatite chondrites (EC) contain highly reduced matrix minerals (e.g.- (Mg,Fe,Mn)S solid solution, CaS) that probably formed in thermodynamic equilibrium with a vapor phase. EC chondrules contain enstatite, Fs5 to Fs30, in which iron was reduced after formation, also by interaction with vapor [1, 2]. The origin and location of this reducing vapor bears upon the formation of the terrestrial planets (Mercury to Mars), the remnant chemical zoning of the asteroid belt (E, S, C, D-types), and the cosmochemistry of metals in the early solar system.

Evidence that Polycyclic Aromatic Hydrocarbons in Two Carbonaceous Chondrites Predate Parent-Body Formation

NASA Technical Reports Server (NTRS)

Plows, F. L.; Elsila, J. E.; Zare, R. N.; Buseck, P. R.

2003-01-01

Organic material in meteorites provides insight into the cosmochemistry of the early solar system. The distribution of polycyclic aromatic hydrocarbons (PAHs) in the Allende and Murchison carbonaceous chondrites was investigated using spatially resolved microprobe laser-desorption laser-ionization mass spectrometry. Sharp chemical gradients of PAHs are associated with specific meteorite features. The ratios of various PAH intensities relative to the smallest PAH, naphthalene, are nearly constant across the sample. These findings suggest a common origin for PAHs dating prior to or contemporary with the formation of the parent body, consistent with proposed interstellar formation mechanisms.

Experiments in Planetary and Related Sciences and the Space Station

NASA Technical Reports Server (NTRS)

Greeley, Ronald (Editor); Williams, Richard J. (Editor)

1987-01-01

Numerous workshops were held to provide a forum for discussing the full range of possible experiments, their science rationale, and the requirements on the Space Station, should such experiments eventually be flown. During the workshops, subgroups met to discuss areas of common interest. Summaries of each group and abstracts of contributed papers as they developed from a workshop on September 15 to 16, 1986, are included. Topics addressed include: planetary impact experimentation; physics of windblown particles; particle formation and interaction; experimental cosmochemistry in the space station; and an overview of the program to place advanced automation and robotics on the space station.

Mass spectrometry.

NASA Technical Reports Server (NTRS)

Burlingame, A. L.; Johanson, G. A.

1972-01-01

Review of the current state of mass spectrometry, indicating its unique importance for advanced scientific research. Mass spectrometry applications in computer techniques, gas chromatography, ion cyclotron resonance, molecular fragmentation and ionization, and isotope labeling are covered. Details are given on mass spectrometry applications in bio-organic chemistry and biomedical research. As the subjects of these applications are indicated alkaloids, carbohydrates, lipids, terpenes, quinones, nucleic acid components, peptides, antibiotics, and human and animal metabolisms. Particular attention is given to the mass spectra of organo-inorganic compounds, inorganic mass spectrometry, surface phenomena such as secondary ion and electron emission, and elemental and isotope analysis. Further topics include mass spectrometry in organic geochemistry, applications in geochronology and cosmochemistry, and organic mass spectrometry.

The Soviet-American Conference on Cosmochemistry of the Moon and Planets, Part 1

NASA Technical Reports Server (NTRS)

Pomeroy, J. H. (Editor); Hubbard, N. J. (Editor)

1977-01-01

The basic goal of the conference was consideration of the origin of the planets of the solar system, based on the physical and chemical data obtained by study of the material of the moon and planets. Papers at the conference were presented in the following sessions: (1) Differentiation of the material of the moon and planets; (2) The thermal history of the moon; (3) Lunar gravitation and magnetism; (4) Chronology of the moon, planets, and meteorites; (5) The role of exogenic factors in the formation of the lunar surface; (6) Cosmochemical hypotheses about the origin and evolution of the moon and planets; and (7) New data about the planets Mercury, Venus, Mars, and Jupiter.

Hydrogen cyanide polymerization: a preferred cosmochemical pathway.

PubMed

Matthews, C N

1992-01-01

Current research in cosmochemistry shows that crude organic solids of high molecular weight are readily formed in planetary, interplanetary and interstellar environments. Underlying much of this ubiquitous chemistry is a low energy route leading directly to the synthesis of hydrogen cyanide and its polymers. Evidence from laboratory and extraterrestrial investigations suggests that these polymers plus water yield heteropolypeptides, a truly universal process that accounts not only for the past synthesis of protein ancestors on Earth but also for reactions proceeding elsewhere today within our solar system, on planetary bodies and satellites around other stars and in the dusty molecular clouds of spiral galaxies. The existence of this preferred pathway - hydrogen cyanide polymerization - surely increases greatly the probability that carbon-based life is widespread in the universe.

Progress in the Early Solar System Chronology: A Sketch of an Ever-Changing Landscape

NASA Technical Reports Server (NTRS)

Amelin, Yuri; Yin, Q.-Z.; Krot, A. N.; Bouvier, A.; Wadhwa, M.; Kleine, T.; Nyquist, L. E.

2011-01-01

The years since the Workshop on the Chronology of Meteorites and the Early Solar System, are marked with ongoing progress in cosmochronology. Rapid improvements in techniques, discovery of new meteorites unlike any previously known, and findings that what was deemed well established constants are actually variables, will be reflected in an updated review of the solar system chronology we are currently preparing. Along with updating the database of meteorite ages, it will involve development of a set of criteria for evaluation of accuracy and consistency of isotopic dates across the entire range of meteorite classes and isotope chronometer systems. Here we present some ideas on what we think is important in meteorite chronology, and invite the cosmochemistry community to discuss them.

Quantum chemical study of relative reactivities of a series of amines and nitriles - Relevance to prebiotic chemistry

NASA Technical Reports Server (NTRS)

Loew, G. H.; Berkowitz, D.; Chang, S.

1975-01-01

Using the Iterative Extended Huckel Theory (IEHT) calculations of the electron distribution and orbital energies of a series of thirteen amines, nitriles and amino-nitriles relevant to prebiotic and cosmo-chemistry have been carried out. Ground state properties such as the energy and nature of the highest occupied (HOMO) and lowest empty (LEMO) molecular orbitals, net atomic charges and number of nonbonding electrons have been identified as criteria for correlating the relative nucleophilicity of amine and nitrile nitrogens and the electrophilicity of nitrile and other unsaturated carbon atoms. The results of such correlations can be partially verified by known chemical behavior of these compounds and are used to predict and understand their role in prebiotic organic synthesis.

Chemical evolution and the origin of life

NASA Technical Reports Server (NTRS)

Oro, J.

1983-01-01

A review is presented of recent advances made in the understanding of the formation of carbon compounds in the universe and the occurrence of processes of chemical evolution. Topics discussed include the principle of evolutionary continuity, evolution as a fundamental principle of the physical universe, the nuclear synthesis of biogenic elements, organic cosmochemistry and interstellar molecules, the solar nebula and the solar system in chemical evolution, the giant planets and Titan in chemical evolution, and comets and their interaction with the earth. Also examined are carbonaceous chondrites, environment of the primitive earth, energy sources available on the primitive earth, the synthesis of biochemical monomers and oligomers, the abiotic transcription of nucleotides, unified prebiotic and enzymatic mechanisms, phospholipids and membranes, and protobiological evolution.

The Impact of International Scientific Teams on Investigations of Yugoslavian Meteorites

NASA Astrophysics Data System (ADS)

Kolomejceva-Jovanovic, L.

2008-10-01

Investigations of scientific heritage is very important for every country. The evidence concerning the meteorites which have fallen upon the territory of former Yugoslavia can be a nice example. The samples of Yugoslav meteorites can be found in the biggest world museums of natural history (in Washington, Moscow, Vienna, Paris, Budapest, Berlin, Prague and London). In such a way scientists engaged in the area of meteorites, cosmochemistry, cosmic mineralogy, astrochemistry, astrophysics and other multidisciplinary scientific branches have the possibility to study these meteorites. The huge impact on the study of Yugoslav meteorites is given by international teams from Institute of Physics (Belgrade), Joint Institute for Nuclear Investigations (Dubna, Russia), Naturhistorisches Museum (Vienna, Austria), Institute of Geochemistry and Analytical Chemistry (Moscow, Russia) and Museum of Natural History (Belgrade).

Environmental geochemistry at the global scale

USGS Publications Warehouse

Plant, J.; Smith, D.; Smith, B.; Williams, L.

2001-01-01

Land degradation and pollution caused by population pressure and economic development pose a threat to the sustainability of the earth's surface, especially in tropical regions where a long history of chemical weathering has made the surface environment particularly fragile. Systematic baseline geochemical data provide a means of monitoring the state of the environment and identifying problem areas. Regional surveys have already been carried out in some countries, and with increased national and international funding they can be extended to cover the rest of the land surface of the globe. Preparations have been made, under the auspices of the International Union of Geological Surveys (IUGS) and the International Association of Geochemistry and Cosmochemistry (IAGC) for the establishment of just such an integrated global database. ?? 2001 NERC. Published by Elsevier Science Ltd.

Current Research at the University of Chicago Enrico Fermi Institute and James Franck Institute

DOE Office of Scientific and Technical Information (OSTI.GOV)

Swordy, Simon

2009-03-04

These talks will give an overview of physics research at the University of Chicago centered in two research institutes. The Enrico Fermi Institute pursues research in some core areas of the physical sciences. These include cosmology, particle physics, theoretical physics, particle astrophysics, and cosmochemistry. The EFI talk will focus on some examples of these activities which together will provide a broad overview of EFI science. Research at the James Franck Institute centers on the intersection between physics, chemistry and materials science, with the aim to unravel the complex connections between structure and dynamics in condensed matter systems. The JFI ismore » also home to the Chicago Materials Research Science and Engineering Center. The JFI talk will provide highlights of current projects by JFI members.« less

NUCLEAR CHEMISTRY RESEARCH AT CARNEGIE INSTITUTE OF TECHNOLOGY 1962-1963. Progress Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

1963-06-01

Progress is reported on: nuclear reaction studies of cross sections of iron and stone meteoritic elements for 130- to 400-Mev protons, simulated cosmic- ray irradiations of thick iron and stone targets with 100-Mev to 3-Bev protons, and induced alpha-activity in short half-life ranges; nuclear geochemistry and cosmochemistry studies of nuclide dating of sediments, pseudo-diffusion in ocean and Maria sediments, cosmogenic radionuclides in iron and stone meteorites, cosmogenic radionuclides in Bondoc Achondrite and Bogou iron, half life of Mn/sup 53/, cosmogenic radioactivity in fragments of Sputnik N, Be/sup 10/ occurrence in tektites, and conversion of sealed anticoincidence shield counters to flow,more » counters; and the search for natural radioactivity in Ca/sup 48/. (B.O.G.)« less

Geochemistry and cosmochemistry of fullerenes 3: Reaction of C60 and C70 with ozone

NASA Technical Reports Server (NTRS)

Heymann, D.; Chibante, L. P. F.

1993-01-01

C60 and C70 dissolved in toluene were treated with O2 gas containing 2.6 volume percent ozone and with O3-free oxygen. No reaction products were detected for 0.1 mole of O2 passed through the solution, but destruction of C60 was clearly detectable for a dose of 10(exp -6) moles of O3. C70 was destroyed more slowly than C60. Among the substances remaining in solution, we identified C60O, C70O, C60O2, C60O3, and C60O4. C60 crystals exposed to O3 at room temperature became less soluble in toluene in a matter of days, but oxides were apparently not formed.

Current Research at the University of Chicago Enrico Fermi Institute and James Franck Institute

ScienceCinema

Swordy, Simon

2017-12-22

These talks will give an overview of physics research at the University of Chicago centered in two research institutes. The Enrico Fermi Institute pursues research in some core areas of the physical sciences. These include cosmology, particle physics, theoretical physics, particle astrophysics, and cosmochemistry. The EFI talk will focus on some examples of these activities which together will provide a broad overview of EFI science. Research at the James Franck Institute centers on the intersection between physics, chemistry and materials science, with the aim to unravel the complex connections between structure and dynamics in condensed matter systems. The JFI is also home to the Chicago Materials Research Science and Engineering Center. The JFI talk will provide highlights of current projects by JFI members.

Comparative Planetary Mineralogy: V/(Cr+Al) Systematics in Chromites as an Indicator of Relative Oxygen Fugacity

NASA Technical Reports Server (NTRS)

Papike, J. J.; Kamer, J. M.; Shearer, C. K.

2004-01-01

As our contribution to the new "Oxygen in the Solar System" initiative of the Lunar and Planetary Institute and the NASA Cosmochemistry Program, we have been developing oxygen barometers based largely on behavior of V which can occur in four valence states V2+, V3+, V4+, and V5+, and record at least 8 orders of magnitude of fO2. Our first efforts in measuring these valence proportions were by XANES techniques in basaltic glasses from Earth, Moon, and Mars. We now address the behavior of V valence states in chromite in basalts from Earth, Moon, and Mars. We have been looking for a "V in chromite oxybarometer" that works with data collected by the electron microprobe and thus is readily accessible to a large segment of the planetary materials community. This paper describes very early results that will be refined over the next two years.

Three Proposed Compendia for Genesis Solar Wind Samples: Science Results, Collector Materials Characterization and Cleaning Techniques

NASA Technical Reports Server (NTRS)

Allton, J. H.; Calaway, M. J.; Nyquist, L. E.; Jurewicz, A. J. G.; Burnett, D. S.

2018-01-01

Final Paper and not the abstract is attached. Introduction: Planetary material and cosmochemistry research using Genesis solar wind samples (including the development and implementation of cleaning and analytical techniques) has matured sufficiently that compilations on several topics, if made publically accessible, would be beneficial for researchers and reviewers. We propose here three compendia based on content, organization and source of documents (e.g. published peer-reviewed, published, internal memos, archives). For planning purposes, suggestions are solicited from potential users of Genesis solar wind samples for the type of science content and/or organizational style that would be most useful to them. These compendia are proposed as living documents, periodically updated. Similar to the existing compendia described below, the curation compendia are like library or archival finding aids, they are guides to published or archival documents and should not be cited as primary sources.

The Urey Instrument: An Advanced In Situ Organic and Oxidant Detector for Mars Exploration

NASA Astrophysics Data System (ADS)

Aubrey, Andrew D.; Chalmers, John H.; Bada, Jeffrey L.; Grunthaner, Frank J.; Amashukeli, Xenia; Willis, Peter; Skelley, Alison M.; Mathies, Richard A.; Quinn, Richard C.; Zent, Aaron P.; Ehrenfreund, Pascale; Amundson, Ron; Glavin Daniel P.; Botta, Oliver; Barron, Laurence; Blaney, Diana L.; Clark, Benton C.; Coleman, Max; Hofmann, Beda A.; Josset, Jean-Luc; Rettberg, Petra; Ride, Sally; Musée, François Robert; Sephton, Mark A.; Yen, Albert

2008-06-01

The Urey organic and oxidant detector consists of a suite of instruments designed to search for several classes of organic molecules in the martian regolith and ascertain whether these compounds were produced by biotic or abiotic processes using chirality measurements. These experiments will also determine the chemical stability of organic molecules within the host regolith based on the presence and chemical reactivity of surface and atmospheric oxidants. Urey has been selected for the Pasteur payload on the European Space Agency's (ESA's) upcoming 2013 ExoMars rover mission. The diverse and effective capabilities of Urey make it an integral part of the payload and will help to achieve a large portion of the mission's primary scientific objective: "to search for signs of past and present life on Mars." This instrument is named in honor of Harold Urey for his seminal contributions to the fields of cosmochemistry and the origin of life.

The Urey instrument: an advanced in situ organic and oxidant detector for Mars exploration.

PubMed

Aubrey, Andrew D; Chalmers, John H; Bada, Jeffrey L; Grunthaner, Frank J; Amashukeli, Xenia; Willis, Peter; Skelley, Alison M; Mathies, Richard A; Quinn, Richard C; Zent, Aaron P; Ehrenfreund, Pascale; Amundson, Ron; Glavin, Daniel P; Botta, Oliver; Barron, Laurence; Blaney, Diana L; Clark, Benton C; Coleman, Max; Hofmann, Beda A; Josset, Jean-Luc; Rettberg, Petra; Ride, Sally; Robert, François; Sephton, Mark A; Yen, Albert

2008-06-01

The Urey organic and oxidant detector consists of a suite of instruments designed to search for several classes of organic molecules in the martian regolith and ascertain whether these compounds were produced by biotic or abiotic processes using chirality measurements. These experiments will also determine the chemical stability of organic molecules within the host regolith based on the presence and chemical reactivity of surface and atmospheric oxidants. Urey has been selected for the Pasteur payload on the European Space Agency's (ESA's) upcoming 2013 ExoMars rover mission. The diverse and effective capabilities of Urey make it an integral part of the payload and will help to achieve a large portion of the mission's primary scientific objective: "to search for signs of past and present life on Mars." This instrument is named in honor of Harold Urey for his seminal contributions to the fields of cosmochemistry and the origin of life.

Possible Impact of Cosmochemistry on Terrestrial Biology: Historical Introduction

NASA Astrophysics Data System (ADS)

Pirie, N. W.

1981-12-01

Until the middle of the nineteenth century most philosophers, scientists and theologians assumed that life, even intelligent life, was not confined to Earth. Few of them, however, assumed that these organisms affected, or had affected, life here. The absence of human remains in ancient strata led, at the beginning of that century, to the suggestion that people were late intruders: later it was suggested that all life had come from Space. These speculations now seem quaint; our own may seem as quaint to our descendants. A few thoughtful scientists pointed out that these `explanations' did not explain anything: they merely transferred problems. The presence of organic matter in meteorites was well known in the nineteenth century. There is now abundant quantitative evidence that molecules of many different types come here from Space; there is no unequivocal evidence that any have a biological origin. Nor is there evidence for the arrival of molecules of types that could not have been synthesized in the probiotic environment here by non-biological processes.

Astrophysical implications of extraterrestrial materials: A special issue for Ernst K. Zinner

NASA Astrophysics Data System (ADS)

Nittler, Larry R.

2018-01-01

This special issue is dedicated to the memory of Dr. Ernst K. Zinner (Fig. 1). Dr. Zinner (1937-2015) was a pioneer in the use of Secondary Ion Mass Spectrometry (SIMS) in geo- and cosmochemistry. His contributions to science were vast, but in addition to his foundational SIMS development work, he is best known for the discovery and detailed characterization of presolar stardust grains in meteorites. This discovery opened up important new connections between astrophysics and meteoritical research and this is the overarching theme of this issue. Throughout his career, Ernst was a teacher, mentor, friend, and generous collaborator to legions of scientists. This issue presents research by many who were taught by, inspired by, and/or collaborated with this innovative cosmochemist and astrophysicist. In addition to the author, Ernst's former students and collaborators Drs. Christine Floss (Washington University) Peter Hoppe (MPI for chemistry, Mainz, Germany), and Kevin McKeegan (University of California, Los Angeles) served as Guest Editors for this issue.

On the Detection and Characterization of Polluted White Dwarfs

NASA Astrophysics Data System (ADS)

Steele, Amy; Debes, John H.; Deming, Drake

2017-06-01

There is evidence of circumstellar material around main sequence, giant, and white dwarf stars. What happens to this material after the main sequence? With this work, we focus on the characterization of the material around WD 1145+017. The goals are to monitor the white dwarf—which has a transiting, disintegrating planetesimal and determine the composition of the evaporated material for that same white dwarf by looking at high-resolution spectra. We also present preliminary results of follow-up photometric observations of known polluted WDs. If rocky bodies survive red giant branch evolution, then the material raining down on a WD atmosphere is a direct probe of main sequence cosmochemistry. If rocky bodies do not survive the evolution, then this informs the degree of post-main-sequence processing. These case studies will provide the community with further insight about debris disk modeling, the degree of post-main-sequence processing of circumstellar material, and the composition of a disintegrating planetesimal.

Planetary Accretion, Oxygen Isotopes and the Central Limit Theorem

NASA Technical Reports Server (NTRS)

Nuth, Joseph A., III; Hill, Hugh G. M.; Vondrak, Richard R. (Technical Monitor)

2001-01-01

The accumulation of presolar dust into increasingly larger aggregates (CAIs and Chondrules, Asteroids, Planets) should result in a very drastic reduction in the numerical spread in oxygen isotopic composition between bodies of similar size, in accord with the Central Limit Theorem. Observed variations in oxygen isotopic composition are many orders of magnitude larger than would be predicted by a simple, random accumulation model that begins in a well-mixed nebula - no matter which size-scale objects are used as the beginning or end points of the calculation. This discrepancy implies either that some as yet unspecified process acted on the solids in the Solar Nebula to increase the spread in oxygen isotopic composition during each and every stage of accumulation or that the nebula was heterogeneous and maintained this heterogeneity throughout most of nebular history. Large-scale nebular heterogeneity would have significant consequences for many areas of cosmochemistry, including the application of some well-known isotopic systems to the dating of nebular events or the prediction of bulk compositions of planetary bodies on the basis of a uniform cosmic abundance.

Accelerator mass spectrometry for measurement of long-lived radioisotopes.

PubMed

Elmore, D; Phillips, F M

1987-05-01

Particle accelerators, such as those built for research in nuclear physics, can also be used together with magnetic and electrostatic mass analyzers to measure rare isotopes at very low abundance ratios. All molecular ions can be eliminated when accelerated to energies of millions of electron volts. Some atomic isobars can be eliminated with the use of negative ions; others can be separated at high energies by measuring their rate of energy loss in a detector. The long-lived radioisotopes (10)Be, (14)C,(26)A1, 36Cl, and (129)1 can now be measured in small natural samples having isotopic abundances in the range 10(-12) to 10(- 5) and as few as 10(5) atoms. In the past few years, research applications of accelerator mass spectrometry have been concentrated in the earth sciences (climatology, cosmochemistry, environmental chemistry, geochronology, glaciology, hydrology, igneous petrogenesis, minerals exploration, sedimentology, and volcanology), in anthropology and archeology (radiocarbon dating), and in physics (searches for exotic particles and measurement of halflives). In addition, accelerator mass spectrometry may become an important tool for the materials and biological sciences.

Accelerator Mass Spectrometry for Measurement of Long-Lived Radioisotopes

NASA Astrophysics Data System (ADS)

Elmore, David; Phillips, Fred M.

1987-05-01

Particle accelerators, such as those built for research in nuclear physics, can also be used together with magnetic and electrostatic mass analyzers to measure rare isotopes at very low abundance ratios. All molecular ions can be eliminated when accelerated to energies of millions of electron volts. Some atomic isobars can be eliminated with the use of negative ions; others can be separated at high energies by measuring their rate of energy loss in a detector. The long-lived radioisotopes 10Be, 14C, 26Al, 36Cl, and 129I can now be measured in small natural samples having isotopic abundances in the range 10-12 to 10-15 and as few as 105 atoms. In the past few years, research applications of accelerator mass spectrometry have been concentrated in the earth sciences (climatology, cosmochemistry, environmental chemistry, geochronology, glaciology, hydrology, igneous petrogenesis, minerals exploration, sedimentology, and volcanology), in anthropology and archeology (radiocarbon dating), and in physics (searches for exotic particles and measurement of half-lives). In addition, accelerator mass spectrometry may become an important tool for the materials and biological sciences.

Present and future prospects of accelerator mass spectrometry

NASA Astrophysics Data System (ADS)

Kutschera, Walter

1988-05-01

Accelerator mass spectrometry (AMS) has become a powerful technique for measuring extremely low abundances (10 -10 to 10 -15 relative to stable isotopes) of long-lived radioisotopes with half-lives in the range from 10 2 to 10 8 years. With a few exceptions, tandem accelerators turned out to be the most useful instruments for AMS measurements. Both natural (mostly cosmogenic) and manmade (anthropogenic) radioisotopes are studied with this technique. In some cases very low concentrations of stable isotopes are also measured. Applications of AMS cover a large variety of fields including anthropology, archaeology, oceanography, hydrology, climatology, volcanology, mineral exploration, cosmochemistry, meteoritics, glaciology, sedimentary processes, geochronology, environmental physics, astrophysics, nuclear and particle physics. Present and future prospects of AMS will be discussed as an interplay between the continuous development of new techniques and the investigation of problems in the above mentioned fields. Depending on the specific problem to be investigated, different aspects of an AMS system are of importance. Typical factors to be considered are energy range and type of accelerator, and the possibilities of dedicated versus partial use of new or existing accelerators.

High pressure cosmochemistry applied to major planetary interiors: Experimental studies

NASA Technical Reports Server (NTRS)

Nicol, M. F.; Johnson, M.; Koumvakalis, A. S.

1984-01-01

Progress is reported on a project to determine the properties and boundaries of high pressure phases of the H2-He-H2O-NH3-CH4 system that are needed to constrain theoretical models of the interiors of the major planets. This project is one of the first attempts to measure phase equilibria in binary fluid-solid systems in diamond anvil cells. Vibrational spectroscopy, direct visual observations, and X-ray diffraction crystallography of materials confined in externally heated cells are the primary experimental probes. Adiabats of these materials are also measured in order to constrain models of heat flow in these bodies and to detect phase transitions by thermal anomalies. Initial efforts involve the NH3-H2O binary. This system is especially relevant to models for surface reconstruction of the icy satellites of Jupiter and Saturn. Thermal analysis experiments were completed for the P-X space, p4GPa:0 or = 0.50, near room temperature. The cryostat, sample handling equipment, and optics needed to extend the optical P-T-X work below room temperature was completed.

Thermochemistry of CaO-MgO-Al2O3-SiO2 (CMAS) and Advanced Thermal and Environmental Barrier Coating Systems

NASA Technical Reports Server (NTRS)

Costa, Gustavo C. C.; Zhu, Dongming

2016-01-01

CaO-MgO-Al2O3-SiO2 (CMAS) oxides are constituents in a broad number of materials and minerals which have recently inferred to discussions in materials science, planetary science, geochemistry and cosmochemistry communities. In materials science, there is increasing interest in the degradation studies of thermal (TBC) and environmental (EBC) barrier coatings of gas turbines by molten CMAS. These coatings have been explored to be applied on silicon-based ceramics and composites which are lighter and more temperature capable hot-section materials of gas turbines than the current Ni-based superalloys. The degradation of the coatings occurs when CMAS minerals carried by the intake air into gas turbines, e.g. in aircraft engines, reacts at high temperatures (1000C) with the coating materials. This causes premature failure of the static and rotating components of the turbine engines. We discuss some preliminary results of the reactions between CMAS and Rare-Earth (RE Y, Yb and Gd) oxide stabilized ZrO2 systems, and stability of the resulting oxides and silicates.

Isotopic homogeneity of iron in the early solar nebula.

PubMed

Zhu, X K; Guo, Y; O'Nions, R K; Young, E D; Ash, R D

2001-07-19

The chemical and isotopic homogeneity of the early solar nebula, and the processes producing fractionation during its evolution, are central issues of cosmochemistry. Studies of the relative abundance variations of three or more isotopes of an element can in principle determine if the initial reservoir of material was a homogeneous mixture or if it contained several distinct sources of precursor material. For example, widespread anomalies observed in the oxygen isotopes of meteorites have been interpreted as resulting from the mixing of a solid phase that was enriched in 16O with a gas phase in which 16O was depleted, or as an isotopic 'memory' of Galactic evolution. In either case, these anomalies are regarded as strong evidence that the early solar nebula was not initially homogeneous. Here we present measurements of the relative abundances of three iron isotopes in meteoritic and terrestrial samples. We show that significant variations of iron isotopes exist in both terrestrial and extraterrestrial materials. But when plotted in a three-isotope diagram, all of the data for these Solar System materials fall on a single mass-fractionation line, showing that homogenization of iron isotopes occurred in the solar nebula before both planetesimal accretion and chondrule formation.

Development of a High Resolution-High Sensitivity Ion Microprobe Facility for Cosmochemical Applications

NASA Technical Reports Server (NTRS)

McKeegan, Kevin D.

1998-01-01

NASA NAGW-4112 has supported development of the CAMECA ims 1270 ion microprobe at UCLA for applications in cosmochemistry. The instrument has been brought to an operational status and techniques developed for accurate, precise microbeam analysis of oxygen isotope ratios in polished thin-sections. We made the first oxygen isotopic (delta(18)O and delta(17)O) measurements of rare mafic silicates in the most chemically primitive meteorites, the a chondrites (Leshin et al., 1997). The results have implications for both high temperature processing in the nebula and low-T aqueous alteration on the CI asteroid. We have performed measurements of oxygen isotopic compositions of magnetite and co-existing olivine from carbonaceous (Choi et al., 1997) and unequilibrated ordinary chondrites (Choi et al., in press). This work has identified a significant new oxygen isotope reservoir in the early solar system: water characterized by a very high Delta(17)) value of approx. 5 % per thousand. We have determined the spatial distributions of oxygen isotopic anomalies in all major mineral phases of a type B CAI from Allende. We have also studied an unusual fractionated CAI from Leoville and made the first oxygen isotopic measurements in rare CAIs from ordinary chondrites.

Searching for Extraterrestrial Amino Acids in a Contaminated Meteorite: Amino Acid Analyses of the Canakkale L6 Chondrite

NASA Technical Reports Server (NTRS)

Burton, A. S.; Elsila, J. E.; Glavin, D. P.; Dworkin, J. P.; Ornek, C. Y.; Esenoglu, H. H.; Unsalan, O.; Ozturk, B.

2016-01-01

Amino acids can serve as important markers of cosmochemistry, as their abundances and isomeric and isotopic compositions have been found to vary predictably with changes in parent body chemistry and alteration processes. Amino acids are also of astrobiological interest because they are essential for life on Earth. Analyses of a range of meteorites, including all groups of carbonaceous chondrites, along with H, R, and LL chondrites, ureilites, and a martian shergottite, have revealed that amino acids of plausible extraterrestrial origin can be formed in and persist after a wide range of parent body conditions. However, amino acid analyses of L6 chondrites to date have not provided evidence for indigenous amino acids. In the present study, we performed amino acid analysis on larger samples of a different L6 chondite, Canakkale, to determine whether or not trace levels of indigenous amino acids could be found. The Canakkale meteor was an observed fall in late July, 1964, near Canakkale, Turkey. The meteorite samples (1.36 and 1.09 g) analyzed in this study were allocated by C. Y. Ornek, along with a soil sample (1.5 g) collected near the Canakkale recovery site.

Physical and Chemical Study of Minerals and Rocks Containing Low-Z Compounds of Interest to Astrobiology and Origin of Life

NASA Technical Reports Server (NTRS)

1999-01-01

Understanding the origins of Life requires a good understanding of the physics and chemistry of biogenic low-z elements H, C, N, O, P, S in terrestrial environments, on Mars, on extraterrestrial bodies such as meteorite parent bodies and comets, and in interstellar space. In this Proposal five Tasks form a coherent program aimed at elucidating various aspects of low-z element geo- and cosmochemistry with special reference to the origin of Life on Earth and to the search for life on Mars, extant or extinct. (i) Formation of organic molecules, in particular oxygenated H-C-0 molecules or precursors thereof of the composition H(x)C(y)O(z)(n-), inside the hard matrix of structurally dense magmatic minerals; (ii) Formation of organic molecules inside the soft matrix of amorphous and crystalline water ice; (iii) Preservation of organic molecules in cherts and other siliceous rocks formed in hot spring or submarine hydrothermal vent environments; (iv) The nature of the elusive Martian soil oxidant; and (v) Prototype development of an XRD instrument, using a new patented XRD camera concept that utilizes a Charge Coupled Device (CCD) as a camera and as a energy-dispersive analyzer.

Reprint Of: Enhanced spatially-resolved trace analysis using combined SIMS-single-stage AMS

NASA Astrophysics Data System (ADS)

Grabowski, K. S.; Groopman, E. E.; Fahey, A. J.

2018-01-01

Secondary ion mass spectrometry (SIMS) provides spatially resolved trace analysis of solid materials, but can be complicated by unresolved abundant molecular isobars. By adding a 300-kV single-stage accelerator mass spectrometer (SSAMS) as a detector for a Cameca ims 4f SIMS, one can measure more abundant positive ions from the SIMS while removing molecular isobars, thus improving very low abundance trace element and isotope analysis. This paper describes important features and capabilities of such an integrated system at the Naval Research Laboratory using charge state +1 ions. Transmission loss is compared to molecule destruction as gas flow to the molecule-destruction cell increases. As most measurements tolerate more modest abundance sensitivities than for 14C analysis, a lower gas flow is acceptable, so good transmission of 20-50% for ions of interest can be maintained for a broad range of ion masses. This new instrument has measured isotope ratios for uranium, lead, rare earths, and other elements from particulates and localized regions, with molecule destruction enabling the measurement at low SIMS mass resolving power and thus high transmission, as examples will show. This new and world-unique instrument provides improved capabilities for applications in nuclear and other forensics, geochemistry, cosmochemistry, and the development of optical, electronic, multifunctional, and structural materials.

Enhanced spatially-resolved trace analysis using combined SIMS-single-stage AMS

NASA Astrophysics Data System (ADS)

Grabowski, K. S.; Groopman, E. E.; Fahey, A. J.

2017-11-01

Secondary ion mass spectrometry (SIMS) provides spatially resolved trace analysis of solid materials, but can be complicated by unresolved abundant molecular isobars. By adding a 300-kV single-stage accelerator mass spectrometer (SSAMS) as a detector for a Cameca ims 4f SIMS, one can measure more abundant positive ions from the SIMS while removing molecular isobars, thus improving very low abundance trace element and isotope analysis. This paper describes important features and capabilities of such an integrated system at the Naval Research Laboratory using charge state +1 ions. Transmission loss is compared to molecule destruction as gas flow to the molecule-destruction cell increases. As most measurements tolerate more modest abundance sensitivities than for 14C analysis, a lower gas flow is acceptable, so good transmission of 20-50% for ions of interest can be maintained for a broad range of ion masses. This new instrument has measured isotope ratios for uranium, lead, rare earths, and other elements from particulates and localized regions, with molecule destruction enabling the measurement at low SIMS mass resolving power and thus high transmission, as examples will show. This new and world-unique instrument provides improved capabilities for applications in nuclear and other forensics, geochemistry, cosmochemistry, and the development of optical, electronic, multifunctional, and structural materials.

CHILI – the Chicago Instrument for Laser Ionization – a new tool for isotope measurements in cosmochemistry

DOE PAGES

Stephan, Thomas; Trappitsch, Reto; Davis, Andrew M.; ...

2016-06-17

Here, we describe CHILI, the Chicago Instrument for Laser Ionization, a new resonance ionization mass spectrometer developed for isotopic analysis at high spatial resolution and high sensitivity of small samples like contemporary interstellar dust grains returned by the Stardust spacecraft. We explain how CHILI addresses the technical challenges associated with such analyses by pushing most technical specifications towards their physical limits. As an initial demonstration, after many years of designing and developing CHILI, we have analyzed presolar silicon carbide grains for their isotopic compositions of strontium, zirconium, and barium. Subsequently, after further technical improvements, we have used CHILI to analyze,more » for the first time without interference, all stable isotopes of iron and nickel simultaneously in presolar silicon carbide grains. With a special timing scheme for the ionization lasers, we separated iron and nickel isotopes in the time-of-flight spectrum such that the isobaric interference between 58Fe and 58Ni was resolved. In-depth discussion of the astrophysical implications of the presolar grain results is deferred to dedicated later publications. Here we focus on the technical aspects of CHILI, its status quo, and further developments necessary to achieve CHILI’s ultimate goals, 10 nm lateral resolution and 30–40% useful yield.« less

CHILI – the Chicago Instrument for Laser Ionization – a new tool for isotope measurements in cosmochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stephan, Thomas; Trappitsch, Reto; Davis, Andrew M.

2016-08-01

We describe CHILI, the Chicago Instrument for Laser Ionization, a new resonance ionization mass spectrometer developed for isotopic analysis at high spatial resolution and high sensitivity of small samples like contemporary interstellar dust grains returned by the Stardust spacecraft. We explain how CHILI addresses the technical challenges associated with such analyses by pushing most technical specifications towards their physical limits. As an initial demonstration, after many years of designing and developing CHILI, we have analyzed presolar silicon carbide grains for their isotopic compositions of strontium, zirconium, and barium. Subsequently, after further technical improvements, we have used CHILI to analyze, formore » the first time without interference, all stable isotopes of iron and nickel simultaneously in presolar silicon carbide grains. With a special timing scheme for the ionization lasers, we separated iron and nickel isotopes in the time-of-flight spectrum such that the isobaric interference between Fe-58 and Ni-58 was resolved. In-depth discussion of the astrophysical implications of the presolar grain results is deferred to dedicated later publications. Here we focus on the technical aspects of CHILI, its status quo, and further developments necessary to achieve CHILI's ultimate goals, similar to 10 nm lateral resolution and 30-40% useful yield.« less

Plausible surface models for Titan

NASA Technical Reports Server (NTRS)

Lunine, Jonathan I.

1992-01-01

Current understanding of the nature of Titan's surface and some new ideas for explaining the curious radar returns from Saturn's largest satellite are reviewed. Pre-Voyager models of the surface, based largely on cosmochemistry and the discovery of atmospheric methane, allowed for a range of possibilities, including pure methane oceans. The Voyager 1 flyby ruled out this last possibility, replacing it with compelling observational arguments in favor of a mixed light hydrocarbon and nitrogen ocean. Ground based radar observations indicated a surprisingly reflective surface which is inconsistent with a hydrocarbon ocean and more reminiscent of the Galilean Satellites. Nonetheless, passive radiometric measurements of the surface do not support the notion that Titan's surface is like that of the Galilean satellites. One of the arguments against hydrocarbon oceans reflecting radar energy is that most solid, complex hydrocarbon and nitriles will be denser than the liquid and sink. Nonetheless, many of the aerosol species will coagulate in highly nonspherical patterns, and some species probably polymerize in long chains. Such chains will have very low sedimendation velocities in the ocean and may remain near the surface through ocean mixing process. The prospect of an oceanic 'soup' of polar polymers acting as volume reflectors at radio wevelengths suggests that the interpretation of radar observations needs evaluation.

High Pressure Cosmochemistry of Major Planetary Interiors: Laboratory Studies of the Water-rich Region of the System Ammonia-water

NASA Technical Reports Server (NTRS)

Nicol, M.; Johnson, M.; Koumvakalis, A. S.

1985-01-01

The behavior of gas-ice mixtures in major planets at very high pressures was studied. Some relevant pressure-temperature-composition (P-T-X) regions of the hydrogen (H2)-helium (He)-water (H2O-ammonia (NH3)-methane (CH4) phase diagram were determined. The studies, and theoretical model, of the relevant phases, are needed to interpret the compositions of ice-gas systems at conditions of planetary interest. The compositions and structures of a multiphase, multicomponent system at very high pressures care characterized, and the goal is to characterize this system over a wide range of low and high temperatures. The NH3-H2O compositions that are relevant to planetary problems yet are easy to prepare were applied. The P-T surface of water was examined and the corresponding surface for NH3 was determined. The T-X diagram of ammonia-water at atmospheric pressure was studied and two water-rich phases were found, NH3-2H2O (ammonia dihydrate), which melts incongruently, and NH3.H2O (ammonia monohydrate), which is nonstoichiometric and melts at a higher temperature than the dihydrate. It is suggested that a P-T surface at approximately the monohydrate composition and the P-X surface at room temperature is determined.

Thermochemistry of CaO-MgO-Al2O3-SiO2 (CMAS) and Advanced Thermal and Environmental Barrier Coating Systems

NASA Technical Reports Server (NTRS)

Costa, Gustavo; Zhu, Dongming

2017-01-01

CaO-MgO-Al2O3-SiO2 (CMAS) oxides are constituents in a broad number of materials and minerals which have recently inferred to discussions in materials science, planetary science, geochemistry and cosmochemistry communities. In materials science, there is increasing interest in the degradation studies of thermal (TBC) and environmental (EBC) barrier coatings of gas turbines by molten CMAS. CMAS minerals usually are carried by the intake air into gas turbines, e.g. in aircraft engines, and their deposits react at high temperatures (1000C) with the coating materials. This causes degradation and accelerated failure of the static and rotating components of the turbine engines. We discuss some preliminary results of the reactions between CMAS and Rare-Earth (RE Y, Yb, Dy, Gd, Nd and Sm) oxide stabilized ZrO2 or HfO2 systems, and the stability of the resulting oxides and silicates. Plasma sprayed hollow tube samples ( 2.2 mm and 26 mm height) were half filled with CMAS powder, wrapped and sealed with platinum foil, and heat treated at 1310 C for 5h. Samples were characterized by differential scanning calorimetry, X-ray diffraction and cross section electron microscopy analysis.

Urey: Mars Organic and Oxidant Detector

NASA Astrophysics Data System (ADS)

Bada, J. L.; Ehrenfreund, P.; Grunthaner, F.; Blaney, D.; Coleman, M.; Farrington, A.; Yen, A.; Mathies, R.; Amudson, R.; Quinn, R.; Zent, A.; Ride, S.; Barron, L.; Botta, O.; Clark, B.; Glavin, D.; Hofmann, B.; Josset, J. L.; Rettberg, P.; Robert, F.; Sephton, M.

One of the fundamental challenges facing the scientific community as we enter this new century of Mars research is to understand, in a rigorous manner, the biotic potential both past and present of this outermost terrestrial-like planet in our solar system. Urey: Mars Organic and Oxidant Detector has been selected for the Pasteur payload of the European Space Agency's (ESA's) ExoMars rover mission and is considered a fundamental instrument to achieve the mission's scientific objectives. The instrument is named Urey in recognition of Harold Clayton Urey's seminal contributions to cosmochemistry, geochemistry, and the study of the origin of life. The overall goal of Urey is to search for organic compounds directly in the regolith of Mars and to assess their origin. Urey will perform a groundbreaking investigation of the Martian environment that will involve searching for organic compounds indicative of life and prebiotic chemistry at a sensitivity many orders of magnitude greater than Viking or other in situ organic detection systems. Urey will perform the first in situ search for key classes of organic molecules using state-of-the-art analytical methods that provide part-per-trillion sensitivity. It will ascertain whether any of these molecules are abiotic or biotic in origin and will evaluate the survival potential of organic compounds in the environment using state-of-the-art chemoresistor oxidant sensors.

Noble Gases

NASA Astrophysics Data System (ADS)

Podosek, F. A.

2003-12-01

The noble gases are the group of elements - helium, neon, argon, krypton, xenon - in the rightmost column of the periodic table of the elements, those which have "filled" outermost shells of electrons (two for helium, eight for the others). This configuration of electrons results in a neutral atom that has relatively low electron affinity and relatively high ionization energy. In consequence, in most natural circumstances these elements do not form chemical compounds, whence they are called "noble." Similarly, much more so than other elements in most circumstances, they partition strongly into a gas phase (as monatomic gas), so that they are called the "noble gases" (also, "inert gases"). (It should be noted, of course, that there is a sixth noble gas, radon, but all isotopes of radon are radioactive, with maximum half-life a few days, so that radon occurs in nature only because of recent production in the U-Th decay chains. The factors that govern the distribution of radon isotopes are thus quite different from those for the five gases cited. There are interesting stories about radon, but they are very different from those about the first five noble gases, and are thus outside the scope of this chapter.)In the nuclear fires in which the elements are forged, the creation and destruction of a given nuclear species depends on its nuclear properties, not on whether it will have a filled outermost shell when things cool off and nuclei begin to gather electrons. The numerology of nuclear physics is different from that of chemistry, so that in the cosmos at large there is nothing systematically special about the abundances of the noble gases as compared to other elements. We live in a very nonrepresentative part of the cosmos, however. As is discussed elsewhere in this volume, the outstanding generalization about the geo-/cosmochemistry of the terrestrial planets is that at some point thermodynamic conditions dictated phase separation of solids from gases, and that the Earth and the rest of the inner solar were made by collecting the solids, to the rather efficient exclusion of the gases. In this grand separation the noble gases, because they are noble, were partitioned strongly into the gas phase. The resultant generalization is that the noble gases are very scarce in the materials of the inner solar system, whence their common synonym "rare gases."This scarcity is probably the most important single feature to remember about noble-gas cosmochemistry. As illustration of the absolute quantities, for example, a meteorite that contains xenon at a concentration of order 10 -10 cm3STP g -1 (4×10-15 mol g-1) would be considered relatively rich in xenon. Yet this is only 0.6 ppt (part per trillion, fractional abundance 10-12) by mass. In most circumstances, an element would be considered efficiently excluded from some sample if its abundance, relative to cosmic proportions to some convenient reference element, were depleted by "several" orders of magnitude. But a noble gas would be considered to be present in quite high concentration if it were depleted by only four or five orders of magnitude (in the example above, 10-10 cm3STP g-1 of xenon corresponds to depletion by seven orders of magnitude), and one not uncommonly encounters noble-gas depletion of more than 10 orders of magnitude.The second most important feature to note about noble-gas cosmochemistry is that while a good deal of the attention given to noble gases really is about chemistry, traditionally a good deal of attention is also devoted to nuclear phenomena, much more so than for most other elements. This feature is a corollary of the first feature noted above, namely scarcity. A variety of nuclear transmutation processes - decay of natural radionuclides and energetic particle reactions - lead to the production of new nuclei that are often new elements. Most commonly, the quantity of new nuclei originating in nuclear transmutation is very small compared to the quantity already present in the sample in question, metaphorically a drop in the bucket. Thus, they are very difficult or impossible to detect and, therefore, in practical terms, attracting little or no interest. When the bucket is empty, or nearly so, however, the "drop" contributed by nuclear transmutations may become observable or even dominant. Traditionally there are two types of (nearly) empty buckets that are most suitable for revealing the effects of nuclear transmutations: short-lived radionuclides (e.g., 10Be and 26Al) which would be entirely absent except for recent nuclear reactions, and the noble gases, renowned for their scarcity.Emphasis on nuclear processes explains what sometimes seems to be an obsession with isotopes in noble-gas geo- and cosmochemistry. Different nuclear processes will produce different isotopes, singly or in suites with well-defined proportions (i.e., "components"), different from one process to another. Much of the traditional agenda of noble-gas geochemistry, and especially cosmochemistry, thus consists of isotopic analysis, and deconvolution of an observed isotopic spectrum into constituent components. (In most geochemical investigations, noble gases are detected by mass spectrometry, a technique that is inherently sensitive to specific isotopes, not just the chemical element. Isotopic data thus emerge naturally in most studies. Noble-gas mass spectrometry can be a much more sensitive technique than other traditional types of mass spectrometry because the gases are "noble," and therefore relatively easy to separate from other elements, and because they are scarce, so that they can be analyzed in "static"-mode (no pumping during analysis) gas-source spectrometers, permitting relatively high detection efficiency without overwhelming blanks.) In realistic terms, it is very difficult to appreciate noble-gas geo-/cosmochemistry without a basic familiarity with noble-gas isotopes: which isotopes occur in nature (i.e., which are stable), in what approximate abundance they are found, how they relate to non-noble neighbors, and, to some extent, how they are associated with specific nuclear processes. Figure 1 provides assistance in this regard. (6K)Figure 1. A display of the isotopes of the noble gases and neighboring isotopes in the familiar "chart of the nuclides" format. The abscissa is neutron number (N) and the ordinate is proton number (Z). The box corresponding to any pair (Z, N) represents an isotope; an element is represented by a horizontal row. Boxes for stable isotopes are shown with solid outline; for the noble gases, approximate solar (in the case of He, protosolar) isotope ratios are shown at the bottom of each box. Selected unstable isotopes are shown as boxes with broken line edges. The left-superscript isotope label is the atomic weight A (=Z+N). The five panels show regions around the five noble gases (excluding Rn). When the goal is to identify and quantify different noble-gas components that may be present in a sample or group of samples, a common approach to this goal is to try to unmix the components, at least partially, to provide some leverage. One path to this end, of course, is analysis of different samples that may contain the components in different proportions, and thus have different isotopic compositions. Another path, available in addition to or instead of the first, is stepwise heating analysis, which has traditionally been very extensively used in noble-gas studies. Noble gases may be released from solid samples by volume diffusion, or by reaction, recrystallization, melting, or even evaporation of their host phases. If different noble-gas components reside in physically distinct locations within a complex sample, they may be liberated, and thus become available for analysis, at different steps in a time-temperature heating sequence. Differential release of isotopically distinct components will then result in variation of the isotopic composition of gas released in different steps (e.g., see Figures 2 and 4). (12K)Figure 2. A three-isotope diagram illustrating compositional variations in lunar samples and meteorites, as observed in stepwise in vacuo etching and pyrolysis. Since the observed isotopic compositions do not lie on a single straight line, at least three isotopically distinct components must contribute in variable proportions. These data are interpreted as superposition of solar wind (SW), solar energetic particles (SEP), and galactic cosmic ray, i.e., spallation (GCR) Ne components (source Wieler, 1998). A common tool for visualization of isotopic variations is the so-called "three-isotope diagram," in which two isotope ratios, each with the same reference (denominator) isotope, are displayed on abscissa and ordinate (e.g., Figure 2). Two isotopically distinct components will plot at distinct points on a three-isotope diagram, and an often-used feature is that mixtures of the two components will plot on the straight line joining those two points. A lever rule applies: the greater the proportion that one component contributes to a mixture, the closer the point representing the mixture will lie to the point representing that end-member component, and there is a linear relationship between fractional distance from one end-member to the other and the fraction that each component contributes to the mixture (specifically to the reference isotope). If observed isotopic data are variable but the variations in two ratios are correlated, so as to be consistent with a straight line on a three-isotope diagram, it can be inferred that at least two components are present and it will often be hypothesized that only two components are present, in which case their compositions can be constrained to lie on the line, one on either side of the data field. If three components are present, not coincidentally collinear on this diagram, mixtures will occupy the triangular field defined by the three compositions, and conversely if observed data are not consistent with linear correlation it can be inferred that at least three components are contributing to the mix. The concept of the three-isotope diagram is readily generalized. Four isotopes defining three ratios (all with the same reference isotope), for example, will define a three-dimensional space in which mixture of two components will produce compositions lying along a straight line, and mixture of three components will produce compositions lying in a plane, etc. Generalization to more dimensions is mathematically straightforward, even if difficult to envision.

Report on the Sixth International Symposium on Isotopomers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bao, H.; Farquhar, J.; Rumble, D.

The ISI 2012 met in Washington, DC, 18-22 June 2012, bringing together researchers and their students spanning an unusually wide range of disciplines including quantum and physical chemistry, cosmochemistry, atmospheric chemistry, chemical oceanography, biogeochemistry, organic and inorganic geochemistry. The diversity of subject matter was matched geographically with 92 attendees hailing from Canada, China, Finland, France, Germany, India, Israel, Japan, the Netherlands, Russia, Switzerland, Taiwan, the United Kingdom, and the USA. Although diverse, the group was united in its commitment to use the light stable isotopes of H, C, N, O, and S, with their equilibrium, kinetic, and intramolecular fractionations, tomore » understand the material cycles and their dynamics between atmosphere, biosphere, hydrosphere, and lithosphere that make life possible on Earth. A distinct benefit of a small meeting like ISI 2012 is the opportunity for everyone to talk to each other. The historic rooms of the Carnegie Institution of Washington offered a cozy and warm atmosphere for participants in ISI 2012 to talk science and life in a casual, relaxed, and in-depth fashion. Graduate students and postdoctoral researchers were particularly appreciative of being able to spend five days together with old and new colleagues in comfortable quarters. Many commented that they had gained a lot more in building their life-long working relationships with colleagues at this meeting than at larger meetings.« less

Insight into Primordial Solar System Oxygen Reservoirs from Returned Cometary Samples

NASA Technical Reports Server (NTRS)

Brownlee, D. E.; Messenger, S.

2004-01-01

The recent successful rendezvous of the Stardust spacecraft with comet Wild-2 will be followed by its return of cometary dust to Earth in January 2006. Results from two separate dust impact detectors suggest that the spacecraft collected approximately the nominal fluence of at least 1,000 particles larger than 15 micrometers in size. While constituting only about one microgram total, these samples will be sufficient to answer many outstanding questions about the nature of cometary materials. More than two decades of laboratory studies of stratospherically collected interplanetary dust particles (IDPs) of similar size have established the necessary microparticle handling and analytical techniques necessary to study them. It is likely that some IDPs are in fact derived from comets, although complex orbital histories of individual particles have made these assignments difficult to prove. Analysis of bona fide cometary samples will be essential for answering some fundamental outstanding questions in cosmochemistry, such as (1) the proportion of interstellar and processed materials that comprise comets and (2) whether the Solar System had a O-16-rich reservoir. Abundant silicate stardust grains have recently been discovered in anhydrous IDPs, in far greater abundances (200 5,500 ppm) than those in meteorites (25 ppm). Insight into the more subtle O isotopic variations among chondrites and refractory phases will require significantly higher precision isotopic measurements on micrometer-sized samples than are currently available.

Urey: Mars Organic and Oxidant Detector

NASA Astrophysics Data System (ADS)

Bada, J. L.; Ehrenfreund, P.; Grunthaner, F.; Blaney, D.; Coleman, M.; Farrington, A.; Yen, A.; Mathies, R.; Amudson, R.; Quinn, R.; Zent, A.; Ride, S.; Barron, L.; Botta, O.; Clark, B.; Glavin, D.; Hofmann, B.; Josset, J. L.; Rettberg, P.; Robert, F.; Sephton, M.

2008-03-01

One of the fundamental challenges facing the scientific community as we enter this new century of Mars research is to understand, in a rigorous manner, the biotic potential both past and present of this outermost terrestrial-like planet in our solar system. Urey: Mars Organic and Oxidant Detector has been selected for the Pasteur payload of the European Space Agency’s (ESA’s) ExoMars rover mission and is considered a fundamental instrument to achieve the mission’s scientific objectives. The instrument is named Urey in recognition of Harold Clayton Urey’s seminal contributions to cosmochemistry, geochemistry, and the study of the origin of life. The overall goal of Urey is to search for organic compounds directly in the regolith of Mars and to assess their origin. Urey will perform a groundbreaking investigation of the Martian environment that will involve searching for organic compounds indicative of life and prebiotic chemistry at a sensitivity many orders of magnitude greater than Viking or other in situ organic detection systems. Urey will perform the first in situ search for key classes of organic molecules using state-of-the-art analytical methods that provide part-per-trillion sensitivity. It will ascertain whether any of these molecules are abiotic or biotic in origin and will evaluate the survival potential of organic compounds in the environment using state-of-the-art chemoresistor oxidant sensors.

Organic geochemistry - A retrospective of its first 70 years

USGS Publications Warehouse

Kvenvolden, K.A.

2006-01-01

Organic geochemistry had its origin in the early part of the 20th century when organic chemists and geologists realized that detailed information on the organic materials in sediments and rocks was scientifically interesting and of practical importance. The generally acknowledged "father" of organic geochemistry is Alfred E. Treibs (1899-1983), who discovered and described, in 1936, porphyrin pigments in shale, coal, and crude oil, and traced the source of these molecules to their biological precursors. Thus, the year 1936 marks the beginning of organic geochemistry. However, formal organization of organic geochemistry dates from 1959 when the Organic Geochemistry Division (OGD) of The Geochemical Society was founded in the United States, followed 22 years later (1981) by the establishment of the European Association of Organic Geochemists (EAOG). Organic geochemistry (1) has its own journal, Organic Geochemistry (beginning in 1979) which, since 1988, is the official journal of the EAOG, (2) convenes two major conferences [International Meeting on Organic Geochemistry (IMOG), since 1962, and Gordon Research Conferences on Organic Geochemistry (GRC), since 1968] in alternate years, and (3) is the subject matter of several textbooks. Organic geochemistry is now a widely recognized geoscience in which organic chemistry has contributed significantly not only to geology (i.e., petroleum geochemistry, molecular stratigraphy) and biology (i.e., biogeochemistry), but also to other disciplines, such as chemical oceanography, environmental science, hydrology, biochemical ecology, archaeology, and cosmochemistry.

Are Fullerenes Relevant to Cosmochemistry? A New Finding

NASA Technical Reports Server (NTRS)

Wilson, T. L.; Mittlefehldt, D. W.

2008-01-01

The abundances of noble gases found in primitive, carbonaceous meteorites are unexpected when compared with our Sun. Known as Q-gases (Q for some unknown carrier dubbed quintessence ), this anomaly has remained a mystery since it was discovered in 1975. Q-gases are characterized by increasing depletions with decreasing atomic number (Z) relative to solar noble gases and normalized to 132Xe (Figure 1). This Q-gas mass fractionation is unexplained, and its investigation is important to understanding the origin of the solar system. However, the subject is fraught with controversy, in part due to the complex nature of Q and in part due to claims of some researchers that cannot be reproduced by other investigators. The topic is discussed in numerous places [e.g., 1-4], with models of Q falling into two basic categories, both involving carbon entrapment of noble gases. First (Group A), there is the conservative two-dimensional view that Q-gases are adsorbed or sorbed onto a "labyrinth" of graphite or carbon grains [5-9], or they undergo active capture onto growing surfaces [6]. Second (Group B), there is the view holding to the remarkable property of carbon discovered in 1985. Carbon can curl up into closed geometries of hexagon- and pentagon-shaped carbon-ring configurations, a property ignored completely by Group A. Group B thinks of Q as a three-dimensional structure of endohedral carbon cages like fullerenes, carbon onions, or some class of carbon nanotubes [3, 4, 10]. Group B does not exclude Group A effects.

Urey: Mars Organic and Oxidant Detector

NASA Astrophysics Data System (ADS)

Bada, J.

2006-12-01

Mars lies at the frontier of planetary exploration science and the question of whether life arose on Mars has been widely debated. One of the fundamental challenges facing the scientific community as we enter this new century of Mars research is to understand in a rigorous manner the biotic potential both past and present of this outermost terrestrial-like planet in our solar system. Urey: Mars Organic and Oxidant Detector has been selected for the Pasteur payload in the European Space Agency's (ESA's) ExoMars rover mission and is considered a fundamental instrument to achieve the mission's scientific objectives. The instrument is named Urey in recognition of Harold Clayton Urey's seminal contributions to cosmochemistry, geochemistry and the study of the origin of life. The overall goal of Urey is to search for organic compounds directly in the regolith of Mars and to assess their origin. Urey will perform a groundbreaking investigation of the Martian environment that will involve searching for organic compounds indicative of life and prebiotic chemistry at a sensitivity many orders of magnitude greater than Viking or other in situ organic detection systems. Urey will perform the first in situ search for key classes of organic molecules using state-of-the-art analytical methods that provide part- per-trillion sensitivity. It will ascertain whether any of these molecules are abiotic or biotic in origin and will evaluate the survival potential of organic compounds in the environment using state-of-the-art chemoresistor oxidant sensors.

Carbon molecules in space: from astrochemistry to astrobiology.

PubMed

Ehrenfreund, Pascale; Sephton, Mark A

2006-01-01

How complex carbonaceous molecules in space are, what their abundance is and on what timescales they form are crucial questions within cosmochemistry. Despite the large heterogeneity of galactic and interstellar regions the organic chemistry in the universe seems to follow common pathways. The largest fraction of carbon in the universe is incorporated into aromatic molecules (gaseous polycyclic aromatic hydrocarbon as well as solid macromolecular aromatic structures). Macromolecular carbon constitutes more than half of the interstellar carbon, approximately 80% of the carbon in meteorites, and is likely to be present in comets. Molecules of high astrobiological relevance such as N-heterocycles, amino acids and pre-sugars have all been identified in trace quantities (ppb) in extracts of carbonaceous meteorites. Their presence in inter- and circumstellar regions is either unknown or contentious. In any event such fragile species are easily destroyed by UV radiation, shocks and thermal processing and are unlikely to survive incorporation into Solar System material without some degradation. The more refractory material, in particular macromolecular carbon may retain an interstellar heritage more faithfully. We present laboratory measurements on the photostability of organic compounds and discuss their survival in regions with elevated UV radiation. We also show recent observations of diffuse interstellar bands indicating the presence of fullerenes. We investigate the link between the carbon chemistry in interstellar space and in the Solar System by analyzing the carbonaceous fraction of meteorites and by reviewing stable isotopic data. It also seems evident that both volatile and refractory material from carbonaceous meteoritic has been substantially altered owing to thermal and aqueous processing within the Solar System.

Crystal structure, stability and spectroscopic properties of methane and CO2 hydrates.

PubMed

Martos-Villa, Ruben; Francisco-Márquez, Misaela; Mata, M Pilar; Sainz-Díaz, C Ignacio

2013-07-01

Methane hydrates are highly present in sea-floors and in other planets and their moons. Hence, these compounds are of great interest for environment, global climate change, energy resources, and Cosmochemistry. The knowledge of stability and physical-chemical properties of methane hydrate crystal structure is important for evaluating some new green becoming technologies such as, strategies to produce natural gas from marine methane hydrates and simultaneously store CO2 as hydrates. However, some aspects related with their stability, spectroscopic and other chemical-physical properties of both hydrates are not well understood yet. The structure and stability of crystal structure of methane and CO2 hydrates have been investigated by means of calculations with empirical interatomic potentials and quantum-mechanical methods based on Hartree-Fock and Density Functional Theory (DFT) approximations. Molecular Dynamic simulations have been also performed exploring different configurations reproducing the experimental crystallographic properties. Spectroscopic properties have also been studied. Frequency shifts of the main vibration modes were observed upon the formation of these hydrates, confirming that vibration stretching peaks of C-H at 2915cm(-1) and 2905cm(-1) are due to methane in small and large cages, respectively. Similar effect is observed in the CO2 clathrates. The guest-host binding energy in these clathrates calculated with different methods are compared and discussed in terms of adequacy of empirical potentials and DFT methods for describing the interactions between gas guest and the host water cage, proving an exothermic nature of methane and CO2 hydrates formation process. Copyright © 2013 Elsevier Inc. All rights reserved.

Final Summary of Research Report to the National Aeronautics and Space Administration Cosmochemistry Program

NASA Technical Reports Server (NTRS)

O'D. Alexander, Conel

2003-01-01

The discovery of presolar grains in meteorites is one of the most exciting recent developments in meteoritics. Six types of presolar grain have been discovered: diamond, Sic, graphite, Si3N4, Al2O3 and MgAl2O4. These grains have been identified as presolar because their isotopic compositions are very different from those of Solar System materials. Comparison of their isotopic compositions with astronomical observations and theoretical models indicates most of the grains formed in the envelopes of highly evolved stars. They are, therefore, a new source of information with which to test astrophysical models of the evolution of these stars. In fact, because several elements can often be measured in the same grain, including elements that are not measurable spectroscopically in stars, the grain data provide some very stringent constraints for these models. Our primary goal is to create large, unbiased, multi-isotope databases of single presolar Sic, Si,N,, oxide and graphite grains in meteorites, as well as any new presolar grain types that are identified in the future. These will be used to: (i) test stellar and nucleosynthetic models, (ii) constrain the galactic chemical evolution (GCE) paths of the isotopes of Si, Ti, O and Mg, (iii) establish how many stellar sources contributed to the Solar System, (iv) constrain relative dust production rates of various stellar types and (v) assess how representative of galactic dust production the record in meteorites is. The primary tool for this project is a highly automated grain analysis system on the Carnegie 6f ion probe.

Final Summary of Research Report to the National Aeronautics and Space Administration Cosmochemistry Program

NASA Technical Reports Server (NTRS)

O'D.Alexander, Conel

2004-01-01

The discovery of presolar grains in meteorites is one of the most exciting recent developments in meteoritics. Six types of presolar grain have been discovered: diamond, Sic, graphite, Si3N4, Al2O3 and MgAl2O4. These grains have been identified as presolar because their isotopic compositions are very different from those of Solar System materials. Comparison of their isotopic compositions with astronomical observations and theoretical models indicates most of the grains formed in the envelopes of highly evolved stars. They are, therefore, a new source of information with which to test astrophysical models of the evolution of these stars. In fact, because several elements can often be measured in the same grain, including elements that are not measurable spectroscopically in stars, the grain data provide some very stringent constraints for these models. Our primary goal is to create large, unbiased, multi-isotope databases of single presolar Sic, Si,N,, oxide and graphite grains in meteorites, as well as any new presolar grain types that are identified in the future. These will be used to: (i) test stellar and nucleosynthetic models, (ii) constrain the galactic chemical evolution (GCE) paths of the isotopes of Si, Ti, 0 and Mg, (iii) establish how many stellar sources contributed to the Solar System, (iv) constrain relative dust production rates of various stellar types and (v) assess how representative of galactic dust production the record in meteorites is. The primary tool for this project is a highly automated grain analysis system we have developed for the Carnegie 6f ion probe.

Potassium isotope cosmochemistry, volatile depletion and the origin of the Earth

NASA Technical Reports Server (NTRS)

Humayun, M.; Clayton, R. N.

1993-01-01

We report the first results obtained by our techniques for the precise and accurate determination of the isotopic composition of potassium to constrain the mechanism of volatile element depletion in the formation of the Earth, Moon, and meteorites. Our measurements of delta(K-41) for six chondrites and ten terrestrial rocks attained an average precision of the individual measurement of plus or minus 0.4 percent (2 sigma; plus or minus 0.2 percent/a.m.u. and yield a net chondrite-Earth difference unresolved at the 99 percent confidence limit, delta(K-41) = 0.32 plus or minus 0.35 percent (3 delta). This sets a firm upper limit of 1.3 plus or minus 1.4 percent Rayleigh evaporation of terrestrial potassium (using alpha = square root of 41/39), compared with an observed approximately equals 85 percent chemical depletion of K relative to C1 chondrites. Similar conclusions are reached for the SNC meteorites, Shergotty and Zagami, for 15495 (lunar mare gabbro), and for the eucrite Juvinas. Our conclusion is that direct evaporation of volatile elements from planets (e.g. from silicate vapor atmospheres following giant impact) can be ruled out, and the cause of volatile loss must be sought elsewhere, e.g. nebular processes. Our present findings do not support the conclusions of Hinton et al., the discrepancy to be resolved at a later date. We also find lunar soil 64801, delta(K-41) = +4.99 plus or minus 0.53 percent, to be distinctly heavy in accord with Garner et al.

Chemical and Isotopic Analysis of Trace Organic Matter on Meteorites and Interstellar Dust Using a Laser Microprobe Instrument

NASA Technical Reports Server (NTRS)

Zare, Richard N.; Boyce, Joseph M. (Technical Monitor)

2001-01-01

Polycyclic Aromatic Hydrocarbons (PAHs) are of considerable interest today because they are ubiquitous on Earth and in the interstellar medium (ISM). In fact, about 20% of cosmic carbon in the galaxy is estimated to be in the form of PAHs. Investigation of these species has obvious uses for determining the cosmochemistry of the solar system. Work in this laboratory has focused on four main areas: 1) Mapping the spatial distribution of PAHs in a variety of meteoritic samples and comparing this distribution with mineralogical features of the meteorite to determine whether a correlation exists between the two. 2) Developing a method for detection of fullerenes in extraterrestrial samples using microprobe Laser Desorption Ionization Mass Spectroscopy and utilizing this technique to investigate fullerene presence, while exploring the possibility of spatially mapping the fullerene distribution in these samples through in situ detection. 3) Investigating a possible formation pathway for meteoritic and ancient terrestrial kerogen involving the photochemical reactions of PAHs with alkanes under prebiotic and astrophysically relevant conditions. 4) Studying reaction pathways and identifying the photoproducts generated during the photochemical evolution of PAH-containing interstellar ice analogs as part of an ongoing collaboration with researchers at the Astrochemistry Lab at NASA Ames. All areas involve elucidation of the solar system formation and chemistry using microprobe Laser Desorption Laser Ionization Mass Spectrometry. A brief description of microprobe Laser Desorption Ionization Mass Spectroscopy, which allows selective investigation of subattomole levels of organic species on the surface of a sample at 10-40 micrometer spatial resolution, is given.

Curation and Analysis of Samples from Comet Wild-2 Returned by NASA's Stardust Mission

NASA Technical Reports Server (NTRS)

Nakamura-Messenger, Keiko; Walker, Robert M.

2015-01-01

The NASA Stardust mission returned the first direct samples of a cometary coma from comet 81P/Wild-2 in 2006. Intact capture of samples encountered at 6 km/s was enabled by the use of aerogel, an ultralow dense silica polymer. Approximately 1000 particles were captured, with micron and submicron materials distributed along mm scale length tracks. This sample collection method and the fine scale of the samples posed new challenges to the curation and cosmochemistry communities. Sample curation involved extensive, detailed photo-documentation and delicate micro-surgery to remove particles without loss from the aerogel tracks. This work had to be performed in highly clean facility to minimize the potential of contamination. JSC Curation provided samples ranging from entire tracks to micrometer-sized particles to external investigators. From the analysis perspective, distinguishing cometary materials from aerogel and identifying the potential alteration from the capture process were essential. Here, transmission electron microscopy (TEM) proved to be the key technique that would make this possible. Based on TEM work by ourselves and others, a variety of surprising findings were reported, such as the observation of high temperature phases resembling those found in meteorites, rarely intact presolar grains and scarce organic grains and submicrometer silicates. An important lesson from this experience is that curation and analysis teams must work closely together to understand the requirements and challenges of each task. The Stardust Mission also has laid important foundation to future sample returns including OSIRIS-REx and Hayabusa II and future cometary nucleus sample return missions.

The Spatial Distribution of Organic Matter and Mineralogical Relationships in Carbonaceous Chondrites

NASA Technical Reports Server (NTRS)

Clemett, S. J.; Messenger, S.; Thomas-Keprta, K. L.; Nakamura-Messenger, K.

2012-01-01

Organic matter present within primitive carbonaceous meteorites represents the complex conglomeration of species formed in a variety of physically and temporally distinct environments including circumstellar space, the interstellar medium, the Solar Nebula & Jovian sub-nebulae and asteroids. In each case, multiple chemical pathways would have been available for the synthesis of organic molecules. Consequently these meteorites constitute a unique record of organic chemical evolution in the Universe and one of the biggest challenges in organic cosmochemistry has been in deciphering this record. While bulk chemical analysis has provided a detailed description of the range and diversity of organic species present in carbonaceous chondrites, there is virtually no hard experimental data as to how these species are spatially distributed and their relationship to the host mineral matrix, (with one exception). The distribution of organic phases is nevertheless critical to understanding parent body processes. The CM and CI chondrites all display evidence of low temperature (< 350K) interaction with aqueous fluids, which based on O isotope data, flowed along thermal gradients within the respective parent bodies. This pervasive aqueous alteration may have led to aqueous geochromatographic separation of organics and synthesis of new organics coupled to aqueous mineral alteration. To address such issues we have applied the technique of microprobe two-step laser desorption / photoionization mass spectrometry (L2MS) to map in situ the spatial distribution of a broad range of organic species at the micron scale in the freshly exposed matrices of the Bells, Tagish Lake and Murchison (CM2) carbonaceous chondrites.

Modification of REE distribution of ordinary chondrites from Atacama (Chile) and Lut (Iran) hot deserts: Insights into the chemical weathering of meteorites

NASA Astrophysics Data System (ADS)

Pourkhorsandi, Hamed; D'Orazio, Massimo; Rochette, Pierre; Valenzuela, Millarca; Gattacceca, Jérôme; Mirnejad, Hassan; Sutter, Brad; Hutzler, Aurore; Aboulahris, Maria

2017-09-01

The behavior of rare earth elements (REEs) during hot desert weathering of meteorites is investigated. Ordinary chondrites (OCs) from Atacama (Chile) and Lut (Iran) deserts show different variations in REE composition during this process. Inductively coupled plasma-mass spectrometry (ICP-MS) data reveal that hot desert OCs tend to show elevated light REE concentrations, relative to OC falls. Chondrites from Atacama are by far the most enriched in REEs and this enrichment is not necessarily related to their degree of weathering. Positive Ce anomaly of fresh chondrites from Atacama and the successive formation of a negative Ce anomaly with the addition of trivalent REEs are similar to the process reported from Antarctic eucrites. In addition to REEs, Sr and Ba also show different concentrations when comparing OCs from different hot deserts. The stability of Atacama surfaces and the associated old terrestrial ages of meteorites from this region give the samples the necessary time to interact with the terrestrial environment and to be chemically modified. Higher REE contents and LREE-enriched composition are evidence of contamination by terrestrial soil. Despite their low degrees of weathering, special care must be taken into account while working on the REE composition of Atacama meteorites for cosmochemistry applications. In contrast, chondrites from the Lut desert show lower degrees of REE modification, despite significant weathering signed by Sr content. This is explained by the relatively rapid weathering rate of the meteorites occurring in the Lut desert, which hampers the penetration of terrestrial material by forming voluminous Fe oxide/oxyhydroxides shortly after the meteorite fall.

Research Report to the National Aeronautics and Space Administration Cosmochemistry Program

NASA Technical Reports Server (NTRS)

Alexander, Conel O'D.

2004-01-01

The discovery of presolar grains in meteorites is one of the most exciting recent developments in meteoritics. Six types of presolar grain have been discovered: diamond, Sic, graphite, Si3N4, Al2O3 and MgAl2O4 (NIITLER, 2003). These grains have been identified as presolar because their isotopic compositions are very different from those of Solar System materials. Comparison of their isotopic compositions with astronomical observations and theoretical models indicates that most of the grains formed in the envelopes of highly evolved stars. They are, therefore, a new source of information with which to test astrophysical models of the evolution of these stars. In fact, because several elements can often be measured in the same grain, including elements that are not measurable spectroscopically in stars, the grain data provide some very stringent constraints for these models. Our primary goal is to create large, unbiased, multi-isotope databases of single presolar Sic, Si3N4, oxide and graphite grains in meteorites, as well as any new presolar grain types that are identified in the future. These will be used to: (i) test stellar and nucleosynthetic models, (ii) constrain the galactic chemical evolution (GCE) paths of the isotopes of Si, Ti, O and Mg, (iii) establish how many stellar sources contributed to the Solar System, (iv) constrain relative dust production rates of various stellar types and (v) assess how representative of galactic dust production the record in meteorites is. The primary tool for this project is a highly automated grain analysis system on the Carnegie 6f ion probe. This proposal was part of a long-standing research effort that is still ongoing.

Recent Advances in Organic Cosmochemistry

NASA Technical Reports Server (NTRS)

Sandford, Scott A.; Witteborn, Fred C. (Technical Monitor)

1994-01-01

The Astrochemistry Laboratory at NASA's Ames Research Center pursues a variety of activities, most of which center around the use of spectroscopy (ultraviolet to far-infrared) for the interpretation of astronomical and meteoritic data. One of our key activities is the study of the chemical and physical properties of cometary, interstellar, and planetary ice analogs and matrix-isolated molecules of astrophysical interest. As a result of these studies it is now known that a significant fraction of the carbon in the interstellar medium (ISM) is in reasonably complex forms, some of which are clearly of interest for exobiology. Examples of compounds known or suspected to be present in space include polycyclic aromatic hydrocarbons (PAHs), microdiamonds, an aliphatic-rich component found in the diffuse interstellar medium, and a variety of molecular species produced by the irradiation of mixed molecular ices in dense clouds. A number of the species produced by irradiation contain nitrogen and appear to offer an additional means of producing some of the amino acids found in meteorites. I will review these complex carbonaceous materials and discuss how they are connected with each other and the organic materials that ultimately ended up as part of our own Solar System. Specific points that will probably be covered include: (1) the composition of the ices in interstellar dense molecular clouds; (2) the more complex organic compounds produced when these ices are irradiated and/or warmed; (3) the detection of microdiamonds in space; (4) the discovery that aliphatic materials may constitute as much as 15% of all the carbon in the diffuse ISM, appears to be present everywhere in the galaxy, and yet seems to be present everywhere in the galaxy, and yet seems to be significantly concentrated towards the center of the galaxy.

Synthesis of Ti Oxides at Reducing Conditions: Implications for Beamline Standards and Cosmochemistry

NASA Technical Reports Server (NTRS)

Righter, K.; Pando, K. A.; Butterworth, A. L.; Gainsforth, Z.; Jilly-Rehak, C. E.; Westphal, A. J.

2017-01-01

These initial experiments demonstrate the great potential for synthesizing customized compounds for use as standards, or in buffering experiments at reducing conditions. We are also investigating Cr and V oxides, as well as compounds containing these elements such as FeV2O4 and FeCr2O4. Oxygen fugacity exerts a major control on mineral major element chemistry and elemental valence of minerals in any plane-tary compositional system [1]. For Earth, Fe is multivalent ranging from nearly Fe0 at low fO2 in the deep mantle to Fe2+ to Fe3+ at high low fO2. For solar nebular and meteoritic materials fO2 ranges from near IW to 10 log fO2 units below the IW buffer [1]. Phases in CAIs, for example, contain no Fe2+, but may contain Ti4+, Ti3+, or Ti2+, and Cr3+ or Cr2+, and V3+ or V2+ [1,2,3]. De-tailed study of inclusions may reveal important differences in fO2 thus reflecting different environments in the solar nebula [4]. XANES, FEG-SEM, and TEM can reveal such variations in micro and nano samples such as Stardust and cosmic dust particles [5], but successful application to reduced conditions depends upon the availability of well characterized standards. Acquiring appropriate standards for reduced phases that contain Ti3+ or Ti2+, Cr3+ or Cr2+, and V3+ or V2+ can be a challenge. Here we report our preliminary results at synthesizing reduced Ti bearing standards, and focus on the preliminary characterization.

The Cosmochemistry of Pluto: A Primordial Origin of Volatiles?

NASA Astrophysics Data System (ADS)

Glein, C. R.; Waite, J. H., Jr.

2017-12-01

Pluto is a wonderland of volatiles. Nitrogen, methane, and carbon monoxide are the principal volatiles that maintain its tenuous atmosphere, and they have also created a mesmerizing landscape of icy geological features, including Pluto's iconic "heart". Recent data, particularly those returned by the New Horizons mission [1-3], allow us to begin testing hypotheses for the cosmochemical origins of these world-shaping species on Pluto. Here, we investigate if Pluto's volatiles could have been accreted in its building blocks. We take both bottom-up and top-down approaches in testing this hypothesis in terms of mass balance. We estimate Pluto's primordial inventory of volatiles by scaling a range of cometary abundances up to the ice mass fraction of Pluto. We also make estimates of the present and lost inventories of volatiles based on surface observations and interpretations, as well as different scenarios of atmospheric photochemistry and escape. We find that, if primordial Pluto resembled a giant comet with respect to volatile abundances, then the initial volatile inventory would have been sufficient to account for the estimated present and lost inventories. This consistency supports a primordial origin for Pluto's volatiles. However, the observed ratio of CO/N2 in Pluto's atmosphere [4] is several orders of magnitude lower than the nominal cometary value. We are currently using phase equilibrium and rate models to explore if volatile layering in Sputnik Planitia, or the destruction of CO in a past or present subsurface ocean of liquid water could explain the apparent depletion of CO on Pluto. References: [1] Moore et al. (2016) Science 351, 1284. [2] Grundy et al. (2016) Science 351, aad9189. [3] Gladstone et al. (2016) Science 351, aad8866. [4] Lellouch et al. (2017) Icarus 286, 289.

Institute of Geophyics and Planetary Physics. Annual report for FY 1994

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryerson, F.J.

1995-09-29

The Institute of Geophysics and Planetary Physics (IGPP) is a Multicampus Research Unit of the University of California (UC). IGPP was founded in 1946 at UC Los Angeles with a charter to further research in the earth and planetary sciences and in related fields. The Institute now has branches at UC campuses in Los Angeles, San Diego, Riverside, and Irvine and at Los Alamos and Lawrence Livermore national laboratories. The University-wide IGPP has played an important role in establishing interdisciplinary research in the earth and planetary sciences. For example, IGPP was instrumental in founding the fields of physical oceanography andmore » space physics, which at the time fell between the cracks of established university departments. Because of its multicampus orientation, IGPP has sponsored important interinstitutional consortia in the earth and planetary sciences. Each of the six branches has a somewhat different intellectual emphasis as a result of the interplay between strengths of campus departments and Laboratory programs. The IGPP branch at Lawrence Livermore National Laboratory (LLNL) was approved by the Regents of the University of California in 1982. IGPP-LLNL emphasizes research in seismology, geochemistry, cosmochemistry, high-pressure sciences, and astrophysics. It provides a venue for studying the fundamental aspects of these fields, thereby complementing LLNL programs that pursue applications of these disciplines in national security and energy research. IGPP-LLNL is directed by Charles Alcock and is structured around three research centers. The Center for Geosciences, headed by George Zandt and Frederick Ryerson, focuses on research in geophysics and geochemistry. The Center for High-Pressure Sciences, headed by William Nellis, sponsors research on the properties of planetary materials and on the synthesis and preparation of new materials using high-pressure processing.« less

Laser ablation inductively coupled plasma mass spectrometry for direct isotope ratio measurements on solid samples

NASA Astrophysics Data System (ADS)

Pickhardt, Carola; Dietze, Hans-Joachim; Becker, J. Sabine

2005-04-01

Isotope ratio measurements have been increasingly used in quite different application fields, e.g., for the investigation of isotope variation in nature, in geoscience (geochemistry and geochronology), in cosmochemistry and planetary science, in environmental science, e.g., in environmental monitoring, or by the application of the isotope dilution technique for quantification purposes using stable or radioactive high-enriched isotope tracers. Due to its high sensitivity, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is today a challenging mass spectrometric technique for the direct determination of precise and accurate isotope ratios in solid samples. In comparison to laser ablation quadrupole ICP-MS (LA-ICP-QMS), laser ablation coupled to a double-focusing sector field ICP-MS (LA-ICP-SFMS) with single ion detection offers a significant improvement of sensitivity at low mass resolution, whereby isotope ratios can be measured with a precision to 0.1% relative standard deviation (R.S.D.). In LA-ICP-SFMS, many disturbing isobaric interferences of analyte and molecular ions can be separated at the required mass resolution (e.g., 40Ar16O+ and 56Fe+ for iron isotope ratio measurements). The precision on isotope ratio measurements was improved by one order of magnitude via the simultaneous detection of mass-separated ion currents of isotopes using multiple ion collectors in LA-ICP-MS (LA-MC-ICP-MS). The paper discusses the state of the art, the challenges and limits in isotope ratio measurements by LA-ICP-MS using different instrumentations at the trace and ultratrace level in different fields of application as in environmental and biological research, geochemistry and geochronology with respect to their precision and accuracy.

DUSTER: collection of meteoric CaO and carbon smoke particles in the upper stratosphere .

NASA Astrophysics Data System (ADS)

Della Corte, V.; Rietmeijer, F. J. M.; Rotundi, A.; Ferrari, M.; Palumbo, P.

Nanometer- to micrometer-size particles present in the upper stratosphere are a mixture of terrestrial and extra-terrestrial origins. They can be extraterrestrial particles condensed after meteor ablation. Meteoric dust in bolides is occasionally deposited into the lower stratosphere around 20 km altitude. Nanometer CaO and pure carbon smoke particles were collected at 38 km altitude in the upper stratosphere in the Arctic during June 2008 using DUSTER (Dust in the Upper Stratosphere Tracking Experiment and Retrieval), a balloon-borne instrument for the non-destructive collection of solid particles between 200 nm to 40 microns. We report the collection of micron sized CaCO_3 (calcite) grains. Their morphologies show evidence of melting and condensation after vaporization suggest at temperatures of approximately 3500 K. The formation environment of the collected grains was probably a dense dust cloud formed by the disintegration of a carbonaceous meteoroid during deceleration in the Earth� atmosphere. For the first time, DUSTER collected meteor ablation products that were presumably associated with the disintegration of a bolide crossing the Earth's atmosphere. The collected mostly CaO and pure carbon nanoparticles from the debris cloud of a fireball, included: 1) intact fragments; 2) quenched melted grains; and 3) vapor phase condensation products. The DUSTER project was funded by the Italian Space Agency (ASI), PRIN2008/MIUR (Ministero dell'Istruzione dell'Universitá e della Ricerca), PNRA 2013(Piano Nazionale Ricerca Antartide). CNES graciously provided this flight opportunity. We thank E. Zona and S. Inarta at the Laboratorio di Fisica Cosmica INAF, Osservatorio Astronomico di Capodimonte-Universitá di Napoli Parthenope. F.J.M.R. was supported by grant NNX07AI39G from the NASA Cosmochemistry Program. We thank three anonymous reviewers who assisted us in introducing our new instrument.

CAMECA IMS 1300-HR3: The New Generation Ion Microprobe

NASA Astrophysics Data System (ADS)

Peres, P.; Choi, S. Y.; Renaud, L.; Saliot, P.; Larson, D. J.

2016-12-01

The success of secondary ion mass spectrometry (SIMS) in Geo- and Cosmo-chemistry relies on its performance in terms of: 1) very high sensitivity (mandatory for high precision measurements or to achieve low detection limits); 2) a broad mass range of elemental and isotopic species, from low mass (H) to high mass (U and above); 3) in-situ analysis of any solid flat polished surface; and 4) high spatial resolution from tens of microns down to sub-micron scale. The IMS 1300-HR3 (High Reproducibility, High spatial Resolution, High mass Resolution) is the latest generation of CAMECA's large geometry magnetic sector SIMS (or ion microprobe), successor to the internationally recognized IMS 1280-HR. The 1300-HR3delivers unmatched analytical performance for a wide range of applications (stable isotopes, geochronology, trace elements, nuclear safeguards and environmental studies…) due to: • High brightness RF-plasma oxygen ion source with enhanced beam density and current stability, dramatically improving spatial resolution, data reproducibility, and throughput • Automated sample loading system with motorized sample height (Z) adjustment, significantly increasing analysis precision, ease-of-use, and productivity • UV-light microscope for enhanced optical image resolution, together with dedicated software for easy sample navigation (developed by University of Wisconsin, USA) • Low noise 1012Ω resistor Faraday cup preamplifier boards for measuring low signal intensities In addition, improvements in electronics and software have been integrated into the new instrument. In order to meet a growing demand from geochronologists, CAMECA also introduces the KLEORA, which is a fully optimized ion microprobe for advanced mineral dating derived from the IMS 1300-HR3. Instrumental developments as well as data obtained for stable isotope and U-Pb dating applications will be presented in detail.

Chemical separation of Mo and W from terrestrial and extraterrestrial samples via anion exchange chromatography.

PubMed

Nagai, Yuichiro; Yokoyama, Tetsuya

2014-05-20

A new two-stage chemical separation method was established using an anion exchange resin, Eichrom 1 × 8, to separate Mo and W from four natural rock samples. First, the distribution coefficients of nine elements (Ti, Fe, Zn, Zr, Nb, Mo, Hf, Ta, and W) under various chemical conditions were determined using HCl, HNO3, and HF. On the basis of the obtained distribution coefficients, a new technique for the two-stage chemical separation of Mo and W, along with the group separation of Ti-Zr-Hf, was developed as follows: 0.4 M HCl-0.5 M HF (major elements), 9 M HCl-0.05 M HF (Ti-Zr-Hf), 9 M HCl-1 M HF (W), and 6 M HNO3-3 M HF (Mo). After the chemical procedure, Nb remaining in the W fraction was separated using 9 M HCl-3 M HF. On the other hand, Nb and Zn remaining in the Mo fraction were removed using 2 M HF and 6 M HCl-0.1 M HF. The performance of this technique was evaluated by separating these elements from two terrestrial and two extraterrestrial samples. The recovery yields for Mo, W, Zr, and Hf were nearly 100% for all of the examined samples. The total contents of the Zr, Hf, W, and Mo in the blanks used for the chemical separation procedure were 582, 9, 29, and 396 pg, respectively. Therefore, our new separation technique can be widely used in various fields of geochemistry, cosmochemistry, and environmental sciences and particularly for multi-isotope analysis of these elements from a single sample with significant internal isotope heterogeneities.

The GENESIS Mission: Solar Wind Isotopic and Elemental Compositions and Their Implications

NASA Astrophysics Data System (ADS)

Wiens, R. C.; Burnett, D. S.; McKeegan, K. D.; Kallio, A. P.; Mao, P. H.; Heber, V. S.; Wieler, R.; Meshik, A.; Hohenberg, C. M.; Mabry, J. C.; Gilmour, J.; Crowther, S. A.; Reisenfeld, D. B.; Jurewicz, A.; Marty, B.; Pepin, R. O.; Barraclough, B. L.; Nordholt, J. E.; Olinger, C. T.; Steinberg, J. T.

2008-12-01

The GENESIS mission was a novel NASA experiment to collect solar wind at the Earth's L1 point for two years and return it for analysis. The capsule crashed upon re-entry in 2004, but many of the solar-wind collectors were recovered, including separate samples of coronal hole, interstream, and CME material. Laboratory analyses of these materials have allowed higher isotopic precision than possible with current in-situ detectors. To date GENESIS results have been obtained on isotopes of O, He, Ne, Ar, Kr, and Xe on the order of 1% accuracy and precision, with poorer uncertainty on Xe isotopes and significantly better uncertainties on the lighter noble gases. Elemental abundances are available for the above elements as well as Mg, Si, and Fe. When elemental abundances are compared with other in situ solar wind measurements, agreement is generally quite good. One exception is the Ne elemental abundance, which agrees with Ulysses and Apollo SWC results, but not with ACE. Neon is of particular interest because of the uncertainty in the solar Ne abundance, which has significant implications for the standard solar model. Helium isotopic results of material from the different solar wind regimes collected by GENESIS is consistent with isotopic fractionation predictions of the Coulomb drag model, suggesting that isotopic fractionation corrections need to be applied to heavier elements as well when extrapolating solar wind to solar compositions. Noble gas isotopic compositions from GENESIS are consistent with those obtained for solar wind trapped in lunar grains, but have for the first time yielded a very precise Ar isotopic result. Most interesting for cosmochemistry is a preliminary oxygen isotopic result from GENESIS which indicates a solar enrichment of ~4% in 16O relative to the planets, consistent with a photolytic self-shielding phenomenon during solar system formation. Analyses of solar wind N and C isotopes may further elucidate this phenomenon. Preliminary results from GENESIS have been reported for N, and results are still pending for C.

Fe isotope composition of bulk chondrules from Murchison (CM2): Constraints for parent body alteration, nebula processes and chondrule-matrix complementarity

NASA Astrophysics Data System (ADS)

Hezel, Dominik C.; Wilden, Johanna S.; Becker, Daniel; Steinbach, Sonja; Wombacher, Frank; Harak, Markus

2018-05-01

Chondrules are a major constituent of primitive meteorites. The formation of chondrules is one of the most elusive problems in cosmochemistry. We use Fe isotope compositions of chondrules and bulk chondrites to constrain the conditions of chondrule formation. Iron isotope compositions of bulk chondrules are so far only known from few studies on CV and some ordinary chondrites. We studied 37 chondrules from the CM chondrite Murchison. This is particularly challenging, as CM chondrites contain the smallest chondrules of all chondrite groups, except for CH chondrites. Bulk chondrules have δ56Fe between -0.62 and +0.24‰ relative to the IRMM-014 standard. Bulk Murchison has as all chondrites a δ56Fe of 0.00‰ within error. The δ56Fe distribution of the Murchison chondrule population is continuous and close to normal. The width of the δ56Fe distribution is narrower than that of the Allende chondrule population. Opaque modal abundances in Murchison chondrules is in about 67% of the chondrules close to 0 vol.%, and in 33% typically up to 6.5 vol.%. Chondrule Al/Mg and Fe/Mg ratios are sub-chondritic, while bulk Murchison has chondritic ratios. We suggest that the variable bulk chondrule Fe isotope compositions were established during evaporation and recondensation prior to accretion in the Murchison parent body. This range in isotope composition was likely reduced during aqueous alteration on the parent body. Murchison has a chondritic Fe isotope composition and a number of chondritic element ratios. Chondrules, however, have variable Fe isotope compositions and chondrules and matrix have complementary Al/Mg and Fe/Mg ratios. In combination, this supports the idea that chondrules and matrix formed from a single reservoir and were then accreted in the parent body. The formation in a single region also explains the compositional distribution of the chondrule population in Murchison.

Composition of matter in the heliosphere

NASA Astrophysics Data System (ADS)

Bochsler, Peter

2009-03-01

The Sun is by far the largest reservoir of matter in the solar system and contains more than 99% of the mass of the solar system. Theories on the formation of the solar system maintain that the gravitational collapse is very efficient and that typically not more than one tenth from the solar nebula is lost during the formation process. Consequently, the Sun can be considered as a representative sample of interstellar matter taken from a well mixed reservoir 4.6 Gy ago, at about 8 kpc from the galactic center. At the same time, the Sun is also a faithful witness of the composition of matter at the beginning of the evolution of the solar system and the formation of planets, asteroids, and comets. Knowledge on the solar composition and a fair account of the related uncertainties is relevant for many fields in astrophysics, planetary sciences, cosmo- and geochemistry. Apart from the basic interest in the chemical evolution of the galaxy and the solar system, compositional studies have also led to many applications in space research, i.e., it has helped to distinguish between different components of diffuse heliospheric matter. The elemental, isotopic, and charge state composition of heliospheric particles (solar wind, interstellar neutrals, pickup ions) has been used for a multitude of applications, such as tracing the source material, constraining parameters for models of the acceleration processes, and of the transport through the interplanetary medium. It is important to realize, that the two mainstream applications, as outlined above - geochemistry and cosmochemistry on one side, and tracing of heliospheric processes on the other side - are not independent of each other. Understanding the physical processes, e.g., of the fractionation of the solar wind, is crucial for the interpretation of compositional data; on the other hand, reliable information on the source composition is the basis for putting constraints on models of the solar wind fractionation.

Applications of the 190Pt-186Os isotope system to geochemistry and cosmochemistry

USGS Publications Warehouse

Walker, R.J.; Morgan, J.W.; Beary, E.S.; Smoliar, M.I.; Czamanske, G.K.; Horan, M.F.

1997-01-01

Platinum is fractionated from osmium primarily as a consequence of processes involving sulfide and metal crystallization. Consequently, the 190Pt-186Os isotope system (190Pt ??? 186Os + ??) shows promise for dating some types of magmatic sulfide ores and evolved iron meteorites. The first 190Pt-186Os isochrons are presented here for ores from the ca. 251 Ma Noril'sk, Siberia plume, and for group IIAB magmatic iron meteorites. Given the known age of the Noril'sk system, a decay constant for 190Pt is determined to be 1.542 ?? 10-12a-1, with ??1% uncertainty. The isochron generated for the IIAB irons is consistent with this decay constant and the known age of the group. The 186Os/188Os ratios of presumably young, mantle-derived osmiridiums and also the carbonaceous chondrite Allende were measured to high-precision to constrain the composition of the modern upper mantle. These compositions overlap, indicating that the upper mantle is chondritic within the level of resolution now available. Our best estimate for this 186Os/188Os ratio is 0.119834 ?? 2 (2??M). The 190Pt/186Os ratios determined for six enstatite chondrites average 0.001659 ?? 75, which is very similar to published values for carbonaceous chondrites. Using this ratio and the presumed composition of the modern upper mantle and chondrites, a solar system initial 186Os/188Os ratio of 0.119820 is calculated. In comparison to the modern upper mantle composition, the 186Os/188Os ratio of the Noril'sk plume was approximately 0.012% enriched in 186Os. Possible reasons for this heterogeneity include the recycling of Pt-rich crust into the mantle source of the plume and derivation of the osmium from the outer core. Derivation of the osmium from the outer core is our favored model. Copyright ?? 1997 Elsevier Science Ltd.

The CN/C15N isotopic ratio towards dark clouds

NASA Astrophysics Data System (ADS)

Hily-Blant, P.; Pineau des Forêts, G.; Faure, A.; Le Gal, R.; Padovani, M.

2013-09-01

Understanding the origin of the composition of solar system cosmomaterials is a central question, not only in the cosmochemistry and astrochemistry fields, and requires various approaches to be combined. Measurements of isotopic ratios in cometary materials provide strong constraints on the content of the protosolar nebula. Their relation with the composition of the parental dark clouds is, however, still very elusive. In this paper, we bring new constraints based on the isotopic composition of nitrogen in dark clouds, with the aim of understanding the chemical processes that are responsible for the observed isotopic ratios. We have observed and detected the fundamental rotational transition of C15N towards two starless dark clouds, L1544 and L1498. We were able to derive the column density ratio of C15N over 13CN towards the same clouds and obtain the CN/C15N isotopic ratios, which were found to be 500 ± 75 for both L1544 and L1498. These values are therefore marginally consistent with the protosolar value of 441. Moreover, this ratio is larger than the isotopic ratio of nitrogen measured in HCN. In addition, we present model calculations of the chemical fractionation of nitrogen in dark clouds, which make it possible to understand how CN can be deprived of 15N and HCN can simultaneously be enriched in heavy nitrogen. The non-fractionation of N2H+, however, remains an open issue, and we propose some chemical way of alleviating the discrepancy between model predictions and the observed ratios. Appendices are available in electronic form at http://www.aanda.orgThe reduced spectra (in FITS format) are available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/557/A65

The kinetics and dynamics of the coma of Halley's comet

NASA Technical Reports Server (NTRS)

Combi, Michael R.

1994-01-01

This grant to the University of Michigan supported the efforts of Michael R. Combi to serve as a co-investigator in collaboration with a larger effort by the principal investigator, William Smyth of Atmospheric and Environmental Research, Inc. The overall objective of this project was to analyze in a self-consistent manner unique optical O((sup 1)D) and NH2 ultra-high resolution line profile data of excellent quality and other supporting lower-resolution spectral data for the coma of comet P/Halley by using highly developed and physically-based cometary coma models in order to determine and explain in terms of physical processes the actual dynamics and photochemical kinetics that occur in the coma. The justification for this work is that it provides a valuable and underlying physical base from which to interpret significantly different types of coma observations in a self-consistent manner and hence bring into agreement (or avoid) apparent inconsistencies that arise from non-physically based interpretations. The level of effort for the Michigan component amounted to less than three person-months over a planned period of three years. The period had been extended at no extra cost to four years because the Michigan grant and the AER contract did not have coincident time periods. An effort of somewhat larger scope was undertaken by the PI. The importance of the O((sup 1)D) profiles is that they provide a direct trace of the water distribution in comets. The line profile shape is produced by the convolution of the outflow velocity and thermal dispersion of the parent water molecules with the photokinetic ejection of the oxygen atoms upon photodissociation of the parent water molecules. Our understanding of the NH2 and its precursor ammonia are important for comet-to-comet composition variations as they relate to the cosmo-chemistry of the early solar nebula. Modeling of the distribution of NH2 is necessary in order to infer the ammonia production rates from NH2 observations.

In Situ Chemical Composition Measurements of Planetary Surfaces with a Laser Ablation Mass Spectrometer

NASA Astrophysics Data System (ADS)

Brigitte Neuland, Maike; Riedo, Andreas; Meyer, Stefan; Mezger, Klaus; Tulej, Marek; Wurz, Peter

2013-04-01

The knowledge of the chemical composition of moons, comets, asteroids or other planetary bodies is of particular importance for the investigation of the origin and evolution of the Solar System. For cosmochemistry, the elemental and isotopic composition of the surface material is essential information to investigate origin, differentiation and evolution processes of the body and therefore the history of our Solar System [1]. We show that the use of laser-based mass spectrometers is essential in such research because of their high sensitivity in the ppm range and their capability for quantitative elemental and isotopic analysis. A miniaturised Laser Ablation Time-of-Flight Mass Spectrometer (LMS) was developed in our group to study the elemental composition of solid samples [2]. The instrument's small size and light weight make it suitable for an application on a space mission to determine the elemental composition of a planetary surface for example [3]. Meteorites offer the excellent possibility to study extraterrestrial material in the laboratory. To demonstrate the sensitivity and functionality of the LMS instrument, a sample of the Allende meteorite has been investigated with a high spatial resolution. The LMS measurements allowed investigations of the elemental abundances in the Allende meteorite and detailed studies of the mineralogy and volatility [4]. These approaches can be of considerable interest for in situ investigation of grains and inhomogeneous materials with high sensitivity on a planetary surface. [1] Wurz, P., Whitby, J., Managadze, G., 2009, Laser Mass Spectrometry in Planetary Science, AIP Conf. Proc. CP1144, 70-75. [2] Tulej, M., Riedo, A., Iakovleva, M., Wurz, P., 2012, Int. J. Spec., On Applicability of a Miniaturized Laser Ablation Time of Flight Mass Spectrometer for Trace Element Measurements, article ID 234949. [3] Riedo, A., Bieler, A., Neuland, M., Tulej, M., Wurz, P., 2012, Performance evaluation of a miniature laser ablation time-of-flight mass spectrometer designed for in-situ investigations in planetary space research, J. Mass Spectrom., in press. [4] Neuland, M.B., Meyer, S., Mezger, K., Riedo, A., Tulej, M., Wurz, P., Probing the Allende meteorite with a miniature Laser-Ablation Mass Analyser for space application, Planetary and Space Science, Special Issue: Terrestrial Planets II, submitted

Mass Wasting and Ground Collapse in Terrains of Volatile-Rich Deposits as a Solar System-Wide Geological Process: The Pre-Galileo View

NASA Technical Reports Server (NTRS)

Moore, Jeffrey M.; Mellon, Michael T.; Zent, Aaron P.

1996-01-01

The polar terrains of Mars are covered in many places with irregular pits and retreating scarps, as are some of the surfaces of the outer-planet satellites. These features are interpreted by us as diagnostic of exogenic degradation due to the loss of a volatile rock-forming matrix or cement. In this study we propose that sublimation degradation is a plausible Solar Systemwide geological process. Candidate examples have been identified on Mars, Io, and Triton, and possibly Europa and Ganymede. We envision this process as having two end-member expressions (pits and scarps), for which we hypothesize two end-member mechanisms (massive localized lenses and areally extensive basal layers). In this study we focus on the role this process may play on the surfaces of the galilean satellites. Our principle modeling results are that for these satellites, H2S, CO2, and NH3 are the only viable candidate volatiles for sublimation degradation of landforms, in light of galilean satellite cosmochemistry. For Io's polar regions only H2S, and then only from slopes that face the Sun and have thin lags, is volatile enough to cause the observed sublimation-induced erosion at those latitudes. SO2 is not a viable candidate as an agent of erosion, especially for these polar landforms. In the case of Europa, only CO2 and H2S are viable candidates (given surface age constraints). Both species could be efficient eroders in nonpolar regions. H2S could generate erosion within the polar regions if the deposition and erosion conditions were essentially identical as those we invoked for Io's polar regions. For Ganymede (and Callisto) NH3 might be an agent of erosion in equatorial terrains of great age. The sublimation of CO2 and H2S is much more robust than NH3. The much slower rate of sublimation degradation from NH3 might be detectable by Galileo and used as a compositional indicator.

The distribution of uranium over Europe: Geological and environmental significance

USGS Publications Warehouse

Plant, J.A.; Reeder, S.; Salminen, R.; Smith, D.B.; Tarvainen, T.; de Vivo, B.; Petterson, M.G.

2003-01-01

The variation of baseline levels of uranium in soil and stream sediments over Europe is described, based on new data prepared by the Forum of European Geological Surveys (FOREGS). The samples have been collected and analysed according to the protocols established for the International Union of Geological Sciences/International Association of Geochemistry and Cosmochemistry (IUGS/IAGC) Working Group on Global Geochemical Baselines. The baseline levels of U vary between 0??21 to 53 mg kg-1 in topsoils, 0??19 to 30 mg kg-1 in subsoils and < 1 to 59 mg kg-1 in stream sediments. There is generally good agreement between the levels of U in the three sample types, and the median concentration in all three media is approximately 2 mg kg-1. The most anomalous baseline levels occur over the Variscan orogen, especially areas into which late post-orogenic radiothermal high heat production (HHP) granites were emplaced. Spiderdiagrams based on trace element levels and rare earth element (REE) plots, confirm the association between the highest U anomalies and evolved radiothermal granites. High values are also associated with parts of the Alpine terrain especially in Slovenia, where there are historical U workings, and Southern Italy, where high values of U reflect contemporary volcanism. In contrast, much of the Caledonides of North West Europe and the Precambrian of the Baltic Shield and East European craton and its overlying sedimentary cover have very low values, generally < 4 mg kg-1. The results suggest that the main concern for the environment and human health from U, and the Th and K with which it is generally associated, is the naturally occurring total gamma radiation and radon potential associated with radiothermal granites. This is likely to be especially important where the granites are mineralised and have been worked historically, for example in the North West of the Iberian Peninsula where U and its decay products are likely to be more dispersed in the surface environment. The study also indicates the value of multi-element data in distinguishing between anthropogenic and naturally occurring anomalies.

ARES Biennial Report 2012 Final

NASA Technical Reports Server (NTRS)

Stansbery, Eileen

2014-01-01

Since the return of the first lunar samples, what is now the Astromaterials Research and Exploration Science (ARES) Directorate has had curatorial responsibility for all NASA-held extraterrestrial materials. Originating during the Apollo Program (1960s), this capability at Johnson Space Center (JSC) included scientists who were responsible for the science planning and training of astronauts for lunar surface activities as well as experts in the analysis and preservation of the precious returned samples. Today, ARES conducts research in basic and applied space and planetary science, and its scientific staff represents a broad diversity of expertise in the physical sciences (physics, chemistry, geology, astronomy), mathematics, and engineering organized into three offices (figure 1): Astromaterials Research (KR), Astromaterials Acquisition and Curation (KT), and Human Exploration Science (KX). Scientists within the Astromaterials Acquisition and Curation Office preserve, protect, document, and distribute samples of the current astromaterials collections. Since the return of the first lunar samples, ARES has been assigned curatorial responsibility for all NASA-held extraterrestrial materials (Apollo lunar samples, Antarctic meteorites - some of which have been confirmed to have originated on the Moon and on Mars - cosmic dust, solar wind samples, comet and interstellar dust particles, and space-exposed hardware). The responsibilities of curation consist not only of the longterm care of the samples, but also the support and planning for future sample collection missions and research and technology to enable new sample types. Curation provides the foundation for research into the samples. The Lunar Sample Facility and other curation clean rooms, the data center, laboratories, and associated instrumentation are unique NASA resources that, together with our staff's fundamental understanding of the entire collection, provide a service to the external research community, which relies on access to the samples. The curation efforts are greatly enhanced by a strong group of planetary scientists who conduct peerreviewed astromaterials research. Astromaterials Research Office scientists conduct peer-reviewed research as Principal or Co-Investigators in planetary science (e. g., cosmochemistry, origins of solar systems, Mars fundamental research, planetary geology and geophysics) and participate as Co-Investigators or Participating Scientists in many of NASA's robotic planetary missions. Since the last report, ARES has achieved several noteworthy milestones, some of which are documented in detail in the sections that follow. Within the Human Exploration Science Office, ARES is a world leader in orbital debris research, modeling and monitoring the debris environment, designing debris shielding, and developing policy to control and mitigate the orbital debris population. ARES has aggressively pursued refinements in knowledge of the debris environment and the hazard it presents to spacecraft. Additionally, the ARES Image Science and Analysis Group has been recognized as world class as a result of the high quality of near-real-time analysis of ascent and on-orbit inspection imagery to identify debris shedding, anomalies, and associated potential damage during Space Shuttle missions. ARES Earth scientists manage and continuously update the database of astronaut photography that is predominantly from Shuttle and ISS missions, but also includes the results of 40 years of human spaceflight. The Crew Earth Observations Web site (http://eol.jsc.nasa.gov/Education/ESS/crew.htm) continues to receive several million hits per month. ARES scientists are also influencing decisions in the development of the next generation of human and robotic spacecraft and missions through laboratory tests on the optical qualities of materials for windows, micrometeoroid/orbital debris shielding technology, and analog activities to assess surface science operations. ARES serves as host to numerous students and visiting scientists as part of the services provided to the research community and conducts a robust education and outreach program. ARES scientists are recognized nationally and internationally by virtue of their success in publishing in peer-reviewed journals and winning competitive research proposals. ARES scientists have won every major award presented by the Meteoritical Society, including the Leonard Medal, the most prestigious award in planetary science and cosmochemistry; the Barringer Medal, recognizing outstanding work in the field of impact cratering; the Nier Prize for outstanding research by a young scientist; and several recipients of the Nininger Meteorite Award. One of our scientists received the Department of Defense (DoD) Joint Meritorious Civilian Service Award (the highest civilian honor given by the DoD). ARES has established numerous partnerships with other NASA Centers, universities, and national laboratories. ARES scientists serve as journal editors, members of advisory panels and review committees, and society officers, and several scientists have been elected as Fellows in their professional societies. This biennial report summarizes a subset of the accomplishments made by each of the ARES offices and highlights participation in ongoing human and robotic missions, development of new missions, and planning for future human and robotic exploration of the solar system beyond low Earth orbit.

The 230Th correction is the 1st priority for accurate dates of young zircons: U/Th partitioning experiments and measurements

NASA Astrophysics Data System (ADS)

Krawczynski, M.; McLean, N.

2017-12-01

One of the most accurate and useful ways of determining the age of rocks that formed more than about 500,000 years ago is uranium-lead (U-Pb) geochronology. Earth scientists use U-Pb geochronology to put together the geologic history of entire regions and of specific events, like the mass extinction of all non-avian dinosaurs about 66 million years ago or the catastrophic eruptions of supervolcanoes like the one currently centered at Yellowstone. The mineral zircon is often utilized because it is abundant, durable, and readily incorporates uranium into its crystal structure. But it excludes thorium, whose isotope 230Th is part of the naturally occurring isotopic decay chain from 238U to 206Pb. Calculating a date from the relative abundances of 206Pb and 238U therefore requires a correction for the missing 230Th. Existing experimental and observational constraints on the way U and Th behave when zircon crystallizes from a melt are not known precisely enough, and thus currently the uncertainty in dates introduced by they `Th correction' is one of the largest sources of systematic error in determining dates. Here we present preliminary results on our study of actinide partitioning between zircon and melt. Experiments have been conducted to grow zircon from melts doped with U and Th that mimic natural magmas at a range of temperatures, and compositions. Synthetic zircons are separated from their coexisting glass and using high precision and high-spatial-resolution techniques, the abundance and distribution of U and Th in each phase is determined. These preliminary experiments are the beginning of a study that will result in precise determination of the zircon/melt uranium and thorium partition coefficients under a wide variety of naturally occurring conditions. This data will be fit to a multidimensional surface using maximum likelihood regression techniques, so that the ratio of partition coefficients can be calculated for any set of known parameters. The results of this study will reduce the largest source of uncertainty in dating young zircons and improve the accuracy of U-Pb dates, improving our ability to tell time during geologic processes. The attainment of more accurate timing of the geologic timescale is important to geologists of all disciplines, from paleontology to planetary cosmochemistry to geobiology.

The Ins and Outs of Water in the Earth's Mantle

NASA Astrophysics Data System (ADS)

Hauri, E. H.; Gaetani, G. A.; Shaw, A. M.; Kelley, K. A.; Saal, A. E.

2005-12-01

Most of the hydrogen in the Earth's upper mantle is dissolved in nominally anhydrous minerals such as olivine, orthopyroxene, clinopyroxene and garnet as structural OH [e.g. 1 ]. Considering the significant influence of hydrogen on mantle properties such as solidus temperature, rheology, conductivity and seismic velocity, it is important to understand both the distribution of water among mantle phases and the mass transfer processes that influence water distribution in the Earth's mantle. Despite the important role of water in the mantle, experimental determinations of the equilibrium distribution of trace amounts of hydrogen among coexisting silicate phases remain extremely limited. Improved analytical techniques have recently paved the way for quantitative investigations of water partitioning and abundances in nominally anhydrous mantle minerals [e.g. 2]. Several studies of submarine glasses have revealed correlated increases in incompatible elements and water contents along segments of mid-ocean ridges approaching hotspots [e.g. 3,4]. A source-related increase in the water content of the mantle is typically postulated to explain such observations, but elevated hotspot H2O contents may also relate to pressure differences in partitioning of water, analogous to the case for rare-earth elements (e.g. the "garnet signature"). New experimental water partitioning data illuminate these differences. Hydrogen isotope ratios vary in submarine glasses from ocean ridges, back-arc basins and hotspots, and in hydrous phases from arcs and hotspots, suggesting significant hydrogen isotopic variability in the mantle, which may be related to the subduction of water. Water clearly enters the upper mantle at subduction zones, however the full water budget for any single subduction zone is highly uncertain [e.g. 5]. This uncertainty in the water budget at convergent margins indicates that we do not even know whether the present-day net flux of water is into or out of the Earth. This talk will highlight areas of both knowledge and ignorance on the origin and distribution of water in the Earth's mantle. [1] Bell, D.R. & Rossman, G.R., 1992, Science, 255: 1391-1397. [2] Koga, K. et. al, 2002, Geochem. Geophys. Geosys. 4, doi: 10.1029/2002GC000378. [3] Dixon, J. E. et. al, 2002, Nature 420, 385-389. [4] Asimow, P. D. et. al, 2003, Geochem. Geophys. Geosys. 5, doi:10.1029/2003GC000568. [5] Hilton D. R.. et. al, 2002, in Noble Gases in Cosmochemistry and Geochemistry, 47:319-370.

A new combined nanoSIMS and continuous-flow IRMS approach to measure hydrogen isotopes from water in hydrated rhyolitic glass

NASA Astrophysics Data System (ADS)

Gatti, E.; Kitchen, N.; Newman, S.; Guan, Y.; Westgate, J.; Pearce, N. J. G.; Nikolic, D.; Eiler, J. M.

2016-12-01

The hydrogen-isotope value of water of hydration (or secondary water) preserved in rhyolitic glasses may provide significant insights regarding the climate at the time of their deposition and the impact of super-eruptions upon the environment. However, the ability of the glass to retain the environmental D/H isotopic signal after hydration needs to be tested, since modifications to the D/H systematics may result from the continuous exchange of D/H with the atmosphere or condensed water after initial glass hydration. Ideal geological archives to test whether the glass retains its original hydrogen signal are sediments in natural waters and ice cores, which preserve tephra in constrained horizons that can be independently isotopically characterised. However, tephra in marine and fresh water sediments and ice cores are often present in concentrations of the order of 1000 grains/cm3 (<5 mg of collectible material). Traditional IRMS methods require much more material ( 100-500 mg) and therefore cannot be applied. We present here a new integrated nanoSIMS and continuous flow IRMS approach to understand how water is distributed within single glass grains (diffusion profiles), quantify the time of hydration of young (Holocene) and old (Miocene) already well-characterised rhyolitic glasses, and measure the D/H ratio of the hydration water on single grains and bulk material consisting of only approximately 0.1-1 mg. The IRMS method measures the absolute abundance of hydrogen released from the sample by continuous-flow mass spectrometry. Current data indicates that the method can accurately measure a hydrogen signal from a rock sample containing at least 400 nanomoles of H2, corresponding to 70 µg of water, which translates to 1 mg of hydrous glass (>3 wt%) or 15 mg of dry ( 0.5 wt%) obsidian chips. The method can be improved by reducing the blank to <1 nmol/min and reducing capillary empty space. The bulk results obtained with the continuous-flow IRMS method will be compared to sub-micron mapping of single-grains using a high-resolution ion microprobe, the CAMECA NanoSIMS 50L, in the Microanalysis Center for Geochemistry and Cosmochemistry at California Institute of Technology, in order to define the reliability of the bulk method and assess natural variability within and among grains.

It's About Time: How Accurate Can Geochronology Become?

NASA Astrophysics Data System (ADS)

Harrison, M.; Baldwin, S.; Caffee, M. W.; Gehrels, G. E.; Schoene, B.; Shuster, D. L.; Singer, B. S.

2015-12-01

As isotope ratio precisions have improved to as low as ±1 ppm, geochronologic precision has remained essentially unchanged. This largely reflects the nature of radioactivity whereby the parent decays into a different chemical species thus putting as much emphasis on the determining inter-element ratios as isotopic. Even the best current accuracy grows into errors of >0.6 m.y. during the Paleozoic - a span of time equal to ¼ of the Pleistocene. If we are to understand the nature of Paleozoic species variation and climate change at anything like the Cenozoic, we need a 10x improvement in accuracy. The good news is that there is no physical impediment to realizing this. There are enough Pb* atoms in the outer few μm's of a Paleozoic zircon grown moments before eruption to permit ±0.01% accuracy in the U-Pb system. What we need are the resources to synthesize the spikes, enhance ionization yields, exploit microscale sampling, and improve knowledge of λ correspondingly. Despite advances in geochronology over the past 40 years (multicollection, multi-isotope spikes, in situ dating), our ability to translate a daughter atom into a detected ion has remained at the level of 1% or so. This means that a ~102 increase in signal can be achieved before we approach a physical limit. Perhaps the most promising approach is use of broad spectrum lasers that can ionize all neutrals. Radical new approaches to providing mass separation of such signals are emerging, including trapped ion cyclotron resonance and multi-turn, sputtered neutral TOF spectrometers capable of mass resolutions in excess of 105. These innovations hold great promise in geochronology but are largely being developed for cosmochemistry. This may make sense at first glance as cosmochemists are classically atom-limited (IDPs, stardust) but can be a misperception as the outer few μm's of a zircon may represent no more mass than a stardust mote. To reach the fundamental limits of geochronologic signals we need to look past the seeming macroscopic nature of our samples to the truly microscopic domains that hold the key temporal information and pursue transcendental approaches to detecting every daughter atom. The central role that geochronology plays in all aspects of historical geology potentially makes the vast majority of Earth scientists our partners in this endeavor.

Trace element analysis by EPMA in geosciences: detection limit, precision and accuracy

NASA Astrophysics Data System (ADS)

Batanova, V. G.; Sobolev, A. V.; Magnin, V.

2018-01-01

Use of the electron probe microanalyser (EPMA) for trace element analysis has increased over the last decade, mainly because of improved stability of spectrometers and the electron column when operated at high probe current; development of new large-area crystal monochromators and ultra-high count rate spectrometers; full integration of energy-dispersive / wavelength-dispersive X-ray spectrometry (EDS/WDS) signals; and the development of powerful software packages. For phases that are stable under a dense electron beam, the detection limit and precision can be decreased to the ppm level by using high acceleration voltage and beam current combined with long counting time. Data on 10 elements (Na, Al, P, Ca, Ti, Cr, Mn, Co, Ni, Zn) in olivine obtained on a JEOL JXA-8230 microprobe with tungsten filament show that the detection limit decreases proportionally to the square root of counting time and probe current. For all elements equal or heavier than phosphorus (Z = 15), the detection limit decreases with increasing accelerating voltage. The analytical precision for minor and trace elements analysed in olivine at 25 kV accelerating voltage and 900 nA beam current is 4 - 18 ppm (2 standard deviations of repeated measurements of the olivine reference sample) and is similar to the detection limit of corresponding elements. To analyse trace elements accurately requires careful estimation of background, and consideration of sample damage under the beam and secondary fluorescence from phase boundaries. The development and use of matrix reference samples with well-characterised trace elements of interest is important for monitoring and improving of the accuracy. An evaluation of the accuracy of trace element analyses in olivine has been made by comparing EPMA data for new reference samples with data obtained by different in-situ and bulk analytical methods in six different laboratories worldwide. For all elements, the measured concentrations in the olivine reference sample were found to be identical (within internal precision) to reference values, suggesting that achieved precision and accuracy are similar. The spatial resolution of EPMA in a silicate matrix, even at very extreme conditions (accelerating voltage 25 kV), does not exceed 7 - 8 μm and thus is still better than laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) or secondary ion mass spectrometry (SIMS) of similar precision. These make the electron microprobe an indispensable method with applications in experimental petrology, geochemistry and cosmochemistry.

Water-rich Martian mantle can account for the elastic thickness in Amazonian era

NASA Astrophysics Data System (ADS)

Katayama, I.; Matsuoka, Y.; Azuma, S.

2016-12-01

Although high water content in the Martian mantle is inferred from cosmochemistry, the direct measurements of water in the SNC meteorites are controversial, because hydrogen is a highly mobile element and the later terrestrial alteration can modify the primarily concentration in the Mars. On the one hand, water has a significant effect on the rock strength in both brittle and ductile fields; consequently, the presence of water can influence the elastic thickness that is primary controlled by stress distribution in the lithosphere. The Martian elastic lithosphere estimated from gravity and topography data indicates different thickness at the time of loading (e.g. McGovern et al. 2002). The increase of elastic thickness from Noachian to Hesperian is most likely related to the secular cooling in the Mars; however, the nearly constant elastic lithosphere in Amazonian cannot be explained by the thermal evolution alone. In this study, we applied recent rheological data to the Martian lithosphere and tested whether water can account for the elastic thickness seen in the Amazonian era. We incorporated the effect of pore fluid pressure in the brittle regime and Peierls mechanism in the ductile regime in the rheological model, which are not applied in the most previous calculation (e.g. Grott and Breuer 2008) but have a significant influence on the stress distribution in the lithosphere. Since the pore pressure reduces the effective normal stress on the fault plane, the maximum stress in the brittle regime is markedly decreased by the presence of pore fluid. The estimate of elastic lithosphere is dependent on thermal structure, and we used the heat production rate obtained from the Mars Odyssey spectrometry as thermal model (Hahn et al. 2011). Our results indicate the elastic thickness in Amazonian era of 120-170 km for dry condition and 80-110 km for wet condition. The thin elastic thickness calculated under wet environments is a result of significant reduction of flexure moment in the lithosphere. Our model indicates that water-rich Martian lithosphere can be responsible for the observed elastic thickness in Amazonian. However, the model is highly sensitive to the thermal structure and curvature, and more realistic data of heat flow targeted by the Insight mission would provide the robust water concentration in the Martian mantle.

Mass-Dependent and -Independent Fractionation of Mercury Isotopes in Aquatic Systems

NASA Astrophysics Data System (ADS)

Bergquist, B. A.; Joel, B. D.; Jude, D. J.

2008-12-01

Mercury is a globally distributed and highly toxic pollutant. Although Hg is a proven health risk, much of the natural cycle of Hg is not well understood and new approaches are needed to track Hg and the chemical transformations it undergoes in the environment. Recently, we demonstrated that Hg isotopes exhibit two types of isotope fractionation: (1) mass dependent fractionation (MDF) and (2) mass independent fractionation (MIF) of only the odd isotopes (Bergquist and Blum, 2007). The observation of large MIF of Hg isotopes (up to 5 permil) is exciting because only a few other isotopic systems have been documented to display large MIF, the most notable of which are oxygen and sulfur. In both cases, the application of MIF has proven very useful in a variety of fields including cosmochemistry, paleoclimatology, physical chemistry, atmospheric chemistry, and biogeochemistry. Both MDF and MIF isotopic signatures are observed in natural samples, and together they open the door to a new method for tracing Hg pollution and for investigating Hg behavior in the environment. For example, fish record MDF that appears to be related to size and age. Additionally, fish display MIF signatures that are consistent with the photo-reduction of methylmercury (Bergquist and Blum, 2007). If the MDF and MIF in ecosystems can be understood, the signatures in fish could inform us about the sources and processes transforming Hg and why there are differences in the bioaccumulation of Hg in differing ecosystems and populations of fish. This requires sampling of a variety of ecosystems, the sampling of many components of the ecosystems, and the use of other tracers such as carbon and nitrogen isotopes. We have expanded our studies of aquatic ecosystems to include several lakes in North America. Similar to other isotopic systems used to study food web dynamics and structure (i.e., C and N), the MDF of Hg in fish appears to be related to size and age. The MDF recorded in fish likely reflects both the sources of Hg to the fish and the excretion of Hg by the fish. Thus, MDF alone provides new insights into sources and bioaccumulation of Hg in food web. Fish populations from different lakes display distinct MIF and relationships between MDF and MIF. The degree of MIF is likely related to the amount of photo-reduction in a lake and dissolved organic carbon. We also sampled food sources and livers of fish to understand processes of isotopic fractionation in the food web.

The Gulliver sample return mission to Deimos

NASA Astrophysics Data System (ADS)

Britt, D. T.; Robinson, M.; Gulliver Team

The Martian moon Deimos presents a unique opportunity for a sample return mission. Deimos is spectrally analogous to type D asteroids, which are thought to be composed of highly primitive carbonaceous material that originated in the outer asteroid belt. It also is in orbit around Mars and has been accumulating material ejected from the Martian surface ever since the earliest periods of Martian history, over 4.4 Gyrs ago. There are a number of factors that make sample return from Deimos extremely attractive. It is Better: Deimos is a repository for two kinds of extremely significant and scientifically exciting ancient samples: (1) Primitive spectral D-type material that may have accreted in the outer asteroid belt and Trojan swarm. This material samples the composition of solar nebula well outside the zone of terrestrial planets and provides a direct sample of primitive material so common past 3 AU but so uncommon in the meteorite collection. (2) Ancient Mars, which could include the full range of Martian crustal and upper mantle material from the early differentiation and crustal-forming epoch as well as samples from the era of high volatile flux, thick atmosphere, and possible surface water. The Martian material on Deimos would be dominated by ejecta from the ancient crust of Mars, delivered during the Noachian Period of basin-forming impacts and heavy bombardment. It is Closer: Compared to other primitive D-type asteroids, Deimos is by far the most accessible. Because of its orbit around Mars, Deimos is far closer than any other D asteroid. It is Safer: Deimos is also by far the safest small body for sample return yet imaged. It is an order of magnitude less rocky than Eros and the NEAR-Shoemaker mission succeeded in landing on Eros with a spacecraft not designed for landing and proximity maneuvering. Because of Viking imagery we already know a great deal about the surface roughness of Deimos. It is known to be very smooth and have moderate topography and gravitational slopes. It is Easier: Deimos is farther from Mars and smaller than Phobos. This location minimizes the delta-V penalties from entering the Martian gravity well; minimizes the energy requirements for sampling maneuvers; and minimizes Martian tidal effects on S/C operations. After initial processing these samples will be made available as soon as possible to the international cosmochemistry community for detailed analysis. The mission management team includes Lockheed Martin Astronautics (flight system, I&T) and JPL (payload, mission ops, and mission management).

Isotope U-Pb age on single zircon and REE distribution in rocks and zircon from paleoproterozoic Kandalaksha-Kolvitsa complex Baltic shield

NASA Astrophysics Data System (ADS)

Steshenko, Ekaterina; Bayanova, Tamara; Drogobuzhskaya, Svetlana; Lyalina, Ludmila; Serov, Pavel; Chashchin, Viktor; Elizarov, Dmitriy

2017-04-01

Kandalaksha-Kolvitsa paleoproterozoic complex located in the N-E part of Baltic shield and consists of three zones. Marginal zone (mesocratic metanorite) lies at the base of the massif. Main zone is composed of leucocratic metagabbro. The upper zone is alteration of mataanorthosite and leucocratic metagabbro. All rocks were subjected to granulate and anorthositic metamorphism. Age of magmatic crystallization of the massif was determined for the first time, using the U-Pb isotope method for single zircon grains. Three fractions of single zircons from anorthosite of the Kandalaksha massif gave precise U-Pb age of 2435.5 ± 4.8 Ma. For the first time REE concentration (WR) was determined using a quadrupole mass spectrometer (Agilent 7500 ce ICP-MS) in the main varieties of rocks of the Kandalaksha-Kolvitsa paleoproterozoic complex. Anorthosite and leucocratic metagabbros (main zone) are characterized by a flat spectrum distribution of HREE, which were normalized by [1]. The REE pattern is characterized by significant positive anomalies of Eu ((Eu / Eu *)n = 3.72-3.91) in anorthosite and leucogabbros and 7.26 - in ortoamfibolitah. General content of individual elements that are common for this type of rocks: Cen = 5.82-8.54, Ybn = 1.54-1.58, which indicates that the process of crystallization of the rock occurred with predominant accumulation of plagioclase. According to geochemical and Nd-Sr isotopic data (ISr=0.702 - 0.706, ɛNd(T) = +1 - (-3)) Kandalaksha Kolvitsa complex, appear to have a general plume source with Paleoproterozoic layered intrusions of the Baltic Shield [2] Distribution of REE (ELAN-9000 ICP-MS) in zircon have a typical magmatic species: a positive Ce, negative Eu anomaly and HREE flat spectrum. Titanium content in zircons were measured for the calculation of their crystallization temperature with 8350C. These data are evidence of magmatic origin of zircon [3]. The scientific researches are supported by RFBR (projects № 15-35-20501, № 16-05-00305, 16-05-00367, 16-05-00427) and theme of state assignment № 0231-2015-0005. References: 1. Boynton W.V. Cosmochemistry of the rare earth elements: meteorite studies // Ed. Henderson P. Rare earth element geochemistry. Amsterdam: Elsevier. 1984. P. 63-114. 2. Watson E. B., Wark D.A., Thomas J.B. Crystallization thermometers for zircon and rutile // Contrib. Miner. Petrol. 2006. V. 151. P. 413-433. 3. Hoskin P.W.O. and Schaltegger U. The Composition of zirconand igneous and metamorphic petrogenesis // Reviews in mineralogy & geochemistry. 2003. V. 53. P. 27-62.

Hydrogen cyanide polymers, comets and the origin of life.

PubMed

Matthews, Clifford N; Minard, Robert D

2006-01-01

Hydrogen cyanide polymers--heterogeneous solids ranging in colour from yellow to orange to brown to black--could be major components of the dark matter observed on many bodies of the outer solar system including asteroids, moons, planets and, especially, comets. The presence on cometary nuclei of frozen volatiles such as methane, ammonia and water subjected to high energy sources makes them attractive sites for the ready formation and condensed-phase polymerization of hydrogen cyanide. This could account for the dark crust observed on Comet Halley in 1986 by the Vega and Giotto missions. Dust emanating from its nucleus would arise partly from HCN polymers as suggested by the Giotto detection of free hydrogen cyanide, CN radicals, solid particles consisting only of H, C and N, or only of H, C, N, O, and nitrogen-containing organic compounds. Further evidence for cometary HCN polymers could be expected from in situ analysis of the ejected material from Comet Tempel 1 after collision with the impactor probe from the two-stage Deep Impact mission on July 4, 2005. Even more revealing will be actual samples of dust collected from the coma of Comet Wild 2 by the Stardust mission, due to return to Earth in January 2006 for analyses which we have predicted will detect these polymers and related compounds. In situ results have already shown that nitriles and polymers of hydrogen cyanide are probable components of the cometary dust that struck the Cometary and Interstellar Dust Analyzer of the Stardust spacecraft as it approached Comet Wild 2 on January 2, 2004. Preliminary evidence (January 2005) obtained by the Huygens probe of the ongoing Cassini-Huygens mission to Saturn and its satellites indicates the presence of nitrogen-containing organic compounds in the refractory organic cores of the aerosols that give rise to the orange haze high in the atmosphere of Titan, Saturn's largest moon. Our continuing investigations suggest that HCN polymers are basically of two types: ladder structures with conjugated -C=N- bonds and polyamidines readily converted by water to polypeptides. Thermochemolysis GC-MS studies show that cleavage products of the polymer include alpha-amino acids, nitrogen heterocycles such as purines and pyrimidines, and provide evidence for peptide linkages. Hydrogen cyanide polymers are a plausible link between cosmochemistry and the origin of informational macromolecules. Implications for prebiotic chemistry are profound. Following persistent bolide bombardment, primitive Earth may have been covered by water and carbonaceous compounds, particularly HCN polymers which would have supplied essential components for establishing protein/nucleic acid life.

Rock magnetic properties of dusty olivine: a potential carrier of pre-accretionary remanence in unequilibrated ordinary chondrites

NASA Astrophysics Data System (ADS)

Lappe, S. C. L. L.; Harrison, R. J.; Feinberg, J. M.

2012-04-01

The mechanism of chondrule formation is an important outstanding question in cosmochemistry. Magnetic signals recorded by Fe-Ni nanoparticles in chondrules could carry clues to their origin. Recently, research in this area has focused on 'dusty olivine' grains within ordinary chondrites as potential carriers of pre-accretionary remanence. Dusty olivine is characterised by the presence of sub-micron Fe-Ni inclusions within the olivine host. These metal particles form via subsolidus reduction of the olivine during chondrule formation and are thought to be protected from subsequent chemical and thermal alteration by the host olivine. Three sets of synthetic dusty olivines have been produced, using natural olivine (average Ni-content of 0.3 wt%), synthetic Ni-containing olivine (0.1wt% Ni) and synthetic Ni-free olivine as starting materials. The starting materials were ground to powders, packed into a 2-3 mm3 graphite crucible, heated up to 1350 °C under a pure CO gas flow and kept at this temperature for 10 minutes. After this the samples were held in a fixed orientation and quenched into water in a range of known magnetic fields, ranging from 0.2 mT to 1.5 mT. We present here for the first time an analysis of a new FORC-based method of paleointensity determination applied to metallic Fe-bearing samples [1, 2]. The method uses a first-order reversal curve (FORC) diagram to generate a Preisach distribution of coercivities and interaction fields within the sample and then physically models the acquisition of TRM as a function of magnetic field, temperature and time using thermal relaxation theory. The comparison of observed and calculated NRM demagnetisation spectra is adversely effected by a large population of particles in the single-vortex state. Comparison of observed and calculated REM' curves, however, yields much closer agreement in the high-coercivity SD-dominated range. Calculated values of the average REM' ratio show excellent agreement with the experimental values - including the observed non-linearity of the remanence acquisition curve - suggesting that this method has the potential to reduce the uncertainties in non-heating paleointensity methods for extraterrestrial samples. [1] AR Muxworthy and D Heslop(2011) A Preisach method for estimating absolute paleofield intensity under the constraint of using only isothermal measurements: 1. Theoretical framework. Journal of Geophysical Research, 116, B04102, doi:10.1029/2010JB007843. [2] AR Muxworthy, D Heslop, GA Paterson, and D Michalk. A Preisach method for estimating absolute paleofield intensity under the constraint of using only isothermal measurements: 2. Experimental testing. Journal of Geophysical Research, 116, B04103, doi:10.1029/2010JB007844.

EURO-CARES: European Roadmap for a Sample Return Curation Facility and Planetary Protection Implications.

NASA Astrophysics Data System (ADS)

Brucato, John Robert

2016-07-01

A mature European planetary exploration program and evolving sample return mission plans gathers the interest of a wider scientific community. The interest is generated from studying extraterrestrial samples in the laborato-ry providing new opportunities to address fundamental issues on the origin and evolution of the Solar System, on the primordial cosmochemistry, and on the nature of the building blocks of terrestrial planets and on the origin of life. Major space agencies are currently planning for missions that will collect samples from a variety of Solar Sys-tem environments, from primitive (carbonaceous) small bodies, from the Moon, Mars and its moons and, final-ly, from icy moons of the outer planets. A dedicated sample return curation facility is seen as an essential re-quirement for the receiving, assessment, characterization and secure preservation of the collected extraterrestrial samples and potentially their safe distribution to the scientific community. EURO-CARES is a European Commission study funded under the Horizon-2020 program. The strategic objec-tive of EURO-CARES is to create a roadmap for the implementation of a European Extraterrestrial Sample Cu-ration Facility. The facility has to provide safe storage and handling of extraterrestrial samples and has to enable the preliminary characterization in order to achieve the required effectiveness and collaborative outcomes for the whole international scientific community. For example, samples returned from Mars could pose a threat on the Earth's biosphere if any living extraterrestrial organism are present in the samples. Thus planetary protection is an essential aspect of all Mars sample return missions that will affect the retrival and transport from the point of return, sample handling, infrastructure methodology and management of a future curation facility. Analysis of the state of the art of Planetary Protection technology shows there are considerable possibilities to define and develop technical and scientific features in a sample return mission and the infrastructural, procedur-al and legal issues that consequently rely on a curation facility. This specialist facility will be designed with con-sideration drawn from highcontainment laboratories and cleanroom facilities to protect the Earth from contami-nation with potential Martian organisms and the samples from Earth contaminations. This kind of integrated facility does not currently exist and this emphasises the need for an innovative design approach with an integrat-ed and multidisciplinary design to enable the ultimate science goals of such exploration. The issues of how the Planetary Protection considerations impact on the system technologies and scientific meaurements, with a final aim to prioritize outstanding technology needs is presented in the framework of sam-ple return study missions and the Horizon-2020 EURO-CARES project.

The Sulfur Cycle at Subduction Zones

NASA Astrophysics Data System (ADS)

de Moor, M. J.; Fischer, T. P.; Sharp, Z. D.

2013-12-01

We present sulfur (S) isotope data for magmatic gases emitted along the Central American (CA) Arc (oxidizing conditions ΔQFM ~+ 1.5) and at the East African Rift (reduced conditions ΔQFM ~0). The results are interpreted through mass balance calculations to characterize the S cycle through subduction zones with implications for the redox conditions of arc magmas. Voluminous gas emissions from Masaya, an open vent basaltic volcano in Nicaragua, represent >20% of the SO2 flux from the CA arc [1]. Samples from the Masaya plume have S isotope compositions of + 4.8 × 0.4 ‰ [2]. Degassing fractionation modeling and assessment of differentiation processes in this oxidized volcano suggest that this value is close to that of the source composition. High T gas samples from other CA volcanoes (Momotombo, Cerro Negro, Poas, Turrialba) range from + 3 ‰ (Cerro Negro) to + 7 ‰ (Poas; [3]). The high δ34S values are attributed to recycling of subducted oxidized sulfur (sulfate ~ + 20 ‰) through the CA arc. The δ34S values of the more reduced samples from East African Rift volcanoes, Erta Ale - 0.5 × 0.6 ‰ [3] and Oldoinyo Lengai -0.7 ‰ to + 1.2 ‰) are far lower and are probably sourced directly from ambient mantle. The subduction of oxidized material at arcs presents a likely explanation for the oxidized nature of arc magmas relative to magmas from spreading centers. We observe no distinguishable change in melt fO2 with S degassing and attribute these differences to tectonic setting. Monte Carlo modeling suggests that subducted crust (sediments, altered oceanic crust, and serpentinized lithospheric mantle) delivers ~7.7 × 2.2 x 1010 mols of S with δ34S of -1.5 × 2.3‰ per year into the subduction zone. The total S output from the arc is estimated to be 3.4 × 1.1 x 1010 mols/yr with a δ34S value similar to that of Masaya gas (+5 × 0.5 ‰). Considering δ34S values for ambient upper mantle (0 ‰ [4]) and slab-derived fluids (+14 ‰ [5]) allows calculation of the flux of S released from slab into the mantle wedge. Based on these constraints, we calculate that 1.2 × 0.4 x 1010 mols of S/yr is released from the slab. If slab-derived S is in the S6+ oxidation state, this flux is enough to oxidize the entire mantle wedge to the Fe3+/Fe2+ observed in typical arc rocks in ~ 20 million years. [1] Hilton et al. (2002) Noble Gases in Geochemistry and Cosmochemistry. pp. 319-370 [2] de Moor et al., (in review) G-cubed [3] Rowe (1994) Chem. Geol., 236:303-322 [4] Sakai et al. (1984) J. Petrol., 52: 1307-1331 [5] Alt et al. (2012) Earth Plan. Sci. Lett., 327: 50-60

Isotopic Investigations of Nebular and Parent Body Processes with a High Sensitivity Ion Microprobe

NASA Technical Reports Server (NTRS)

McKeegan, Kevin D.

2005-01-01

NASA supported the development of the CAMECA ims 1270 ion microprobe at UCLA for applications in cosmochemistry. The primary investigations centered on measuring the microscopic distributions of key isotopic abundances in primitive meteoritic materials as a means of constraining the nature of important thermal and chemical processes in the solar nebula and the timescales associated with those processes. Our prior work on oxygen isotope anomalies in a wide variety of meteoritic materials had led us to a view of a spatially heterogeneous nebula, and in particular, a restricted region for CAI formation that is characterized by O-16-rich gas. Because of its production of CAIs in the energetic local environment near the protosun, the existence of a natural transport mechanism via bipolar outflows, and a general astrophysical plausibility, we were attracted to the fluctuating X-wind model which had been put forward by Frank Shu, Typhoon Lee, and colleagues. With our collaborators, we undertook a series of investigations to test the viability of this hypothesis; this work led directly to the discovery of live Be in CAIs and a clear demonstration of the existence of 160-rich condensates, which necessarily implies an O-16-rich gaseous reservoir in the nebula. Both of these observations fit well within the context of X-wind type models, i.e. formation of CAIs (or condensation of their precursors) in the reconnection ring sunward of the inner edge of the accretion disk, however much work remains to be done to test whether the physical parameters of the model can quantitatively predict not only the thermal histories of CAIs but also their radioactivity. The issue of spatial heterogeneity in the nebula, central to the X-wind model, is also at the heart of any chronology based on short-lived radioisotopes. In this work, we followed up on strong hints for presence of exireme:j: (53 day) short-lived Be-7, and have prepared a manuscript (in revision). We also measured A1-Mg systematics by a combined approach of high-precision multiple-collector SIMS analyses, traditional analyses on the UCLA ims 1270, and high-spatial resolution analyses using a NanoSIMS instrument. The data help to deconvolve effects due to partial resetting of the A1-Mg system by multiple thermal events. Finally, we initiated investigations related to nebular heterogeneity with a new initiative of in situ high-precision sulfur isotope analyses of sulfides from a wide variety of components of chondrites. The ultimate goal of all this work is to help develop a better understanding of the relationships between CAIs and chondrules, the astrophysical environments in which they formed, and the timescales of nebular processes. As detailed in Table 1, for the project period, 14 manuscripts were published and 17 abstracts were presented describing the work.

Europlanet Research Infrastructure: Planetary Sample Analysis Facilities

NASA Astrophysics Data System (ADS)

Cloquet, C.; Mason, N. J.; Davies, G. R.; Marty, B.

2008-09-01

EuroPlanet The Europlanet Research Infrastructure consortium funded under FP7 aims to provide the EU Planetary Science community greater access for to research infrastructure. A series of networking and outreach initiatives will be complimented by joint research activities and the formation of three Trans National Access distributed service laboratories (TNA's) to provide a unique and comprehensive set of analogue field sites, laboratory simulation facilities, and extraterrestrial sample analysis tools. Here we report on the infrastructure that comprises the third TNA: Planetary Sample Analysis Facilities. The modular infrastructure represents a major commitment of analytical instrumentation by three institutes and together forms a state-of-the-art analytical facility of unprecedented breadth. These centres perform research in the fields of geochemistry and cosmochemistry, studying fluids and rocks in order to better understand the keys cof the universe. Europlanet Research Infrastructure Facilities: Ion Probe facilities at CRPG and OU The Cameca 1270 Ion microprobe is a CNRS-INSU national facility. About a third of the useful analytical time of the ion probe (about 3 months each year) is allocated to the national community. French scientists have to submit their projects to a national committee for selection. The selected projects are allocated time in the following 6 months twice a year. About 15 to 20 projects are run each year. There are only two such instruments in Europe, with cosmochemistry only performed at CRPG. Different analyses can be performed on a routine basis, such as U-Pb dating on Zircon, Monazite or Pechblende, Li, B, C, O, Si isotopic ratios determination on different matrix, 26Al, 60Fe extinct radioactivity ages, light and trace elements contents . The NanoSIMS 50L - producing element or isotope maps with a spatial resolution down to ≈50nm. This is one of the cornerstone facilities of UKCAN, with 75% of available instrument time funded and committed to UK cosmochemical activity - but the remainder is free for other applications and users. The UK activity is managed by the UKCAN management committee and vetted through a local working group. Management of the remaining 25% of other activity will be organised through the local working group. This is the newest, and most advanced of three instruments of this type in Europe which routinely address cosmochemical analyses. The instrument is capable of providing high spatial resolution (down to 50nm) elemental and isotope distribution maps for a wide range of elements from across the periodic table. It is also capable of high precision (per mil) isotopic spot measurements with a spatial resolution of a few microns for a range of elements including C, N, O, S, Si, Mg, etc. Noble Gases facilities at CRPG and OU Ar/Ar Nu Instruments Noblesse is coupled with an ultra-low volume extraction line and with a choice of 213 nm UV laser or 1090 nm IR lasers, providing a wide range of analytical capability in Ar/Ar dating of lunar and meteorite samples. This instrument is unique with a mass resolution of 3000, and with the UV laser it has the capability to measure Ar isotope variation on a ca. 30 -micron resolution enabling detailed mapping of age and apparent age variation within minerals. The 1090 nm laser provides the capability to step-heat small samples. The laboratory is fully supported by sample preparation facilities and technical expertise in lunar and meteorite Ar/Ar analysis. Helium isotope facility. Analysis of the isotopes of helium in rocks and minerals. Determining the origin of gases in meteorites and ET return samples, dating surface exposure with cosmogenic 3He using the latest He isotope mass spectrometer, the GV Helix SFT, the first instrument installed in Europe. CRPG is an European leader in this domain. Non-Traditional stable Isotopes and radiogenic isotopes at VUA and CRPG The specific facility proposed for the TNA is the geochemistry labs used for the study of long (e.g. Rb- Sr, Sm-Nd…) and short-lived radioisotope (e.g. Mg- Al, Hf-W..), including also Os isotopes, stable and non traditional stable isotope facilities (e.g. Fe, Pb, Zn…). The facility comprises three multicollector Thermal ionization mass spectrometers (TIMS) and two multi-collector ICP-MS one of which is fitted with 193 nm laser for in situ work. In addition these instruments are fully supported by sample preparation labs (crushing, mineral separation/picking), a clean lab and geochemical support (XRF; ICP; ICP-MS etc). Data that can be obtained on samples containing sub nano gram to nanogram amounts. Organic matter analysis at OU Leco Pegasus IV GCxGC-TOFMS - mass spectrometric complete characterisation of very complex mixtures of organic materials. The Pegasus EPSC Abstracts, Vol. 3, EPSC2008-A-00437, 2008 European Planetary Science Congress, Author(s) 2008 4D GCxGC-TOFMS system, from Leco, provides the analyst with four dimensions of analytical resolution for significantly more complete sample analysis compared to conventional GC-Mass Spectrometry. The main advantages include: 1) The significantly increased sensitivity over the whole mass range (5- 1000 amu); 2)The separation of compounds that coelute on standard gas chromatograph systems; 3) Separation of analytes by volatility and polarity enables traditionally unresolved mixtures to be examined in detail, and vastly increases the number of compounds identified; 4) Greatly increased signal to noise ratio, due to compounds being separated from the column bleed of the first column on the second GC column and an enormous increase in the Spectral Generation Rate. A number of different pyrolysis and injection sample introduction facilities are available and access to off-line data processing and reference libraries. This is the only instrument of this type in a European laboratory with a significant focus on extraterrestrial materials. Thermo MAT 253 GC-IRMS -isotopic measurements of H, C or N on individual organic compounds in complex mixtures. One of only a few instruments of this type worldwide primarily dedicated to the analysis of extra-terrestrial materials. Supported by fully equipped sample preparation laboratories and GC-Mass Spectrometers required to develop the exact methodology necessary for optimal analysis of each sample. A number of different sample introduction injection and pyrolysis systems are available. Open University is one of the leading laboratories in the world for compound specific isotopic measurements of extra-terrestrial organics and this is one of a very few instruments of this type in the world largely dedicated to extra-terrestrial materials. Conclusion Currently planetary research is limited to meteorites and lunar samples but future return missions will provide enough material from comets and asteroids. A major focus of research in the next 5-10 years will be comparative planetology to understand the types of geochemical processes that can be expected on the (former) water rich regions of Mars to be sure that the detection of past life is unambiguous. The aim of this infrastructure is to provide a structured access to state of the art analytical facilities for European users.

Feasibility of Iodine and Bromine analysis in Genesis AloS collectors

NASA Astrophysics Data System (ADS)

Pravdivtseva, O.; Meshik, A.; Hohenberg, C. M.; Burnett, D. S.

2011-12-01

Comparison of solar, meteoritic and terrestrial elemental abundances provides understanding of the formation and evolution of the solar system. Yet, the majority of the solar abundances are based on meteoritic values [1-6]. As a continuation of our noble gas measurements of the Solar Wind (SW) [7] we attempted to evaluate the possibility of SW-iodine and SW-bromine analyses in the Genesis Solar Wind Aluminum on Sapphire collectors (AloS) using the conversions: 127I(n,γβ)128Xe, 79Br(n,γβ)80Kr and 81Br(n,γβ)82Kr. To estimate the extent of terrestrial halogen contamination in Genesis collectors, several flown fragments of AloS were submerged in methanol (for 1 hour and for 48 hours), rinsed, dried, sealed under vacuum in fused quartz ampoules and irradiated at the Missouri University Research Reactor receiving fluence ˜ 2E+19 thermal neutrons/cm2. Single step laser extraction using 1064 nm laser ablation of 0.7 cm2 area demonstrated clear signature of solar wind as indicated by 129Xe/132Xe = 1.045 ± 0.005, while 128Xe/132Xe = 1.01 ± 0.03 had a 12-fold excess compared to the solar value. Longer washing apparently reduces iodine contamination 4 times, implying that it is surface correlated. Krypton analysis showed 17% excess in 82Kr and 3-fold excess in 80Kr in agreement with their production ratio. A longer 48-hour washing reduced Br contamination 50 times. In order to better separate SW halogens from ubiquitous terrestrial contamination we employed a depth-profiling of AloS using 266 nm laser ablation. Laser beam power was increased in 12 consecutive steps using a combination of controlled defocusing and attenuation by a polarizing beamsplitter. Depth profile analysis revealed that terrestrial halogen contamination is present at the surface and at the interface between Al and sapphire substrate and is more pronounced for iodine, as indicated by 128Xe/132Xe ratio that is higher than atmospheric and solar wind values in all 12 rasters. While washing procedure reduced surface contamination, it did not affect iodine and bromine associated with the interface. Thus, cleaner Si-based Genesis collectors could be more suitable for SW halogen analyses. Our first results suggest that determination of solar iodine and bromine is potentially feasible, considering the possibility of analyzing larger collector areas irradiated with higher neutron fluence in order to improve counting statistics of the measurements. Supported by NASA grant NNX07AM76G. [1] Anders E. and Ebihara M. 1982. GCA 46:2363-2380. [2] Anders E. and Grevesse N. 1989. GCA 53:197-214. [3] Cameron A. G. W. 1968. in Origin and distribution of the elements (Ahrens L. H., ed.), Pergamon, Oxford:125-143. [4] Cameron A. G. W. 1973. Space Science Revues 15:121-146. [5] Suess H. E. and Urey H. C. 1956. Revisions of Modern Physics 28:53-74. [6] Lodders K. 2010. in: Principles and Perspectives in Cosmochemistry. 379-417. [7] Meshik A. et all. 2011. 74th Meteoritical Society Meeting, Abstract#5471.

Sulfur and Hydrogen Isotope Anomalies in Organic Compounds from the Murchison Meteorite

NASA Technical Reports Server (NTRS)

Cooper, G. W.; Thiemens, M. H.; Jackson, T.; Chang, Sherwood

1996-01-01

Isotopic measurements have been made on organic sulfur and phosphorus compounds recently discovered in the Murchison meteorite. Carbon, hydrogen and sulfur measurements were performed on individual members of the organic sulfur compounds, alkyl sulfonates; and carbon and hydrogen measurements were made on bulk alkyl phosphonates. Cooper and Chang reported the first carbon isotopic measurements of Murchison organic sulfonates, providing insight into the potential synthetic mechanisms of these and, possibly, other organic species. Hydrogen isotopic measurements of the sulforiates now reveal deuterium excesses ranging from +660 to +2730 %. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low temperature astrophysical environment consistent with that of dense molecular clouds. Measurements of the sulfur isotopes provide further constraints on the origin and mechanism of formation of these organic molecules. Recently, there has been growing documentation of sulfur isotopic anomalies in meteoritic material. Thiemens and Jackson have shown that some bulk ureilites possess excess S-33 and Thiemens et al. have reported excess S-33 in an oldhamite separate from the Norton County meteorite. Rees and Thode reported a large S-33 excess in an Allende acid residue, however, attempts to verify this measurements have been unsuccessful, possibly due to the heterogeneous nature of the carrier phase. With the recognition that sulfur isotopes may reflect chemistry in the protosolar nebula or the precursor molecular cloud, identification of potential carriers is of considerable interest. In the present study, the stable isotopes of sulfur were measured in methane sulfonic acid extracted from the Murchison meteorite. The isotopic composition was found to be: (delta)S-33 = 2.48 %, (delta)S-34 = 2.49 % and (delta)S-36 = 6.76 %. Based upon analysis of more than 60 meteoritic and numerous terrestrial samples, the mass fractionation lines are defined by Delta-33 = (delta)S-33 -0.50(delta)S-34 and Delta-36 = (delta)s-36 - 1.97 (delta)S-34. From these relationships Delta-33 = 1.24 % and Delta-36 = 0.89 % are observed. These anomalies, particularly the Delta-33, lie well outside the range of analytical uncertainty. They are the largest observed in any meteoritic component and the first found in an organosulfur compound. As discussed by Thiemens and Jackson, due to it's position on the periodic chart, sulfur undergoes chemically induced mass independent isotopic fractionations as does oxygen. Experiments by Mauersberger et. al. show that in such processes, the magnitude of fractionation for the different isotopically substituted species varies with mass and angular momentum; thus, anomalies are expected for both S-33 and S-36, but not necessarily of the same magnitude. Laboratory experiments have also confirmed that chemically produced, mass independent fractionations are mediated by molecular symmetry factors. A chemical source of fractionation requires that the sulfur isotopic anomaly was established in the gas phase, probably in reactions involving symmetric CS2. The discovery of an anomalous sulfur isotopic composition in a specific molecule containing excess deuterium is an important advance in the understanding of the cosmochemistry of sulfur. This evidence suggests that methanesulfonic acid was synthesized by interstellar processes. Further measurements and details of possible synthesis and fractionation mechanisms will be presented.

Rock magnetic properties of dusty olivine: comparison and calibration of non-heating paleointensity methods

NASA Astrophysics Data System (ADS)

Lappe, S. L.; Harrison, R. J.; Feinberg, J. M.

2012-12-01

The mechanism of chondrule formation is an important outstanding question in cosmochemistry. Magnetic signals recorded by Fe-Ni nanoparticles in chondrules could carry clues to their origin. Recently, research in this area has focused on 'dusty olivine' in ordinary chondrites as potential carriers of pre-accretionary remanence. Dusty olivine is characterised by the presence of sub-micron Fe-Ni inclusions within the olivine host. These metal particles form via subsolidus reduction of the olivine during chondrule formation and are thought to be protected from subsequent chemical and thermal alteration by the host olivine. Three sets of synthetic dusty olivines have been produced, using natural olivine (average Ni-content of 0.3 wt%), synthetic Ni-containing olivine (0.1wt% Ni) and synthetic Ni-free olivine as starting materials. The starting materials were ground to powders, packed into a 8-27 mm3 graphite crucible, heated up to 1350°C under a pure CO gas flow and kept at this temperature for 10 minutes. After this the samples were held in fixed orientation and quenched into water in a range of known magnetic fields from 0.2 mT to 1.5 mT. We present a comparison of all non-heating methods commonly used for paleointensity determination of extraterrestrial material. All samples showed uni-directional, single-component demagnetization behaviour. Saturation REM ratio (NRM/SIRM) and REMc ratio show non-linear behaviour as function of applied field and a saturation value < 1. Using the REM' method the samples showed approximately constant REM' between 100 and 150 mT AF-field. Plotting the average values for this field range again shows non-linear behaviour and a saturation value < 1. Another approach we examined to obtain calibration curves for paleointensity determination is based on ARM measurents. We also present an analysis of a new FORC-based method of paleointensity determination applied to metallic Fe-bearing samples [1, 2]. The method uses a first-order reversal curve (FORC) diagram to generate a Preisach distribution of coercivities and interaction fields within the sample and then physically models the acquisition of TRM as function of magnetic field, temperature and time using thermal relaxation theory. The comparison of observed and calculated NRM demagnetisation spectra is adversely effected by a large population of particles in the single-vortex state. Comparison of observed and calculated REM' curves, however, yields much closer agreement in the high-coercivity SD-dominated range. Calculated values of the average REM' ratio show excellent agreement with the experimental values - including the observed non-linearity of the remanence acquisition curve - suggesting that this method has the potential to reduce the uncertainties in non-heating paleointensity methods for extraterrestrial samples. [1] AR Muxworthy and D Heslop(2011) A Preisach method for estimating absolute paleofield intensity under the constraint of using only isothermal measurements: 1. Theoretical framework. Journal of Geophysical Research, 116, B04102, doi:10.1029/2010JB007843. [2] AR Muxworthy, D Heslop, GA Paterson, and D Michalk. A Preisach method for estimating absolute paleofield intensity under the constraint of using only isothermal measurements: 2. Experimental testing. Journal of Geophysical Research, 116, B04103, doi:10.1029/2010JB007844.

HCN Polymers: Toward Structure Comprehension Using High Resolution Mass Spectrometry

NASA Astrophysics Data System (ADS)

Bonnet, Jean-Yves; Thissen, Roland; Frisari, Ma; Vuitton, Veronique; Quirico, Eric; Le Roy, Léna; Fray, Nicolas; Cottin, Hervé; Horst, Sarah; Yelle, Roger

A lot of solar system materials, including cometary ices and Titan aerosols, contain dark matter that can be interpreted as complex nitrogen bearing organic matter [1]. In laboratory experi-ments, HCN polymers are thus analogs of great interest. In fact they may be present in Titan atmosphere and in comet nuclei and then reprocessed as a CN distributed source [2], when ices began to sublimate and ejects from the nucleus organic matter grains [3]. The presence of HCN polymers is suggested because HCN molecule has been directly observed in 1P/Halley comet [4] and others. HCN polymers are also of prebiotic interest [5] as it can form amino acid under hydrolysis conditions. Even if they have been studied during the last decades, their chemical composition and structure are still poorly understood, and a great analytical effort has to be continued. In this way we present a high resolution mass spectrometry (HRMS) and a high resolution tandem mass spectrometry (MS/HRMS) analysis of HCN polymers. It was shown [6] that this is a suitable technique to elucidate composition and structure of the soluble part of tholins analogs of Titan's atmosphere aerosols. HCN polymers have never been studied by HRMS, thus we used a LTQ-Orbitrap XL high resolution mass spectrometer to analyse the HCN polymers. These are produced at LISA by direct polymerisation of pure liquid HCN, catalyzed by ammonia. HCN polymers have been completely dissolved in methanol and then injected in the mass spectrometer by ElectroSpray Ionization (ESI). This atmospheric pressure ionization process produces protonated or deprotonated ions, but it does not fragment molecules. Thus HRMS, allows a direct access to the stoechiometry of all the ionizable molecules present in the samples. Fragmentation analyses (MS/MS) of selected ions have also been performed. Thess analysis provide information about the different chemical fonctionnalities present in HCN poly-mers and also about their structure. Thus we are able to derive quantitative and qualitative parameters, (H/C, N/C ratios for exemple). [1] D. P. Cruikshank, H. Imanaka, and C. M. Dalle Ore. Tholins as coloring agents on outer Solar System bodies. Advances in Space Research, 36:178-183, 2005. [2] H. Cottin and N. Fray. Distributed Sources in Comets. Space Science Reviews, 138:179-197, July 2008. [3] J. Kissel, R. Z. Sagdeev, J. L. Bertaux, V. N. Angarov, J. Audouze, J. E. Blamont, K. Buchler, E. N. Evlanov, H. Fechtig, M. N. Fomenkova, H. von Hoerner, N. A. Inogamov, V. N. Khromov, W. Knabe, F. R. Krueger, Y. Langevin, B. Leonasv, A. C. Levasseur-Regourd, G. G.Managadze, S. N. Podkolzin, V. D. Shapiro, S. R. Tabaldyev, and B. V. Zubkov. Com-position of comet Halley dust particles from VEGA observations. Nature, 321:280-282, May 1986. [4] D. Despois, J. Crovisier, D. Bockelee-Morvan, E. Gerard, and J. Schraml. Observations of hydrogen cyanide in comet halley. Astronomy and Astrophysics, 160:L11+, May 1986. [5] C. N. Matthews and R. D. Minard. Hydrogen cyanide polymers connect cosmochemistry and biochemistry. In IAU Symposium, volume 251 of IAU Symposium, pages 453-458, October 2008. [6] N. Sarker, A. Somogyi, J. I. Lunine, and M. A. Smith. Titan Aerosol Analogues: Analysis of the Nonvolatile Tholins. Astrobiology, 3:719-726, December 2003.

187Re- 187Os Nuclear Geochronometry: Dating Peridotitic Diamond Sulphide Inclusions

NASA Astrophysics Data System (ADS)

Roller, Goetz

2015-04-01

Nuclear geochronometry [1-2] is a new dating method which combines principles of geochronology with nuclear astrophysics. It is embedded in other scientific fields like cosmochemistry, cosmology and nuclear theory, which pose tight constraints for nuclear geochronometry. It is based upon identified Re/Os element ratios ˜ 1, interpreted as the nuclear production ratio, and ultra-subchondritic initial 187Os/188Os ratios within terrestrial rocks, suggesting that Earth's core still contains element ratios and isotopic signatures of at least two rapid (r) neutron-capture process [3] events. The 13.78 Ga old component, represented by the isotopic signature of a komatiitic basalt [5085 BasKom] [4] from the Barberton Greenstone Belt (Onverwacht Group, South Africa), is assigned to the Earth's inner core. The other isotopic signatures identified so far within pyroxenites / komatiites are assigned to its outer core due to at least one gravitational collapse of the old component, commencing ˜ 3.48 Ga [2] and resulting in one or more additional r-process event(s). Here I show that 187Re-187Os nuclear geochronometry can also be successfully applied for dating peridotitic diamond sulphide inclusions by means of two-point-isochrones (TPI), using a so-called nuclear geochronometer always as the second data point in a TPI diagram. It turns out that the method may have a huge potential to constrain the chemical evolution of the SCLM. For example, TPI ages for Ellendale (Australia) peridotitic diamond sulphide inclusions EL50, EL23, EL54-1, EL54-3, EL55-1 and EL65 reported in the literature [5] reveal at least two main fractionation events. The age cluster between 1.4 Ga and 1.5 Ga is consistent with a previously reported isochrone age [5]. The event ˜ 2.3 ± 0.3 Ga overlaps the Great Oxidation Event (GOE) between 2.22 Ga and 2.46 Ga. While the ˜ 1.4 Ga to 1.5 Ga events lead to fractionation of the 187Re/188Os ratios towards values typical for mantle peridotite, the latter caused only minor disturbance of the 187Re/188Os nuclear production ratio assigned to the outer core. It cannot be excluded that a major change in oxygen/sulfur fugacitiy across the core - mantle boundary (CMB), coincident with the GOE, is responsible for the 187Re/188Os fractionation of the EL50 sample. Because of its minor degree of fractionation, EL50 can still be used as a so-called fractionated chronometer for dating those Ellendale peridotitic diamond sulphide inclusions, which do not show open system behaviour. Whether the ˜ 1.4 Ga to 1.5 Ga fractionation events are due to an even more pronounced change in oxygen and/or sulfur fugacities across the CMB, within the mantle or, alternatively/additionally, reworking of the mantle because of mantle convection and/or subduction of oceanic crust, remains an open question. This question will be addressed in future studies. [1] Roller (2014), GSA Abstr. with Programs, 46, 323. [2] Roller (2014), Abstract S51B-4444, Fall Meeting, AGU 2014. [3] Burbidge et al. (1957) Revs. Mod. Phys. 29, 547 - 650. [4] Birck et al. (1994), EPSL 124, 139 - 148. [5] Smit et al. (2010) GCA 74, 3292 - 3306.

Sulfur and Hydrogen Isotope Anomalies in Organic Compounds from the Murchison Meteorite

NASA Astrophysics Data System (ADS)

Cooper, G. W.; Thiemens, M. H.; Jackson, T.; Chang, S.

1995-09-01

Carbon, hydrogen and sulfur isotopic measurements have been made on individual members of a recently discovered class of organic sulfur compounds, alkyl sulfonates, in the Murchison meteorite. Cooper and Chang (1) reported the first carbon isotopic measurements of Murchison organic sulfonates, providing insight into potential synthetic mechanisms of these, and possibly other, organic species. Hydrogen isotopic measurements of the sulfonates now reveal deuterium excesses ranging from +660 to +2730 per mil. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low temperature astrophysical environment consistent with that of dense molecular clouds. Measurement of the sulfur isotopes provide further constraints on the origin and mechanism of formation of these organic molecules. Recently, there has been growing documentation of sulfur isotopic anomalies in meteoritic material. Thiemens and Jackson (2) have shown that some bulk ureilites possess excess 33S and Thiemens et al. (3) have reported excess 33S in an oldhamite separate from Norton County. Rees and Thode (4) reported a large 33S excess in an Allende acid residue, however, attempts to verify this measurement have been unsuccessful, possibly due to the heterogeneous nature of the carrier phase. With the recognition that sulfur isotopes may reflect nebular chemistry, identification of potential carriers is of considerable interest. In the present study the three stable isotopes of sulfur were measured in methane sulfonate extracted from the Murchison meteorite. The isotopic composition was found to be delta 33S=2.48, delta 34S=2.49 and delta 36S = 6.76 per mil. Based upon analysis of more than 60 meteoritic, and numerous terrestrial samples, the mass fractionation lines are defined by 33Delta = delta 33S-0.50 delta 34S and 36Delta = delta 36S -1.97 delta 34S. From these relations a 33Delta = 1.24 per mil and 36Delta = 0.89 per mil is observed. These anomalies, particularly the 33Delta, are well outside the range of analytical uncertainty, especially for the 33Delta, and are the largest observed in any meteoritic component. As discussed by Thiemens and Jackson (2), due to its position on the periodic chart, sulfur chemically produces mass independent fractionations, as does oxygen. From experiments by Mauersberger et al. (5) it is observed that in a chemically produced mass independent fractionation process, the magnitude of fractionation for the different isotopically substituted species varies with mass and angular momentum, thus, anomalies are expected for both 33S and 36S, but not necessarily of the same magnitude. Laboratory experiments have also confirmed that chemically produced, mass independent fractionations occur , which are mediated by molecular symmetry factors (6). If the source of the fractionation is chemical, this requires that the sulfur isotopic anomaly was established in the gas phase, possibly from nebular reactions involving symmetric CS2. The discovery of an anomalous sulfur isotopic composition in a specific molecule containing excess deuterium is an important advance in the understanding of the cosmochemistry of sulfur. Further measurements and details of possible synthesis and fractionation mechanisms will be presented. References: [1] Cooper G. W. and S. Chang (1995) LPS XXVI, 281. [2] Thiemens M. H. and Jackson T. (1995) LPS XXVI, 1405. [3] Thiemens et al. (1994) Meteoritics, 29, 540. [4] Rees C. E. and Thode H. G. (1977) GCA, 57, 3171. [5] Mauersberger et al. (1993) GRL, 20, 1031. [6] Bains-Sahota S. K. and Thiemens M. H. (1989) J. Chem. Phys., 90, 6099.

High Precision 142Nd/144Nd and 143Nd/144Nd Isotope Ratio Measurements in Rock Samples

NASA Astrophysics Data System (ADS)

Ali, A.; Srinivasan, G.

2009-05-01

The long-lived 147Sm-143Nd system with a half-life (T1/2) of 106 Gyr is generally used for geochronology. The short-lived 146Sm-142Nd system (T1/2= 103 Myr) is used as a geological tracer to track early (˜500 Ma) silicate differentiation [1] events in different planetary bodies. The isotope composition measurements by thermal ionization mass spectrometry (TIMS) require purification of Nd using chemical separation methods. This is important as an impure sample will give both a very poor ion yield and cause beam instability in the mass spectrometer, potentially resulting in a poor analysis [2]. The separation of Nd for 143Nd isotope measurement is, fairly straightforward because there is no isobaric interference of any other REE. While 142Nd isotope analysis needs chemically separated Nd fraction to be ˜100% Ce-free as latter is composed of a substantial amount of 142Ce isotope. A 4-steps technique, modified from Caro et al., [3], for the separation of Nd is established at the Cosmochemistry Laboratory of University of Toronto, Canada and applied to the measurement of Nd isotope ratios in geological reference sample BCR-2 (USGS, Columbia River basalt) using TIMS. Results of the isotopic ratios obtained for BCR-2 are in good agreement with published values [e.g., 4]. Analytical work on the samples discovered as the oldest rocks on Earth [5] from Nuvvuagittuq greenstone belt in Québec, Canada and various meteorites is in progress. An account of the procedures involved is briefly described here. All working solutions and acids were prepared using >18.2 MΩ.cm-1 H2O from a Milli-Q water system. Experiments were performed under Class 100 clean work bench with acid-cleaned apparatus and plastic-ware. The whole rock powders were weighed (20-30 mg) and dissolved in a mixture of HF and HNO3 using PFA vials and heated at 110°C. Further decomposition was done in Teflon bomb in the oven at 205°C. Later on contents of the Teflon bomb were transferred to vials and fluorides were removed with a mixtures of HClO4 and HCl. Finally the digested samples were dissolved in 4N HCl prior to the column chromatography. The separation of alkalis and REE was achieved with 2 ml BioRad column using AG®50W-X12 resin; following which the separation of Nd and Sm fractions was achieved using Ln-Spec resin in PFA column. Results: Triple filament geometry was used to measure Nd as a metal in multi-dynamic mode using Isoprobe-T TIMS. About 600x10-9 g of JNdi-1 standard [6] produced a 142Nd beam strength of ~5×10-11 A; 400 cycles constituted one measurement, where each cycle consisted of 4 sequences of 10 second counting time. A set of ˜10 measurements of JNdi-1 gave extremely accurate and precise ratios for 142/144, 143/144 and 145/144 with internal precision better than 4 ppm and an external precision of less than 7 ppm in all cases. The BCR-2 samples were loaded ˜200 ng (factor of 4 less than JNdi-1) and therefore their operating signal strength for 142Nd was ˜1×10-11 A. Based on our analyses we conclude that the internal precision for BCR-2 samples in the range of 8-9 ppm and their external precision is comparable to JNdi-1. References: [1] Caro et al, (2008) Nature 452, 336-339; [2] Míková & Denková, (2007) Geosciences 52, 221-226; [3] Caro et al, (2003) Nature 432, 428-432; [4] Raczek et al., (2003) Geostandards Newsletter 27, No.2, 173-179; [5] O'Neil et al, (2008) Science 321, 1828-1831; [6] Tanaka et al., (2000) Chem Geol, 168, 279-281.

Thermal history of type-3 chondrites in the NASA antarctic collection

NASA Astrophysics Data System (ADS)

Bonal, L.; Quirico, E.; Montagnac, G.

2014-07-01

Chondrites are the most primitive meteorites. However, they were all modified in some ways by post-accretion geological processes operating on their asteroidal parent bodies. Hence, to decipher the formation(s) and origin(s) of their components, we must first understand how chondritic materials were modified in their asteroidal parent bodies. The modifications induced by secondary processes should not be underestimated and have to be precisely estimated before any interpretation of chondrite properties in terms of cosmochemistry. In particular, all chondrites contain some organic components that were potentially chemically and physically modified through post-accretion processes. A thin understanding of the induced evolution is required to allow for pertinent comparisons with other primitive extraterrestrial materials, such as cometary grains, to finally address questions such as the origin of organics in the Solar System. Type 3 chondrites experienced thermal metamorphism on their asteroidal parent body due to the radioactive decay of elements such as ^{26}Al. Temperatures higher than 300 °C were experienced on timescales of several thousands of years. Still, type 3 chondrites remain as unequilibrated rocks and common mineralogical thermometers cannot be applied. The polyaromatic carbonaceous matter is sensitive to thermal episodes (of long and short duration) experienced by the host meteorite. In particular, its structural order directly reflects the thermal history experienced on their parent bodies. The structural modification of the aromatic carbonaceous matter towards a higher order is irreversible, and independent of the mineralogy and degree of aqueous alteration. It is mainly controlled by the peak metamorphic temperature. Moreover, under the assumption of fairly similar organic precursors among chondrites of distinct groups, the structural order of polyaromatic organic matter allows for a direct comparison of their metamorphic grades. It is then possible to evaluate the metamorphic grade of the objects and to assign a petrologic type along a unique petrologic scale [1-4]. This technique has been successfully applied to type 3 Unequilibrated Ordinary Chondrites [1], carbonaceous CV chondrites [2], and CO chondrites [3]. The interpretation of the structural order of the polyaromatic carbonaceous matter in terms of thermal history is thus reliable. Raman spectroscopy enables the determination of the degree of structural order of the polyaromatic organic matter present in the matrix of chondrites. Both falls and finds, from Antarctica [4] and elsewhere, have been analyzed. It does not require a large amount of samples and is relatively easy to implement. Raman spectroscopy is particularly sensitive to the lowest petrologic types (3.0-3.2). The present NASA collection of Antarctic meteorites represents an incredible source of precious samples for our community. The present work finely characterizes the thermal history of most of the type 3 chondrites (UOCs, CVs, and COs) from that collection. At the present time, the objectives are threefold: (i) determination of reliable petrologic types indispensable for our community; (ii) identification of the most primitive type 3 chondrites (petrologic type ≤ 3.1); and (iii) identification of potential ''anomalous'' samples having experienced a slightly different thermal history. The JSC Meteorite Working Group generously allocated us with more than 150 chondrites (UOCs, CVs, and COs). The following points summarize the main results. (i) At the present time, the thermal histories of more than 100 samples have been characterized. (ii) The terrestrial weathering experienced by several chondrites (˜25 chondrites) has been too pervasive for the method to be applied. For these meteorites, as signatures of oxide minerals dominate Raman spectra of the matrix, the organic matter might have been significantly altered through oxidation. (iii) Real discrepancies with the preliminary JSC petrologic type attributions were found for several chondrites with mostly underestimations of the metamorphic grades. (iv) The structural grade of the polyaromatic carbonaceous matter is fairly homogeneous in most of the considered chondrites with a few exceptions, interpreted in terms of shock events. (v) Recently, there were some promising advances (e.g. [5,6]) in terms of interpretation of the structural order of the polyaromatic carbonaceous matter as a geothermometer for terrestrial rocks of low maturity grades. The used spectral tracers will be considered and the thermometry potentially applied to infer new constraints on the metamorphic temperature experienced by these type 3 chondrites.

Foreword

NASA Astrophysics Data System (ADS)

Jorissen, A.; Goriely, S.; Rayet, M.; Siess, L.; Boffin, H.

The international conference The Future Astronuclear Physics was held at the Université Libre de Bruxelles (ULB) from August 20 to 22, 2003, to celebrate Marcel Arnould on the occasion of his sixtieth birthday. Marcel Arnould is full professor at ULB and was appointed director of the Institut d'Astronomie et d'Astrophysique (IAA) of this university in 1983, when he was still a Research Associate of the National Fund for Scientific Research (FNRS). Since the late sixties he has played a leading role in the development of a trans-disciplinary field of research, the object of which is the study of nuclear phenomena in astrophysics. Those phenomena being the main source of energy in stellar interiors and being also responsible for the synthesis of the chemical elements, the study of the often peculiar, sometimes exotic, nuclear physics in a rich variety of astrophysical conditions, is crucial to understand almost all stages of stellar evolution as well as the chemical and isotopic content of the neighboring and remote places of our universe. All along his scientific career, Marcel Arnould has worked to give the so-called nuclear astrophysics, born in the second half of the twentieth century and marked by a few prominent physicists in the United States and in Canada, a fertile ground for development inside Europe as a fully grown discipline, collecting the knowledge on the infinitely small with that on the infinitely large, a true interdisciplinary science that ought to be more appropriately called “astronuclear physics". We like to remind that to achieve this goal, Marcel Arnould has promoted and directed two important projects in the framework of the EU scientific programs. The first one (1989 1992), “Nuclear Astrophysics: experimental and theoretical studies", involved 11 European research centers and led to the first measurement, at the Louvain-la-Neuve cyclotron facility, of a nuclear reaction rate involving a short-lived nuclide, ^{13}N. This experiment was performed using a radioactive ion beam technique, a new and powerful tool of investigation in nuclear astrophysics, which has since been developed worldwide. The second program, “Nuclear Astrophysics: measurement, evaluation and compilation of reaction rates, and their impact on stellar evolution and nucleosynthesis" (1992 1997), gave the scientific community the first European compilation of astrophysical reaction rates. This work was meant to supersede the compilations performed during more than forty years by a team led by the late Nobel Prize winner, William A. Fowler, at the California Institute of Technology. A relentless scientific advisor amongst astrophysicists as well as nuclear physicists, Marcel deplores the persistent lack of communication between those two communities. For years, his hope has been to see the rise of a generation of true astronuclear physicists, but one has to admit with him that this goal is far from being achieved yet and that one still has to fight, despite all the expressions of good intentions, against the barriers that, as is usual, separate scientific disciplines. It is therefore in tribute to the transdisciplinary and visionary nature of Marcel Arnould's scientific work that his close collaborators at the IAA decided to organize this conference, which is explicitely devoted to future developments in the field of astronuclear physics and not, as is often the case, to already completed, or even published, works. The audience has been limited from the start to invited participants chosen for the quality of their human and scientific relations with Marcel, as well as for their contribution to the domains he is exceptionally found of. The conference program was on purpose centered on a few fields that for many years now have been central to the activities of the IAA: the stellar nucleosynthesis and its relations to stellar physics, to nuclear physics and to cosmochemistry. The organizers' choice was to concentrate on a few challenging problems: abundance determinations in stars and modeling of atmospheres, special topics in stellar evolution (rotation, mixing, binarity), multi-D modeling of stellar explosions, future progress in experimental and theoretical nuclear physics for astrophysics. The speakers were asked to give, starting from their own topic, a prospective (or “visionary") view on the evolution of astronuclear physics for the next twenty years. Of course this demand requires time and explains why the organizers chose to limit the number of speeches rather than the time allocated to each speaker. In each of the four sessions, round tables gave the participants plenty of time for discussions or for more formal contributions, some of which have been included in the present proceedings. We hope that the reader will find the same pleasure in reading these proceedings as those who lived the three days of the Conference in a studious and friendly enthusiasm. Scientific Organizing Committee: H. Boffin (Observatoire Royal de Belgique/European Southern Observatory), S. Goriely (IAA), A. Jorissen (IAA), P. Leleux (Université Catholique de Louvain, Institut de Physique Nucléaire), M. Rayet (IAA). Local Organizing Committee: S. Goriely, S. Jancart, A. Jorissen, Y. Levasseur, D. Pourbaix, M. Rayet, L. Siess, S. Van Eck.

The narrative power of astrobiology

NASA Astrophysics Data System (ADS)

Billings, Linda

The narrative power of astrobiology: Telling the story of the quest to understand life's origins and the search for evidence of extraterrestrial life INTRODUCTION The story of the origins and evolution of life is a narrative with nearuniversal appeal. The story of life on Earth is meaningful to all people, and the search for life elsewhere is appealing across cultural boundaries. The U.S. National Aeronautics and Space Administration (NASA) funds an Astrobiology Program in NASA's Science Mission Directorate that is dedicated to the study of the origin, evolution, distribution, and future of life in the universe. Because public interest in astrobiology is great and advances in the field are rapid, the NASA Astrobiology Program aims to integrate communication, education, and outreach into all aspects of program planning and execution. This strategic approach to communication is intended to promote the widest possible dissemination of timely and useful information about scientific discoveries, technology development, new knowledge, and greater understanding produced by the Astrobiology Program. This paper will address how scientists in the field of astrobiology can participate in the telling of an ongoing story of interest to multicultural audiences and why it is important to tell this story. SUMMARY Astrobiology research addresses three fundamental questions: How does life begin and evolve? Is there life beyond Earth and how can we detect it? What is the future of life on Earth and in the universe? The field of astrobiology is an endeavor that brings together researchers in a broad range of disciplines including Earth and planetary science, astrophysics, heliophysics, microbiology and evolutionary biology, and cosmochemistry. Goals of the NASA Astrobiology Program range from determining the nature and distribution of habitable environments in the Solar System and beyond to understanding the emergence of life from cosmic and planetary precursors, the interaction of past life on Earth with its changing environment, the formation and evolution of planets, links between planetary and biological evolution, the effects of climate and geology on habitability, and life's precursors and habitats in the outer solar system. Research dedicated to fulfilling these goals is conducted on Earth and in space, with a growing number of astrobiology investigations flying on planetary exploration missions. Since 1995, the field of astrobiology has grown rapidly, and the pace of discovery has been brisk. The possibility of extraterrestrial life is now a serious scientific question. Research findings over the past decade that are relevant to this question include the controversial 1996 claim of fossil evidence for microbial life in a martian meteorite, evidence of past and perhaps even present liquid water on Mars, the likelihood of a liquid water ocean on Europa, the possibility of liquid water beneath the surface of Titan, observations of a growing number of extrasolar planets, and identification of new forms of microbial life in an ever-widening range of extreme Earth environments. In the 21st century, the tempo of robotic planetary exploration is speeding up, and scientific and public attention is increasingly focusing on astrobiology research, especially the search for signs of life on Mars and other planetary bodies in our solar system. Mars is currently considered the best site in the solar system to search for evidence of past or present extraterrestrial life. And as Mars exploration proceeds, astrobiological interest in Enceladus, Europa, and Titan - outer solar system bodies that might have liquid water, prebiotic chemistry, or even life - is growing as new data are collected and analyzed. With an expanding array of solar system exploration endeavors involving and advancing astrobiology research, the NASA Astrobiology Program employs a communication strategy designed to establish that communication is an integral element of program planning and activities and an activity of fundamental importance to this scientific enterprise. This strategy can aid astrobiologists in explaining why their research is useful, relevant, and worthy of public funding. It can also help scientists determine how their research fits into broader cultural narratives that resonate with a wide variety of expert and non-expert audiences. Science means different things to different people in different situations, and thus public understanding of science, and science communication, are not simple things. Science can be a set of practices, a body of knowledge, a process of investigation, or a world view, for example. The story of astrobiology is a story about science, but more than a science story. The story of the search for life elsewhere is unfolding in the context of a broader cultural narrative, a story about who we are and where we are going (and why). Every researcher in the field of astrobiology has a unique and valuable contribution to make to this ongoing story of our quest to understand our place in the universe. This paper will explore whether and how the story of the study of the origins of life on Earth and the search for evidence of extraterrestrial life may transcend cultural boundaries and address ecumenical concerns.

Science at the ends of the Earth: astrobiology field expeditions as outreach tools

NASA Astrophysics Data System (ADS)

Billings, Linda

INTRODUCTION This paper will report on and evaluate communication, education, and outreach initiatives conducted in conjunction with NASA Astrobiology Science and Technology for Exploring Planets (ASTEP) field campaigns, addressing the costs and benefits of linking students, teachers, and other interested citizens with researchers in the field. This paper will highlight success stories, lessons learned, and promising practices regarding educational programs in scientific research environments. The Astrobiology Program in the U.S. National Aeronautics and Space Administration's (NASA's) Science Mission Directorate studies the origin, evolution, distribution, and future of life in the universe. Public interest in astrobiology is great, and advances in the field are rapid. Hence, the Astrobiology Program supports the widest possible dissemination of timely and useful information about scientific discoveries, technology development, new knowledge, and greater understanding produced by its investigators, employing an approach described as strategic communication planning. That is, the Astrobiology Program aims to integrate communication, education, and outreach into all aspects of program planning and execution. The Program encourages all of its investigators to contribute to the ongoing endeavor of informing public audiences about Astrobiology. The ASTEP element of the Astrobiology Program sponsors terrestrial field campaigns to further scientific research and technology development relevant to future solar system exploration missions. ASTEP science investigations are designed to further biological research in terrestrial environments analogous to those found on other planets, past or present. ASTEP sponsors the development of technologies to enable remote searches for, and identification of, life in extreme environments. ASTEP supports systems-level field campaigns designed to demonstrate and validate the science and technology in extreme environments on Earth. This paper will report on and evaluate communication, education, and outreach initiatives conducted in conjunction with ASTEP field campaigns, addressing the costs and benefits of linking students, teachers, and other interested citizens with researchers in the field. This paper will highlight success stories, lessons learned, and promising practices regarding educational programs in scientific research environments. SUMMARY The Astrobiology Program in NASA's Science Mission Directorate studies the origin, evolution, distribution, and future of life in the universe. Astrobiology research addresses three fundamental questions: How does life begin and evolve? Is there life beyond Earth and how can we detect it? What is the future of life on Earth and in the universe? Goals of the Astrobiology Program range from determining the nature and distribution of habitable environments in the Solar System and beyond to understanding the emergence of life from cosmic and planetary precursors, the interaction of past life on Earth with its changing environment, the formation and evolution of planets, links between planetary and biological evolution, the effects of climate and geology on habitability, and life's precursors and habitats in the outer solar system. Research dedicated to fulfilling these goals is conducted on Earth and in space, with a growing number of astrobiology investigations flying on planetary exploration missions. The field of astrobiology is an endeavor that brings together researchers in a broad range of disciplines including Earth and planetary science, astrophysics, heliophysics, microbiology and evolutionary biology, and cosmochemistry. Since 1995, the field of astrobiology has grown rapidly, and the pace of discovery has been brisk. The possibility of extraterrestrial life is now a serious scientific question. Research findings over the past decade that are relevant to this question include the controversial 1996 claim of fossil evidence for microbial life in a martian meteorite, evidence of past and perhaps even present liquid water on Mars, the likelihood of a liquid water ocean on Europa, the possibility of liquid water beneath the surface of Titan, observations of a growing number of extrasolar planets, and identification of new forms of microbial life in an ever-widening range of extreme Earth environments. Consequently, in the 21st century the pace of robotic planetary exploration is speeding up and scientific and public attention is increasingly focusing on astrobiology research, especially the search for signs of life on Mars and in other environments in our solar system. NASA's ASTEP program is sponsoring field campaigns to test science strategies and robotic technologies that could be useful in conducting astrobiological investigations in planetary environments, focusing on Mars and Europa. Public interest in astrobiology research is substantial, and advances in the field are rapid. Thus the NASA Astrobiology Program encourages Principal Investigators to incorporate communication, education, and public outreach initiatives in their research plans. NASA ASTEP projects provide especially good opportunities for communication, education, and outreach. The work of ASTEP projects takes place in remote terrestrial environments, places typically inaccessible to "civilians": the Norwegian protectorate of Svalbard, above the Arctic Circle; the far-northern reaches of the Arctic Ocean; the dry valleys of Antarctica; deep-sea hydrothermal vent systems and other unmapped underwater environments. ASTEP projects involve human researchers working with robotic adjuncts. ASTEP teams often combine include senior and student researchers. Some have even included "embedded" journalists and public affairs officers. ASTEP expeditions typically unfold in visually interesting, sometimes stunning, physical environments. ASTEP expeditions are virtually always intensive learning experiences for their researchers, and thus they provide good opportunities to demonstrate how science is actually done. Science means different things to different people in different situations, and thus public understanding of science, and science communication, are not simple things. Science can be a set of practices, a body of knowledge, a process of investigation, or a world view. In attempting to improve public understanding of science, it is useful to provide non-scientists with a window into the working world of science. ASTEP expeditions provide such windows. With the proliferation of miniaturized and increasingly affordable digital communication technology - still and video cameras, recorders, laptop computers - connections between the remote locations of ASTEP expeditions and students, teachers, and other interested citizens around the world are easier to make. Thanks to these technologies, interactive communications are also becoming easier. This paper will report on communication, education, and outreach activities for recent ASTEP field expeditions in the Arctic and Pacific oceans, Svalbard, and Mexico, highlighting success stories, lessons learned, and promising practices.

Uranium isotopic compositions of the crust and ocean: Age corrections, U budget and global extent of modern anoxia

NASA Astrophysics Data System (ADS)

Tissot, François L. H.; Dauphas, Nicolas

2015-10-01

The 238U/235U isotopic composition of uranium in seawater can provide important insights into the modern U budget of the oceans. Using the double spike technique and a new data reduction method, we analyzed an array of seawater samples and 41 geostandards covering a broad range of geological settings relevant to low and high temperature geochemistry. Analyses of 18 seawater samples from geographically diverse sites from the Atlantic and Pacific oceans, Mediterranean Sea, Gulf of Mexico, Persian Gulf, and English Channel, together with literature data (n = 17), yield a δ238U value for modern seawater of -0.392 ± 0.005‰ relative to CRM-112a. Measurements of the uranium isotopic compositions of river water, lake water, evaporites, modern coral, shales, and various igneous rocks (n = 64), together with compilations of literature data (n = 380), allow us to estimate the uranium isotopic compositions of the various reservoirs involved in the modern oceanic uranium budget, as well as the fractionation factors associated with U incorporation into those reservoirs. Because the incorporation of U into anoxic/euxinic sediments is accompanied by large isotopic fractionation (ΔAnoxic/Euxinic-SW = +0.6‰), the size of the anoxic/euxinic sink strongly influences the δ238U value of seawater. Keeping all other fluxes constant, the flux of uranium in the anoxic/euxinic sink is constrained to be 7.0 ± 3.1 Mmol/yr (or 14 ± 3% of the total flux out of the ocean). This translates into an areal extent of anoxia into the modern ocean of 0.21 ± 0.09% of the total seafloor. This agrees with independent estimates and rules out a recent uranium budget estimate by Henderson and Anderson (2003). Using the mass fractions and isotopic compositions of various rock types in Earth's crust, we further calculate an average δ238U isotopic composition for the continental crust of -0.29 ± 0.03‰ corresponding to a 238U/235U isotopic ratio of 137.797 ± 0.005. We discuss the implications of the variability of the 238U/235U ratio on Pb-Pb and U-Pb ages and provide analytical formulas to calculate age corrections as a function of the age and isotopic composition of the sample. The crustal ratio may be used in calculation of Pb-Pb and U-Pb ages of continental crust rocks and minerals when the U isotopic composition is unknown. In cosmochemistry, the search for 247Cm (t1/2 = 15.6 Myr), an extinct short-lived radionuclide that decays into 235U, is important for understanding how r-process nuclides were synthesized in stars and learning about the astrophysical context of solar system formation (Chen and Wasserburg, 1981; Wasserburg et al., 1996; Nittler and Dauphas, 2006; Brennecka et al., 2010b; Tissot et al., 2015). In both terrestrial and extraterrestrial samples, variations in the 238U/235U ratio affect Pb-Pb ages (and depending on the analytical protocols, U-Pb ages). Therefore, samples dated by these techniques need to have their U isotopic compositions measured (Stirling et al., 2005, 2006; Weyer et al., 2008; Amelin et al., 2010; Brennecka et al., 2010b; Brennecka and Wadhwa, 2012; Connelly et al., 2012; Goldmann et al., 2015) or uncertainties on the U isotopic composition should be propagated into age calculations. In low temperature aqueous geochemistry, U isotopic fractionation between U4+ and U6+ (driven in part by nuclear field shift effects; Bigeleisen, 1996; Schauble, 2007; Abe et al., 2008), makes U isotopes potential tracers of paleoredox conditions (Montoya-Pino et al., 2010; Brennecka et al., 2011a; Kendall et al., 2013, 2015; Asael et al., 2013; Andersen et al., 2014; Dahl et al., 2014; Goto et al., 2014; Noordmann et al., 2015). The present paper aims at constraining some aspects of the global budget of uranium in the modern oceans using 238U/235U isotope variations, which involves characterizing the U isotopic composition of seawater and several reservoirs involved in the uranium oceanic budget. Uranium can exist in two oxidation states in terrestrial surface environments: U4+ is insoluble in seawater while U6+ is soluble (Langmuir, 1978). The contrasting behaviors of the two oxidation states of uranium explains why the disappearance of detrital uraninite after the Archean marks the rise of oxygen in Earth's atmosphere/hydrosphere (Ramdohr, 1958; Rasmussen and Buick, 1999; Frimmel, 2005). More recently, significant effort has focused on using U isotopes to constrain the past extents of anoxic/euxinic vs. oxic or suboxic sediments in modern and ancient oceans (Montoya-Pino et al., 2010; Brennecka et al., 2011a; Asael et al., 2013; Kendall et al., 2013, 2015; Andersen et al., 2014; Dahl et al., 2014; Goto et al., 2014; Noordmann et al., 2015). A virtue of this system is that it can potentially reflect the global redox state of Earth's oceans. At the same time, several difficulties have been encountered in applying U isotopes as paleo-redox indicators. For example, detrital contributions can blur the authigenic signal and have to be corrected for (Asael et al., 2013; Andersen et al., 2014; Noordmann et al., 2015), uranium isotopes can be affected by diagenesis and exchange with porewater (Romaniello et al., 2013; Andersen et al., 2014), and the exact isotopic fractionation factors relevant to various conditions of deposition are uncertain. While significant progress has already been made to address these difficulties (Asael et al., 2013; Romaniello et al., 2013; Andersen et al., 2014; Noordmann et al., 2015), this system and others are missing some of the groundwork studies on modern environments that are needed to gain trust in their applications to ancient sediments.In the modern ocean, water-soluble uranium behaves conservatively (i.e., U concentration correlates linearly to water salinity, Ku et al., 1977; Owens et al., 2011) and has a long residence time of ∼400 kyr (Ku et al., 1977). The ocean is therefore a large repository of uranium, exceeding the total inventory of land-based deposits (Lu, 2014). The riverine input (40-46 Mmol/yr) is balanced by several sinks; including suboxic sediments, anoxic/euxinic sediments, carbonates, altered oceanic crust, salt marshes and Fe-Mn nodules. Barnes and Cochran (1990), Morford and Emerson (1999), Dunk et al. (2002), and Henderson and Anderson (2003) each proposed estimates for the oceanic uranium budget that differ substantially in the fluxes that they use. Uranium isotopes are sensitive to ocean redox conditions because uranium removal in anoxic/euxinic sediments imparts large uranium isotopic fractionation, so that the areal extent of this sink influences greatly the U isotopic composition of seawater relative to the riverine input. In the present paper, we report double-spike uranium isotopic measurements of 18 seawater samples, 18 continental crust lithologies, 7 individual minerals, 6 oyster samples, 3 modern evaporites samples, 2 lake water samples, 1 large river water sample and 1 coral sample. These measurements are supplemented by compilations of literature data. With this large data set (n = 444), we are able to constrain the flux of uranium into anoxic/euxinic sediments, as well as the global extent of anoxia in the modern ocean (percent of seafloor covered by anoxic/euxinic sediments). Our findings compare well with independent estimates and rule out the most recent U budget of Henderson and Anderson (2003).As part of our effort, we also present a data reduction method for double-spike measurements that is both comprehensive in the way the errors are propagated and simple to implement.

Terrestrial microbes in martian and chondritic meteorites

NASA Astrophysics Data System (ADS)

Airieau, S.; Picenco, Y.; Andersen, G.

2007-08-01

Introduction: The best extraterrestrial analogs for microbiology are meteorites. The chemistry and mineralogy of Asteroid Belt and martian (SNC) meteorites are used as tracers of processes that took place in the early solar system. Meteoritic falls, in particular those of carbonaceous chondrites, are regarded as pristine samples of planetesimal evolution as these rocks are primitive and mostly unprocessed since the formation of the solar system 4.56 billion years ago. Yet, questions about terrestrial contamination and its effects on the meteoritic isotopic, chemical and mineral characteristics often arise. Meteorites are hosts to biological activity as soon as they are in contact with the terrestrial biosphere, like all rocks. A wide biodiversity was found in 21 chondrites and 8 martian stones, and was investigated with cell culture, microscopy techniques, PCR, and LAL photoluminetry. Some preliminary results are presented here. The sample suite included carbonaceous chondrites of types CR, CV, CK, CO, CI, and CM, from ANSMET and Falls. Past studies documented the alteration of meteorites by weathering and biological activity [1]-[4]. Unpublished observations during aqueous extraction for oxygen isotopic analysis [5], noted the formation of biofilms in water in a matter of days. In order to address the potential modification of meteoritic isotopic and chemical signatures, the culture of microbial contaminating species was initiated in 2005, and after a prolonged incubation, some of the species obtained from cell culture were analyzed in 2006. The results are preliminary, and a systematic catalog of microbial contaminants is developing very slowly due to lack of funding. Methods: The primary method was cell culture and PCR. Chondrites. Chondritic meteorite fragments were obtained by breaking stones of approximately one gram in sterile mortars. The core of the rocks, presumably less contaminated than the surface, was used for the present microbial study, and the remaining fragments of the samples were used for amino acid and isotopic analyses [6]. Some samples were fragments of dried and wet meteorites isolated in centrifuge tubes after a 10-day water extraction. Sabouraud Dextrose (dilutions 1:10 and 1:1000), Bacto Agar, LB Broth Miller (dilutions 1:10 and 1:1000), and R2A agar (1:1 and 1:1000), were autoclaved and cooled in culture plates inside a clean hood for cell culture. Some controls retained sterile moist agar still adhering to the perimeter of the plates for up to 18 months, and validated the sterile technique. Cell culture, PCR and microscopy documented a diversity of archea, prokaryotes and eukaryotes in these samples [7]. The plates displaying microbial growth at room temperature after 6 weeks or less were used to produce streak plates and isolate colonies of individual species for long term freezing in Eppendorf tubes. Any plate with biological growth along the perimeter of the plate was discarded. The plates without microbial activity after 6 weeks were stored in a fridge for 18 months. Control plates, exposed to the clean hood, laboratory room, used gloves, and weighing paper used in the analyses, sustained the prolonged storage with no sign of microbial activity that could be related to the analysis method. Dust grains and water extracts from the meteorites were spread on agar surfaces in cell culture Petri dishes in a clean hood. SNC samples.In early 2005, the surface of SNC stones in the USNM curation facility were brushed with sterile swabs. Fallen dust grains were collected on weighing paper and isolated in sterile tubes. The sample suite included Zagami USNM 6545, Lafayette USNM 1505, Los Angeles USNM 7052, Shergotty USNM 321, Nakhla USNM 5892, Nakhla USNM 426 (117.4 g) and Nakhla USNM 426 (18.2 g), and Chassigny USNMMNHN 2524. The controls, worker's gloves, blank swabs, and weighing paper exhibited no microbial activity in subsequent months. The cell culture was conducted with Sabouraud Dextrose and R2A only, by deposition of dry grains onto the surface of agar in culture plates that were incubated at 20 Celsius 2 weeks, then at 35 Celsius 3 days, and finally at 4 Celsius for 18 months. Limulus Amoebocyte Lysate (LAL Assay) measurements of the swabs [7] revealed low biological activity in all SNCs, except in a small piece of Nakhla USNM 426 (18.2 g) (activity below detection limit) and Chassigny (data unavailable). The LAL technique assesses gram negative bacterial equivalents. Culture sample material was recovered from the agar plates using sterile pipette tips. The material was added to 100 uL sterile water. This material was boiled for 15 min. in a water bath to lyse the cells and inactivate enzymes. 10 uL of the boiled lysate was used as template in PCR. Universal bacterial primers (27F and 1492R) were used to amplify a major portion of the 16S rRNA gene. PCR product was purified using a Qiagen MinElute PCR Purification kit and then sent for sequencing. Results and Comments: GRA 95229. Biological growth out of dust grains deposited on the agar surface was visible with the naked eye, and occurred after incubation in a fridge for 10 months. Leoville. Biological growth occurred at the contact of a dust grain and the agar surface after 1 month. It continued to expand outside a dust grain deposited on Sabouraud Dextrose 1:1000, while stored at 20 Celsius for 12 months. The fan shaped outgrowth reached about 1 cm on either side of the meteorite grain and dried. DNA was recovered, and PCR products yielded sequences of a Bacillus spp. Bacillus is a common soil bacterial genus, and the close sequence relatives of this isolate were no exception. They were rock or soil Bacillus, and have been found in Allende [4]. EET 87770. Rock fragments were wet for 8 months (Millipore water) in a sterile centrifuge tube, and were used to make a spread plate that dried over a period of 10 months. The yellow dried colonies yielded good PCR product and the sequences were compared to other GenBank sequences using the BLAST program. The closest matches were in the genus Microbacterium. Soil and plant isolates were close relatives by sequence comparison. Los Angeles. After 11 months of incubation in a fridge, a yellow colony grew at the center of a culture plate of Los Angeles dust grains (1:1000 R2A). There was no cell activity in the other agars. A DNA extraction yielded no usable results [7]. Sequencing was not performed because the culture plate became contaminated with outside organisms that overtook the colony of interest. Conclusions: The sequences for EET 87770 and Leoville were of a good quality and the sequence reads were long, so the data are clear that these are typical soil and/or plant-related bacteria commonly found in Earth habitats. Microbial species present in a dozen chondritic samples from isolates are not yet identified, and the contaminant in Los Angeles needs to be recovered. In addition, isotopic analyses of samples with various amounts of microbial contamination could help quantified isotopic impact of microbes on protoplanetary chemistry in these rocks. References : [1] Gounelle, M. and Zolensky M. LPS, (2001) LPS XXXII, Abstract #999. [2] Fries, M. et al. (2005) Meteoritical Society Meeting 68, Abstract # 5201. [3] Burckle, L. H. and Delaney, J. S (1999) Meteoritics & Planet. Sci., 32, 475-478. [4] Whitby, C. et al. (2000) ) LPS XXXI, Abstract #1732. [5] Airieau, S. A. et al (2005) Geochim. Cosmochim. Acta, 69, 4166-4171. [6] Unpublished data, with H. J. Cleaves, A. Aubrey, J. Bada (Scripps Institution of Oceanography), M. Thiemens (UC San Diego) and M. Fogel (Carnegie Institution of Washington). [7] Unpublished data, with A. Steele (CIW), and N. Wainwright (Marine Biological Laboratory). Acknowledgements: Lisa Welleberger for access to SNC samples at USNM; Ralph Harvey for organizing ANSMET; Denise C. Thiry and Andrew Steele for long term storage of samples, NormWainwright for LAL measurements. A small portion of this work was funded with a NASA Cosmochemistry grant, ( P. I. Thiemens).