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Chemical state of pre-solar matter

Consideration is given to several features of the chemical state of interstellar matter that may be relevant to the observed properties of chondrules if they are formed from aggregates of pre-existing particles. First, a brief summary of the numbers and types of interstellar particles as indicated by the extinction of starlight is given. Second, a model of the free decay interval required by the low solar abundance of 129-I is advanced. This model can support variations in the 129-I/127-I ratio that are larger than typical isotopic anomalies. Third, a new steady-state model of the chemical state of the interstellar medium is presented as a first step toward a quantitative distribution of the abundances among different chemical forms. Last, the advantages of fusing chondrules from aggregates of pre-solar dust by the action of exothermic chemistry are enumerated.

Clayton, D. D.↗

CO observations of galaxies 1985-1989

This catalog lists all publications containing new observations of CO isotopes in galaxies that have appeared since the submission of Verter (1985) and before the end of 1989. For each publication the number and nature of the observations are summarized. Condensations of this information can be used to evaluate the current status and direction of observational research on molecular gas in external galaxies.

Verter, Frances↗

Lunar Meteorites and Implications for Compositional Remote Sensing of the Lunar Surface

Lunar meteorites (LMs) are rocks found on Earth that were ejected from the Moon by impact of an asteroidal meteoroid. Three factors make the LMs important to remote-sensing studies: (1) Most are breccias composed of regolith or fragmental material; (2) all are rocks that resided (or breccias composed of material that resided) in the upper few meters of the Moon prior to launch and (3) most apparently come from areas distant from the Apollo sites. How Many Lunar Locations? At this writing (June 1999), there are 18 known lunar meteorite specimens. When unambiguous cases of terrestrial pairing are considered, the number of actual LMs reduces to 13. (Terrestrial pairing is when a single piece of lunar rock entered Earth's atmosphere, but multiple fragments were produced because the meteoroid broke apart on entry, upon hitting the ground or ice, or while being transported through the ice.) We have no reason to believe that LMs preferentially derive from any specific region(s) of the Moon; i.e., we believe that they are samples from random locations. However, we do not know how many different locations are represented by the LMs; mathematically, it could be as few as 1 or as many as 13. The actual maximum is < 13 because in some cases a single impact appears to have yielded more than one LM. Yamato 793169 and Asuka 881757 are considered "source-crater paired" or "launch paired" because they are compositionally and petrographically similar to each other and distinct from the others, and both have similar cosmic-ray exposure (CRE) histories. The same can be said of QUE 94281 and Y 793274. Thus the 13 meteorites probably represent a maximum of 11 locations on the Moon. The minimum number of likely source craters is debated and in flux as new data for different isotopic systems are obtained. Conservatively, considering CRE data only, a minimum of about 5 impacts is required. Compositional and petrographic data offer only probabilistic constraints. An extreme, but not unreasonable viewpoint, is that such data offer no constraint. For example, if one were to cut up the Apollo 17 landing site (which was selected for its diversity) into softball-sized pieces, some of those pieces (e.g., sample 70135) would be crystalline mare basalts like Y 793169 whereas others (e.g., sample 73131 would be feldspathic regolith breccias like MAC 88104/ 88105. However, nature is not so devious. Warren argues that LMs come from craters of only a few kilometers in diameter. If so, even though CRE data allow, for example, that ALHA 81005 and Y 791197) were launched simultaneously from the same crater, the probability is nevertheless low because the two meteorites are compositionally and mineralogically distinct. Thus, within the allowed range (5-11) for the number of locations represented by the LMs, values at the high end of the range are probably more likely. Mare Meteorites: Three LMs consist almost entirely of mare basalt. Two, Y 793169 and Asuka 881757, are unbrecciated, low-Ti, crystalline rocks that are compositionally and mineralogically similar (but not identical) to each other; they probably derive from a single lunar-mare location. The third, EET 87521/96008, is a fragmental breccia consisting predominantly of VLT mare basalt. Thus, these LMs probably represent only two lunar mare locations. The basaltic LMs have mineral and bulk compositions distinct from Apollo mare basalts. The petrography of Calcalong Creek has not been described in detail, but compositionally it is unique in that it corresponds to a mixture (breccia) of about one-half feldspathic material (i.e., the mean composition of the feldspathic lunar meteorites, below), one-fourth KREEP norite, one-fourth VLT mare basalt (like EET 87521), and 1% CI chondrite. With 4 micro g/g Th and correspondingly high concentrations of other incompatible elements, it is the only lunar meteorite that is likely to have come from within the Procellarum KREEP Terrane (PKT). Yamato 793274 and QUE 94281 are together distinct in being fragmental breccias containing subequal parts of feldspathic highland material and VLT mare basalt. Jolliff et al. estimate a mare to highland ratio of 54:46 for QUE 94281 and 62:38 for Y 793274; this difference is well within the range observed for soils collected only centimeters apart (in cores) at interface site like Apollo 15 and 17 [11]. Although the two meteorites were found on opposite sides of Antarctica, they are probably launch-paired. The strongest evidence is that the pyroclastic glass spherules that occur in both are of two compositional groups and the two groups are essentially the same in both meteorites. Yamato 791197 is nominally a feldspathic lunar meteorite (below), but among FLMs, it probably contains the highest abundance of clasts and glasses of mare derivation. As a consequence, its composition is at the high-Fe, low-Mg end of the range for FLMs and is not included in the FLM average of Table 1. Its composition is consistent with about 10% mare-derived material. Similarly, the two small (Y 82) pieces of Y 82192/82193186032 are more mafic than the large (Y 86) piece, probably as a result of about 7% mare-derived material. All Apollo missions went to areas in or near the PKT, and, consequently, all Apollo regolith samples are contaminated with Th-rich material from the PKT. At the nominally "typical" highland site, Apollo 16, about 30% of the regolith (<1-mm fines) is Th-rich ejecta from the Imbrium impact and about 6% is mare material probably derived from mare basins. Thus Apollo 16 regolith is not typical of the highlands. Among Apollo rocks, the compositions of the FLMs correspond most closely to the feldspathic granulitic breccias of Apollo 16 and 17. (Additional information is contained in original)

Korotev, R. L.↗

2-Methylhopanoids: Biomarkers for Cyanobacteria and for Oxygenic Photosynthesis

This paper reports new biomarker and carbon isotopic data for cultured cyanobacteria, cyano-bacterially- dominated ecosystems and ancient sedi-ments and petroleum. We found that cyanobacteria are the predominant source of a distinctive membrane lipid biomarker, namely 2- methylbacteriohopanepolyol (2-Me-BHP). We then sought evidence for a geochemical record of the fossil hydrocarbon analogues of these compounds (2- methylhopanes) and found a trend toward their in-creased relative abundance in marine sediments going back through geological time to 2500 Ma. We conclude that cyanobacteria were the dominant form of phytoplankton and source of molecular oxygen in the Proterozoic ocean. Extending the geological record of cyanobacteria further to Archean times is now a matter of finding a suitably preserved rock record. Additional information is contained in the original extended abstract.

Summons, R. E.↗

Collaborative Study for Analysis of High Resolution Infrared Atmospheric Spectra Between NASA Langley Research Center and the University of Denver

The Langley-D.U. collaboration on the analysis of high resolultion infrared atmospheric spectra covered a number of important studies of trace gases identification and quantification from field spectra, and spectral line parameters analysis. The collaborative work included: 1) Quantification and monitoring of trace gases from ground-based spectra available from various locations and seasons and from balloon flights; 2) Identification and preliminary quantification of several isotopic species, including oxygen and Sulfur isotopes; 3) Search for new species on the available spectra, including the use of selective coadding of ground-based spectra for high signal to noise; 4) Update of spectroscopic line parameters, by combining laboratory and atmospheric spectra with theoretical spectroscopy methods; 5) Study of trends and correlations of atmosphere trace constituents; and 6) Algorithms developments, retrievals intercomparisons and automatization of the analysis of NDSC spectra, for both column amounts and vertical profiles.

Goldman, A.↗

Assessment of Volatile Depletion Mechanisms for the Moon - Pre-Cursors, Giant Impact, Core Formation, Post-Impact Loss

The volatile element depletions in the Moon have been recognized for decades. Multiple explanations have been debated, and arguments have become more quantitative, in large part due to new elemental partitioning and isotopic data. Depletions in pre-cursor materials and due to post-accretion degassing have been evaluated using isotopic data. Partitioning of many volatile elements into metallic cores can now be evaluated for many volatile siderophile elements (VSE). Here is presented an evaluation of the role of core formation for 12 volatile siderophile elements for which partitioning data is now available. Examination of all 12 elements at once allows recognition of general trends, without undue focus on one element. Ga, Ge, Zn, Sn, As, Sb, Cd, Ag, Bi, P, In, Cu are all moderately to highly volatile, and will be discussed in their order of volatility as gauged by their 50 percent condensation temperature.

Righter, K.↗

Os isotopes in SNC meteorites and their implications to the early evolution of Mars and Earth

A new development on the measurement of the Os isotopic composition by mass spectrometry using negative ions opened a new field of applications. The Re-Os systematic provides time information on the differentiation of the nobel metals. The nobel metals are strongly partitioned into metal and sulphide phases, but also the generation of silicate melts might fractionate the Re-Os system. Compared to the other isotopic systems which are mainly dating the fractionation of the alkalis and alkali-earth elements, the Re-Os system is expected to disclose entirely new information about the geochemistry. Especially the differentiation and early evolution of the planets such as the formation of the core will be elucidated with this method.

Jagoutz, E.↗

Ag isotopic and chalcophile element evolution of the terrestrial and martian mantles during accretion: new constraints from Bi, Pd, and Ag metal-silicate partitioning.

The Earth’s timing of accretion and acquisition of moderately volatile compounds is uncertain. Hafnium-W and Mn-Cr isotopic data can bracket the timing of early planetary differentiation and core formation. The Ag-Pd system has also been utilized but its application has been limited by a lack of high pressure and temperature metal-silicate partitioning for Pd and Ag. Be-cause Ag (and Bi) are volatile chalcophile siderophile elements, understanding their early distribution can constrain the origin of volatile elements in differentiated bodies and planets. Unfortunately, neither Ag or Bi have been studied across the wide range of pressure and temperature conditions that are relevant to accretion and core-mantle differentiation. Here, new high-pressure and temperature multi-anvil metal-silicate equilibrium experiments for Bi and Ag have been carried out at conditions relevant to planetary accretion and metal silicate differentiation that allow a more refined and complete understanding of element partitioning during core formation. The new metal-silicate partitioning data utilized to predict the distributions of Bi, Pd, and Ag at conditions of accretion for Earth and Mars and show that the Pd/Ag ratio is significantly fractionated during accretion, allowing for the production of detectable 107Ag anomalies produced while 107Pd (half life = 6.5 M.y.) was still extant. Application of the new partitioning results to Earth shows that D(Bi) and D(Ag) (D = metal/silicate concentration ratio) are lowered due to the effect of pressure and Si alloyed in the metallic liquid, resulting in higher predicted mantle Bi and Ag abundances than in the bulk silicate Earth (BSE), as well as high and variable Pd/Ag. The unradiogenic Ag isotopic composition of the BSE could have been generated by early accretion of volatile-poor (high Pd/Ag) precursors, followed by later accretion of volatile–rich (low Pd/Ag) material, in agreement with earlier studies of Pd-Ag and Mn-Cr (Schönbächler et al., 2010). However, these main accretion phases would have to be followed by segregation of a sulfide liquid (at least 1.5% of magma ocean) at high pressures (>30 GPa), to explain the PUM Bi, Pd, and Ag, as well as Au, Pt, Cu and Ni concentrations as proposed previously. If the early accreted bulk Earth was volatile depleted with high Pd/Ag ratios, portions of the mantle may contain ancient domains that developed positive 107Ag isotopic anomalies (as also argued by noble gases, Nd, W, and Os isotopes). In comparison, Bi, Pd, and Ag concentrations in the martian mantle could have been set by simple metal-silicate equilibrium. Mars accreted and differentiated relatively rapidly, while also developing a deep magma ocean with a high Pd/Ag ratio that could have evolved positive 107Ag anomalies, in contrast to Earth. Measurements on shergottites may reveal these predicted Ag isotopic anomalies.

accretion↗

Molybdenum Isotopic Composition of Iron Meteorites, Chondrites and Refractory Inclusions

Recent Mo isotopic studies of meteorites reported evidence for differences in isotopic compositions for whole rocks of some primitive and differentiated meteorites relative to terrestrial materials. Enrichments of r- and p-process isotopes of up to 3-4 units (e unit = parts in 10(exp 4) over s-process dominated isotopes are the most prominent features. Certain types of presolar grains show large enrichments in s-process isotopes, however, it was concluded on grounds of mass balance that incomplete digestion of such grains cannot explain the enrichments of r- and p-process isotopes in whole rocks of primitive chondrites. If the reported variability in r- and p-process isotope enrichments reflects the true isotopic characteristics of the whole rocks, the implications are quite profound. It would suggest the presence of large scale Mo isotopic heterogeneity within the solar accretion disk with likely collateral effects for other elements. However, such effects were not found for Ru isotopes, nor for Zr isotopes. Another recent Mo isotopic study by multi collector ICP-MS could not confirm the reported deviations in Allende, Murchison or iron meteorites. Here, we present new results for the Mo isotopic composition of iron meteorites, chondrites and CAIs obtained by negative thermal ionization mass spectrometry (NTIMS). We discuss analytical aspects and the homogeneity of Mo isotopic compositions in solar system materials.

Becker, H.↗

Resonance ionization mass spectrometry for isotopic abundance measurements

Resonance ionization mass spectrometry (RIMS) is a relatively new laser-based technique for the determination of isotopic abundances. The resonance ionization process depends upon the stepwise absorption of photons from the laser, promoting atoms of the element of interest through progressively higher electronic states until an ion is formed. Sensitivity arises from the efficiency of the resonant absorption process when coupled with the power available from commercial laser sources. Selectivity derives naturally from the distinct electronic structure of different elements. This isobaric discrimination has provided the major impetus for development of the technique. Resonance ionization mass spectrometry was used for analysis of the isotopic abundances of the rare earth lutetium. Isobaric interferences from ytterbium severely effect the ability to measure small amounts of the neutron-deficient Lu isotopes by conventional mass spectrometric techniques. Resonance ionization for lutetium is performed using a continuous-wave laser operating at 452 nm, through a sequential two-photon process, with one photon exciting the intermediate resonance and the second photon causing ionization. Ion yields for microgram-sized quantities of lutetium lie between 10(6) and 10(7) ions per second, at overall ionization efficiencies approaching 10(-4). Discrimination factors against ytterbium greater than 10(6) have been measured. Resonance ionization for technetium is also being explored, again in response to an isobaric interference, molybdenum. Because of the relatively high ionization potential for Tc, three-photon, two-color RIMS processes are being developed.

Miller, C. M.↗

In Situ Measurement of Atmospheric Krypton and Xenon on Mars with Mars Science Laboratory

Mars Science Laboratorys Sample Analysis at Mars (SAM) investigation has measured all of the stable isotopes of the heavy noble gases krypton and xenon in the martian atmosphere, in situ, from the Curiosity Rover at Gale Crater, Mars. Previous knowledge of martian atmospheric krypton and xenon isotope ratios has been based upon a combination of the Viking missions krypton and xenon detections and measurements of noble gas isotope ratios in martian meteorites. However, the meteorite measurements reveal an impure mixture of atmospheric, mantle, and spallation contributions. The xenon and krypton isotopic measurements reported here include the complete set of stable isotopes, unmeasured by Viking. The new results generally agree with Mars meteorite measurements but also provide a unique opportunity to identify various non-atmospheric heavy noble gas components in the meteorites. Kr isotopic measurements define a solar-like atmospheric composition, but deviating from the solar wind pattern at 80Kr and 82Kr in a manner consistent with contributions originating from neutron capture in Br. The Xe measurements suggest an intriguing possibility that isotopes lighter than 132Xe have been enriched to varying degrees by spallation and neutron capture products degassed to the atmosphere from the regolith, and a model is constructed to explore this possibility. Such a spallation component, however, is not apparent in atmospheric Xe trapped in the glassy phases of martian meteorites.

Conrad, P. G.↗

How Will Sea Ice Loss Affect the Greenland Ice Sheet? On the Puzzling Features of Greenland Ice-Core Isotopic Composition

The modern cryosphere, Earth's frozen water regime, is in fast transition. Greenland ice cores show how fast theses changes can be, presenting evidence of up to 15 C warming events over timescales of less than a decade. These events, called Dansgaard/Oeschger (D/O) events, are believed to be associated with rapid changes in Arctic sea ice, although the underlying mechanisms are still unclear. The modern demise of Arctic sea ice may, in turn, instigate abrupt changes on the Greenland Ice Sheet. The Arctic Sea Ice and Greenland Ice Sheet Sensitivity (Ice2Ice Chttps://ice2ice.b.uib.noD) initiative, sponsored by the European Research Council, seeks to quantify these past rapid changes to improve our understanding of what the future may hold for the Arctic. Twenty scientists gathered in Copenhagen as part of this initiative to discuss the most recent observational, technological, and model developments toward quantifying the mechanisms behind past climate changes in Greenland. Much of the discussion focused on the causes behind the changes in stable water isotopes recorded in ice cores. The participants discussed sources of variability for stable water isotopes and framed ways that new studies could improve understanding of modern climate. The participants also discussed how climate models could provide insights into the relative roles of local and nonlocal processes in affecting stable water isotopes within the Greenland Ice Sheet. Presentations of modeling results showed how a change in the source or seasonality of precipitation could occur not only between glacial and modern climates but also between abrupt events. Recent fieldwork campaigns illustrate an important role of stable isotopes in atmospheric vapor and diffusion in the final stable isotope signal in ice. Further, indications from recent fieldwork campaigns illustrate an important role of stable isotopes in atmospheric vapor and diffusion in the final stable isotope signal in ice. This feature complicates the quantitative interpretation of ice core signals but also makes the stable ice isotope signal a more robust regional indicator of climate, speakers noted. Meeting participants agreed that to further our understanding of these relationships, we need more process-focused field and laboratory campaigns.

Greenland↗

Lead isotope systematics of three Apollo 17 mare basalts

The paper deals with new and more accurate determinations of uranium, thorium, and isotopic lead data for five bulk samples and separate pyroxene, ilmenite, and plagioclase from basalt 71055. In a concordia diagram, the samples suggest a postcrystallization disturbance of the U-Pb systems of the rock. There is no compelling reason, from U-Pb data, to believe that the moon is younger than 4.55 AE.

Tilton, G. R.↗

Voyager measurements of the isotopic composition of cosmic-ray aluminum and implications for the propagation of cosmic rays

We report a new measurement of the cosmic-ray isotopic composition of aluminum in the low-energy range form 75 to 206 MeV per nucleon.This measurement was made using the high-energy telescope of the CRS experiment on the Voyager 1 and 2 spacecraft during the time period from 1977 to 1993 with an average solar modulation level about 497 MV, roughly the same as at Earth near sunspot minimum. We obtain approximately 430 Al events of which approximately 35 are Al-26 and 395 are Al-27. The Al isotopes were separated with an average mass resolution sigma of 0.35 amu. Our interpretation of the isotopic composition of cosmic-ray aluminum is based on a standard Leaky-Box model for the interstellar propagation of cosmic-ray nuclei using the latest cross sections of the New Mexico-Saclay collaboration as well as a disk-halo diffusion model. From our observed ratio Al-26/Al-27 of 8.3 +/- 2.4 % we deduce an average interstellar density of about 0.52 (+0.26, -0.2) atoms per cu cm. This density is larger than the value of 0.28 (+0.14, -0.11) atoms per cu cm we found from an analysis of the observed abundance of the longer lived Be-10 made using data from the Voyager detectors over almost the same time interval and using essentially the same propagation program.

Lukasiak, A.↗

Endemic isotopic anomalies in titanium

Abundances of the titanium isotopes were determined using a new high-precision technique that shows terrestrial, lunar, and bulk meteorite samples to be indistinguishable. Ca-Al-Ti-rich inclusions in the Allende meteorite are found to contain Ti of widely varying isotopic composition reflecting the presence of at least three nucleosynthetic components. The anomalies in Ti appear to be relatively widespread and, when correlated with Ca data, provide a clue to nucleosynthesis in the neighborhood of the iron peak and to the late-stage nucleosynthetic processes which immediately preceded formation of the solar nebula.

Niederer, F. R.↗

Lu-Hf and Sm-Nd Isotopic Studies of Shergottites and Nakhlites: Implications for Martian Mantle Sources

We present a new Lu-Hf and Sm-Nd isotope systematics study of four enriched shergottites (Zagami, Shergotty, NWA856 and Los Angeles), and three nakhlites (Nakhla, MIL03346 and Yamato 000593) in order to further understand processes occurring during the early differentiation of Mars and the crystallization of its magma ocean. Two fractions of the terrestrial petrological analogue of nakhlites, the Archaean Theo's flow (Ontario, Canada) were also measured. The coupling of Nd and Hf isotopes provide direct insights on the mineralogy of the melt sources. In contrast to Sm/Nd, Lu/Hf ratios can be very large in minerals such as garnet. Selective partial melting of garnet bearing mantle sources can therefore lead to characteristic Lu/Hf signatures that can be recognized with Hf-176/Hf-177Hf ratios.

Debaille, V.↗

Diffusion-controlled magnesium isotopic fractionation of a single crystal forsterite evaporated from the solid state

Though the origin of calcium- and aluminum-rich inclusions (CAI's) in carbonaceous chondrites is till a disputed issue, evaporation is no doubt one of the most important processes for the formation of CAI's in the early solar nebula. The mechanism for production of large isotopic mass fractionation effects in magnesium, silicon, oxygen, and chromium in CAI's can be better understood by examining isotopic fractionation during the evaporation of minerals. New evaporation experiments were performed on single-crystal forsterite. The magnesium isotopic distribution near the evaporating surfaces of the residues using a modified AEI IM-20 ion microprobe to obtain rastered beam depth profiles was measured. A theoretical model was used to explain the profiles and allowed determination of the diffusion coefficient of Mg(++) in forsterite at higher temperatures than previous measurements. The gas/solid isotopic fractionation factor for magnesium for evaporation from solid forsterite was also determined and found to be nearly the same as that for evaporation of liquid Mg2SiO4.

Wang, Jianhua↗