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NASA NTRS1976

Volatile element depletion and K-39/K-41 fractionation in lunar soils

Evidence for selective loss and isotopic fractionation (in the case of K) of volatile elements during formation of agglutinates by micrometeoritic bombardment of lunar soils is presented. Concentrations and isotopic compositions of volatile elements (K, Rb, Pb) and nonvolatile elements (U, Th, Ba, Sr, rare earths) in separates taken from soils 14163, 14259, 15041, 68501, and 71500 are examined. Rayleigh fractionation calculations applied to K-39/K-41 isotopic data indicate ten-fold recycling of bulk soil, to account for observed isotopic anomalies. The lunar soil fines fraction seems to be a site of deposition for volatile or labile Pb produced during agglutination. Local fines (below 75 microns) are viewed as representative of the parent material for agglutinates formed in situ by micrometeoritic impact. Magnetic separation of agglutinates from soil 68501 revealed a bimodal population, with one class comprising welded blocky magnetic glasses.

Church, S. E.↗

NASA NTRS1981

Crustal influence in the generation of continental flood basalts

The suggestion that primordial undifferentiated material may exist in the earth's mantle has recently been revived on the strength of Nd isotope data for two types of young continental rocks - flood basalts and kimberlites. The limited published data show a clustering of Nd isotopic compositions close to those for meteorites with chondritic relative rare-earth (REE) abundance. In contrast, data are presented for samples from the Columbia flood basalt province of the northwestern United States which show large isotopic variability suggestive of mixing processes acting after the separation of the primary magmas from their mantle source.

Carlson, R. W.↗

NASA NTRS1986

Recent progress in Precambrian paleobiology

Ongoing studies at UCLA include the following: (1) investigations in Archean and Proterozoic sequences of various locations; (2) laboratory and field studies of modern microbial biocoenoses (analogues of Precambrian microbial communities) especially those at Laguna Mormona, Baja California, Mexico; (3) development of new laboratory techniques for the separation and concentration of minute cellularly preserved fossils for isotopic and organic geochemical analyses; and (4) assembly of a computerized database for assessment of the timing and nature of major events occurring during Precambrian biotic evolution, and of the potential applicability of ancient microbiotas to problems of global biostratigraphy and biogeography.

Schopf, J. W.↗

NASA NTRS1993

The EET87513 clast N: A CM2 fragment in an HED polymict breccia

Xenoliths of material resembling carbonaceous chondrites have been found in several HED polymict breccias. Most workers concluded that these clasts are related to CM2 meteorites on the basis of texture, bulk composition, and mineralogy. Data on clast N, a carbonaceous chondrite fragment from the howardite EET87513 large enough (approximately 4x5mm on the surface of the slab from which it was separated) to extract bulk samples for INAA and oxygen isotope analysis and to provide a thin section for electron microprobe, SEM, and TEM analysis is reported. Preliminary data for this clast were previously reported. INAA was performed at Oregon State University and bulk oxygen isotopic composition was determined at the University of Chicago. These data confirm that EET87513 clast N is a fragment of CM2 material.

Buchanan, P. C.↗

NASA NTRS1994

Oxygen isotopes in circumstellar Al203 grains from meteorites and stellar nucleosynthesis

We have found a approximately 3 micrometer Al2O3 grain (B39) in the Bishunpur LL3.1 chondrite that is enriched in 0-17 by a factor of approximately 6.8 (0-16/0-17 = 385 +/- 9) and depleted in 0-18 by almost 60% (0-16/0-18 = 853 +/- 30) relative to solar system oxygen and has an initial Al-26/Al-27 = 1.7 +/- 0.2 x 10 (exp 3), approximately 34 times greater than the initial solar system value. The isotopic compositions of B39 and two other Al2O3 grains previously reported from the Orgueil and Murchison meteorites show that these grains formed directly from the ejecta of low-mass AGB stars with C/O less than 1. A simple theoretical analysis is presented showing that the oxygen systematics of the grains are a natural consequence of main-sequence evolution followed by first dredge-up Al-26 is the result of third dredge-up. Circumstellar Al2O3 grains provide very precise isotopic data for stellar ejecta that complement spectroscopic observations of oxygen-rich stars. Isotopic differences indicate that the Al2O3 grains come from separate stars of different mass and intital oxygen composition that originated in molecular clouds different from the one in which the solar system formed.

Huss, Gary R.↗

NASA NTRS2006

Initial Isotopic Heterogeneities in ZAGAMI: Evidence of a Complex Magmatic History

Interpretations of Zagami s magmatic history range from complex [1,2] to relatively simple [3]. Discordant radiometric ages led to a suggestion that the ages had been reset [4]. In an attempt to identify the mechanism, Rb-Sr isochrons were individually determined for both fine-grained and coarse-grained Zagami [5]. Ages of approx.180 Ma were obtained from both lithologies, but the initial Sr-87/Sr-86 (ISr) of the fine-grained lithology was higher by 8.6+/-0.4 e-units. Recently, a much older age of approx.4 Ga has been advocated [6]. Here, we extend our earlier investigation [5]. Rb-Sr Data: In [5] we applied identical, simplified, procedures to both lithologies to test whether a grain-size dependent process such as thermally-driven subsolidus isotopic reequilibration had caused age-resetting. Minerals were separated only by density. In the present experiment, purer mineral separates were analysed with improved techniques. Combined Rb-Sr results give ages (T) = 166+/-12 Ma and 177+/-9 Ma and I(subSr) = 0.72174+/-9 and 0.72227+/-7 for the coarse-grained and fine-grained lithologies, respectively. ISr in the fine-grained sample is thus higher than in the coarse-grained sample by 7.3+/-1.6 e-units. The results for the coarse-grained lithology are in close agreement with T = 166+/-6 Ma, ISr = 0.72157+/-8 for an adjacent sample [7] and T = 178+/-4 Ma, ISr = 0.72151+/-5 [4, adjusted] for a separate sample. Thus, fine-grained Zagami appears on average to be less typical of the bulk than coarse-grained Zagami.

Nyquist, L. E.↗

NASA NTRS1993

Ages of pristine noritic clasts from lunar breccias 15445 and 15455

The Rb-Sr and Sm-Nd isotopic ages were determined for two Apollo 15 pristine lunar breccias, 15445 and 15455, collected near Spur Crater on the Apennine Front. The analyses of mineral separates from two norite samples in breccia 15445 showed that the Sm-Nd isotopic system for both norites from the large Clast B of 15445 was well defined, yielding precise ages of 4.28 +/- 0.03 Ga and 4.46 +/- 0.07 Ga, suggesting that the Cast B is a mixture of two or more lithologies. The overall age results indicate that some Mg-suite rocks are as old as ferroan-anorthosite-suite rocks. Moreover, age data of three major crustal rocks (a Mg suite, a ferroan-anorthosite suite, and an evolved suite) show that they all have variable ages.

Shih, C.-Y.↗

NASA NTRS1996

Meteoritic Sulfur Isotopic Analysis

Funds were requested to continue our program in meteoritic sulfur isotopic analysis. We have recently detected a potential nucleosynthetic sulfur isotopic anomaly. We will search for potential carriers. The documentation of bulk systematics and the possible relation to nebular chemistry and oxygen isotopes will be explored. Analytical techniques for delta(sup 33), delta(sup 34)S, delta(sup 36)S isotopic analysis were improved. Analysis of sub milligram samples is now possible. A possible relation between sulfur isotopes and oxygen was detected, with similar group systematics noted, particularly in the case of aubrites, ureilites and entstatite chondrites. A possible nucleosynthetic excess S-33 has been noted in bulk ureilites and an oldhamite separate from Norton County. High energy proton (approximately 1 GeV) bombardments of iron foils were done to experimentally determine S-33, S-36 spallogenic yields for quantitation of isotopic measurements in iron meteorites. Techniques for measurement of mineral separates were perfected and an analysis program initiated. The systematic behavior of bulk sulfur isotopes will continue to be explored.

Thiemens, Mark H.↗

NASA NTRS2014

Hydrogen (H) Isotope Composition of Type II Kerogen Extracted by Pyrolysis-GC-MS-IRMS: Terrestrial Shale Deposits as Martian Analogs

Described here is a technique for H isotope analysis of organic compounds pyrolyzed from kerogens isolated from gas‐ and liquids‐rich shales. Application of this technique will progress the understanding of the use of H isotopes not only in potential kerogen occurrences on Mars, but also in terrestrial oil and gas resource plays. H isotope extraction and analyses were carried out utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC interfaced with a Thermo MAT 253 IRMS. Also, a split of GC‐separated products was sent to a DSQ II quadrupole MS to make qualitative and semi‐quantitative compositional measurements of these products. Kerogen samples from five different basins (type II and II‐S) were dehydrated (heated to 80 C overnight under vacuum) and analyzed for their H isotope compositions by Pyrolysis‐GC‐MS‐TC‐IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C), which quantitatively forms H2. Samples ranging from ~0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. and separated on a Poraplot Q GC column. H isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight. H2O average delta D = ‐215.2 per mille (V‐SMOW), ranging from ‐ 271.8 per mille for the Marcellus Shale to ‐51.9 per mille for a Polish shale. Higher molecular weight compounds like toluene (C7H8) have an average delta D of ‐89.7 per mille, ranging from ‐156.0 per mille for the Barnett Shale to ‐50.0 per mille for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during basin formation. Since hydrocarbon H isotopes readily exchange with water, these data may provide some useful information on gas‐water or oil‐water interaction in resource plays, and further as a possible indicator of paleoenvironmental conditions. Alternatively, our data may be an indication of H isotope exchange with water and/or acid during the kerogen isolation process. Either of these interpretations will prove useful when deciphering H isotope data derived from kerogen analyses. Understanding the role that these H‐bearing compounds play in terrestrial shale paleo‐environmental reconstruction may also prove useful as analogs for understanding the interactions of water and potential kerogen/organic compounds on the planet Mars.

Socki, Richard A.↗

NASA NTRS1992

Solar-type xenon - Isotopic abundances in Pesyanoe

Elemental and isotopic abundances of Ar and Xe were measured in three grain-size separates in the dark phase of the enstatite achondrite Pesyanoe by stepwise heating, using a combination of pyrolysis and combustion steps. The data reveal a low-temperature gas fraction with Ar/Xe ratios close to the solar ratio and isotopically similar to solar-type Ar and Xe observed in lunar samples. The gas released at intermediate temperature steps shows that Ar and Xe are isotopically fractionated, compared to the low-temperature components. Pesyanoe does not have excess Ar-40 and fission Xe, which means its parent body was too small for ion reimplantation. It is concluded that solar-type Xe isotopic abundances can be inferred from the low-temperature component. A comparison of Pesyanoe and lunar data shows that isotopic signatures of solar-wind Xe, as sampled at two different points in solar system space and time, are identical within experimental error.

Kim, J. S.↗

NASA NTRS2013

Compound Specific Hydrogen Isotope Composition of Type II and III Kerogen Extracted by Pyrolysis-GC-MS-IRMS

The use of Hydrogen (H) isotopes in understanding oil and gas resource plays is in its infancy. Described here is a technique for H isotope analysis of organic compounds pyrolyzed from oil and gas shale-derived kerogen. Application of this technique will progress our understanding. This work complements that of Pernia et al. (2013, this meeting) by providing a novel method for the H isotope analysis of specific compounds in the characterization of kerogen extracted by analytically diverse techniques. Hydrogen isotope analyses were carried out entirely "on-line" utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC Ultra interfaced with a Thermo MAT 253 IRMS. Also, a split of GC-separated products was sent to a DSQ II quadrupole MS to make semi-quantitative compositional measurements of the extracted compounds. Kerogen samples from five different basins (type II and III) were dehydrated (heated to 80 C overnight in vacuum) and analyzed for their H isotope compositions by Pyrolysis-GC-MS-TC-IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C) which quantitatively forms H2, following a modified method of Burgoyne and Hayes, (1998, Anal. Chem., 70, 5136-5141). Samples ranging from approximately 0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. Compounds were separated on a Poraplot Q GC column. Hydrogen isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight compounds. Water (H2O) average deltaD = -215.2 (V-SMOW), ranging from -271.8 for the Marcellus Shale to -51.9 for the Polish Shale. Higher molecular weight compounds like toluene (C7H8) have an average deltaD of -89.7 0/00, ranging from -156.0 for the Barnett Shale to -50.0 for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during formation within each basin. Since hydrocarbon H isotopes readily exchange with water, these data may provide some useful information on gas-water or oil-water interaction in resource plays, and further as a possible indicator of paleo-environmental conditions. Alternatively, our data may be an indication of H isotope exchange with water and/or acid during the kerogen isolation process. Either of these interpretations will prove useful when deciphering H isotope data derived from kerogen analysis. More experiments are planned to discern these two or other possible scenarios.

Socki, Richard A.↗

NASA NTRS1992

Evolution of isotopic signatures in lunar-regolith nitrogen - Noble gases and nitrogen in grain-size fractions from regolith breccia 79035

Ilmenite and pyroxene grain-size separates from 79035 were analyzed for trapped N; the ilmenite was also analyzed for trapped Xe. Ilmenite N contains two or more isotopically distinct trapped components differing in release temperature and therefore plausibly in implantation energy. The isotopically light, higher-temperature (higher-energy?) component has a delta N-15 value equal to -180 percent, significantly above the minimum value observed in bulk 79035, suggesting that parts of 79035 were exposed on the lunar surface earlier than the ilmenite. Using trapped Ar-40/Ar-36 and cosmogenic Ne-21 (Benkert, 1989) a compaction age of about 1 Ga was derived for the ilmenite. This implies a considerably more recent exposure than previously thought, and suggests that the long-term change in delta N-15 of regolith N was more rapid than generally believed. Comparison of these results with those for black/orange glass from 74001/74002 (compaction age 3.7 Ga; delta N-15 in the range -36 to +18 percent (Kerridge et al., 1991) indicates that the long-term trend may have followed a complex evolutionary path. Data for 79035 pyroxenes are consistent with the ilmenite compaction age but suggest a more complex exposure history.

Kerridge, J. F.↗

NASA NTRS1976

Petrography of isotopically-dated clasts in the Kapoeta howardite and petrologic constraints on the evolution of its parent body

Results are presented for petrographic and electron microprobe studies of the isotopically dated A, B, C, and rho basaltic rock fragments separated from the howardite Kapoeta. Other lithic clasts and numerous mineral fragments in thin sections of Kapoeta are investigated in order to outline the range in lithology and chemistry of the source materials from which the Kapoeta meteorite is derived. The data obtained are compared to those from other meteorite and lunar samples, with particular reference to the observational consequences for the evolution of the Kapoeta parent body. A major conclusion is that there is no clearcut evidence for young magmatism on the Kapoeta parent body. The observations preclude the interpretation that the Kapoeta is a simple mixture of eucrites and diogenites. In contrast to the moon, a source of anorthositic rocks does not appear to have been present on the Kapoeta parent body which involved chiefly pyroxene. The FeO-MnO relationships suggest that the source of the materials in the Kapoeta parent planet are fundamentally related.

Dymek, R. F.↗

NASA NTRS1976

Noble gases in 60009-60010 drive tube samples - Trapped gases and irradiation history

Concentrations and isotopic composition of noble gases are reported for grain size separates: nine soils from the 60010-60009 double drive tube, two soils from the 60007 drill core section, and surface soil 65501. Data are reported on concentrations of solar wind gases, surface-correlated gases (involving solar wind and lunar atmosphere), surface maturity indices, cosmogenic gases, possible soil mixing, and irradiation by cosmic rays. Good correlation is found between solar wind gases in 60009 soils and such surface maturity indices as petrographic agglutinates, magnetic soil fraction, and fine-grained iron. Cosmogenic He-3, Ne-21, Ar-38, Kr-80, and Xe-126 all display close correlations in the drive tube soils.

Bogard, D. D.↗

NASA NTRS1984

Tests of the lunar hypothesis

The concept that the Moon was fissioned from the Earth after core separation is the most readily testable hypothesis of lunar origin, since direct comparisons of lunar and terrestrial compositions can be made. Differences found in such comparisons introduce so many ad hoc adjustments to the fission hypothesis that it becomes untestable. Further constraints may be obtained from attempting to date the volatile-refractory element fractionation. The combination of chemical and isotopic problems suggests that the fission hypothesis is no longer viable, and separate terrestrial and lunar accretion from a population of fractionated precursor planetesimals provides a more reasonable explanation.

Taylor, S. R.↗

NASA NTRS1990

Noble gases in the howardites Bholghati and Kapoeta

Analyses of noble gases in whole rock samples of the howardites Bholghati and Kapoeta and grain-size separates of Kapoeta yield evidence for excesses of the Xe isotopes Xe-129 , Xe-131, Xe-132, Xe-134, and Xe-136 in a low-temperture component, similar to lunar excess fission Xe. Such a component may be able to provide chronometric information if the relative abundances of radioactive progenitors (I-129, Pu-244, and U-238) can be determined, but the isotopic spectra obtained are not sufficiently precise to do so. Eucritic clast BH-5 in Bholghati contains Xe produced in situ by the decay of Pu-244. Calculated fission Xe retention ages are 30-70 Ma after the formation of the solar system, consistent with the apparent presence of Sm-146 decay products. Both the clast and the matrix of Bholghati have K-Ar ages of about 2 Ga, suggesting a common thermal event at least that recently.

Swindle, T. D.↗

NASA NTRS2014

Ar-Ar Analysis of Chelyabinsk: Evidence for a Recent Impact

The Chelyabinsk meteorite is an LL5 ordinary chondrite that fell as a spectacular fireball on February 15th, 2013, over the Ural region in Russia. The meteoroid exploded at an altitude of 25-30 km, producing shockwaves that broke windowpanes in Chelyabinsk and surrounding areas, injuring some 1500 people. Analyses of the samples show that the meteorite underwent moderate shock metamorphism (stage S4; 25-35 GPa) [1]. Most of the samples have a fusion crust ranging from ~0.1-1mm thick, and roughly a third of the samples were composed of a dark fine-grained impact melt with chondrule fragments which were targeted for chronometry. A Pb-Pb age obtained by [2] of a shock-darkened and potentially melted sample of Chelyabinsk is reported as 4538.3 +/- 2.1 Ma, while a U-Pb study [3] gave an upper concordia intercept of 4454 +/- 67 Ma and a lower intercept of 585 +/- 390. Galimov et al. 2013 [1] suggest the Sm-Nd system records a recent impact event [~290 Ma] that may represent separation from the parent body, while the Rb-Sr isotopic system is disturbed and does not give any definitive isochron. In order to better understand its history, we have performed 40Ar-39Ar analysis on multiple splits of two Chelyabinsk samples; clast- rich MB020f,2 and melt-rich MB020f,5. The term "clast-rich" lithology is meant to indicate a mechanical mixture of highly shock-darkened and less shocked components, both with some shock melt veining.

Beard, S. P.↗

NASA NTRS2014

Distribution of Amino Acids in Lunar Regolith

One of the most eagerly studied questions upon initial return of lunar samples was whether significant amounts of organic compounds, including amino acids, were present. Analyses during the 1970s produced only tentative and inconclusive identifications of indigenous amino acids. Those analyses were hampered by analytical difficulties including relative insensitivity to certain compounds, the inability to separate chiral enantiomers, and the lack of compound-specific isotopic measurements, which made it impossible to determine whether the detected amino acids were indigenous to the lunar samples or the results of contamination. Numerous advances have been made in instrumentation and methodology for amino acid characterization in extraterrestrial samples in the intervening years, yet the origin of amino acids in lunar regolith samples has been revisited only once for a single lunar sample, (3) and remains unclear. Here, we present initial data from the analyses of amino acid abundances in 12 lunar regolith samples. We discuss these abundances in the context of four potential amino acid sources: (1) terrestrial biological contamination; (2) contamination from lunar module (LM) exhaust; (3) derivation from solar windimplanted precursors; and (4) exogenous delivery from meteorites.

Elsila, J. E.↗