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At least 55 records · Page 3

Development of microchannel plates in advanced wind-tunnel instrumentation

Microchannel plate (MCP) electron multiplier dynamic range has been increased 3 to 4 orders of magnitude at ambient temperatures, through enhanced input count rate capability and reduced background or 'dark' noise. The previous upper limit of roughly 10(exp 7) - 10(exp 8) cm(exp -2)s(exp -1) at ambient has been extended to levels approach 10(exp 10) cm(exp -2)s(exp -1) under continuous dc operation. The lower limit, previously set by an irreducible background component (approximately 0.6 cm(exp -2)s(exp -1)), has been lowered to the cosmic ray limit of .01 cm(exp -2)s(exp -1). The high end improvement was achieved by conductively cooling a very low resistance MCP by bonding it to a heat sink, while maintaining pulse-counting operation with multianode readouts. The low-end improvement was achieved by removing all radioisotopes from the MCP matrix glass. The detectors will benefit optical and mass spectrometry, flow visualization, plasma diagnostics, magnetometry, and other high signal flux applications. Very low MCP background noise will benefit X-ray and UV astronomy, medical imaging, trace isotope mass spectrometry, and other applications where the signal flux is often extremely low.

Feller, W. Bruce↗

Mare basalt genesis - Modeling trace elements and isotopic ratios

Various types of mare basalt data have been synthesized, leading to the production of an internally consistent model of the mare basalt source region and mare basalt genesis. The model accounts for the mineralogical, major oxide, compatible siderophile trace element, incompatible trace element, and isotopic characteristics of most of the mare basalt units and of all the pyroclastic glass units for which reliable data are available. Initial tests of the model show that it also reproduces the mineralogy and incompatible trace element characteristics of the complementary highland anorthosite suite of rocks and, in a general way, those of the lunar granite suite of rocks.

Binder, A. B.↗

A Rb-Sr and Sm-Nd Isotope Geochronology and Trace Element Study of Lunar Meteorite LaPaz Icefield 02205

Rubidium-strontium and samarium-neodymium isotopes of lunar meteorite LaPaz Icefield (LAP) 02205 are consistent with derivation of the parent magma from a source region similar to that which produced the Apollo 12 low-Ti olivine basalts followed by mixing of the magma with small amounts (1 to 2 wt%) of trace element-enriched material similar to lunar KREEP-rich sample SaU 169. The crystallization age of LAP 02205 is most precisely dated by an internal Rb-Sr isochron of 2991+/-14 Ma, with an initial Sr-87/Sr-88 at the time of crystallization of 0.699836+/-0.000010. Leachable REE-rich phosphate phases of LAP 02205 do not plot on a Sm-Nd mineral isochron, indicating contamination or open system behavior of the phosphates. Excluding anomalous phases from the calculation of a Sm-Nd isochron yields a crystallization age of 2992+/-85 (initial Epsilon Nd-143 = +2.9+/-0.8) that is within error of the Rb-Sr age, and in agreement with other independent age determinations for LAP 02205 from Ar-Ar and U-Pb methods. The calculated Sm-147/Nd-144 source ratios for LAP 02205, various Apollo 12 and 15 basalts, and samples with strong affinities to KREEP (SaU 169, NWA 773, 15386) are uncorrelated with their crystallization ages. This finding does not support the involvement of a common KREEP component as a heat source for lunar melting events that occurred after crystallization of the lunar magma ocean.

Rankenburg, K.↗

Trace Element and Isotopic Evidence for Bennu's Primitive Provenance

The delivery of material from asteroid (101955) Bennu by NASA’s OSIRIS-REx mission provides the opportunity to investigate some of the most pristine material from the early Solar System [1]. Our team at Lawrence LivermoreNational Laboratory (LLNL) utilized the equivalent of 5.0 mg from Bennu sampleOREX-803015-100 to quantify the major and trace element contents and investigate major element isotopics (Ca, Ti, Cr, Fe, and Ni). Our 5.0 mg aliquot ofOREX-803015-100 was a subsample of dissolved homogenized material representing 20.66 mg [2]. A separate 5.0 mg aliquot was sent to ETH Zürich and is discussed in a companion abstract [3]. Before any chemical separation on our 5.0 mg aliquot, the equivalent of 0.5 mg was removed and analyzed for elemental abundances at LLNL using a ThermoScientific Element XR. Our data agree exceptionally well with those reported by[2], showing that Bennu is primitive and compositionally similar to CI chondrites, Ryugu [4], and the solar photosphere [5]. The remaining ~4.5 mg underwent purification procedures to chemically isolate and purify Ca, Ti, Cr, Fe, and Ni from one another and the sample matrix. Their isotopic compositions were measured on either the Triton TIMS (Ca) at JohnsonSpace Center in Houston, Neoma MC-ICPMS (Ti, Cr) at LLNL, or the Neptune MC-ICPMS (Fe, Ni) at LLNL. Results from the Ca, Ti, Cr, Fe, and Ni isotopic compositions suggest that Bennu is closely related to CI chondrites—consistent with conclusions from elemental composition [2] and oxygen isotopics [6]reported for Bennu. The major element isotope compositions that we will present demonstrate that Bennu likely formed in a similar region of the SolarSystem as CI chondrites and potentially at a similar time of Solar System evolution.

Greg Brennecka↗

Trace element and isotope studies in oxide/phosphate/silicate inclusions of iron meteorites

Under the above grant research was funded in the following areas: 1. Pallasites: Rare earth element measurements in phosphates to determine if all pallasites fit into only two trace element groups. This work has been completed. 2. HIAB irons: To complete work on the only known silicate inclusion in a IIIAB iron meteorite. This work has been completed. 3. IIIAB irons: To continue the search for Cr-53 excesses in IIIAB iron meteorite phosphates. A part of this work has been completed 4. IIIAB irons: To complete the identification of the phosphate minerals in IIIAB iron meteorites and try to determine the phase relations and chemical history of trace element distributions during the core formation process. Work on this has been largely completed and preliminary results have been reported. The final work is being assessed prior to preparation of a manuscript for publication. 5. IIE irons: To complete work on the unique silicate assemblage in the IIE iron meteorite. Work on this was completed and a paper published. 6. Ungrouped irons: A partially devitrified silicate glass inclusion has been found in the ungrouped iron meteorite. Preliminary work on this has been reported. All the work on this has been now completed and a manuscript has been prepared and submitted for publication.

Olsen, Edward J.↗

Isotopic, optical, and trace element properties of large single SiC grains from the Murchison meteorite

Ion probe mass spectrometry is used to analyze 41 large SiC grains from the Murchison CM2 chondrite, ranging up to 15 x 26 microns, for the isotopic compositions of C, N, Mg, and Si, and the concentrations of Al, Ti, V, Fe, Zr, and Ba. The majority were found to have large isotopic anomalies. Only two grains, characterized by extremely heavy carbon, give evidence for fossil Mg-26. On the basis of C and Si isotopic composition, 29 of the grains fall into three compact clusters, presumably from three discrete sources. The clustering of coarse-grained SiC stands in sharp contrast to the quasi-continuous distribution of finer-grained SiC and suggests that the top 0.1 percent of the mass distribution is a distinct population. The C and N isotopic compositions of the anomalous grains are not very diagnostic, being consistent with H-burning in the CNO cycle. The Si-isotopic compositions qualitatively show the signature of neutron capture in He-burning shells of highly evolved stars.

Virag, Alois↗

Rn-222 tracing and stable isotope measurements of biogenic gas fluxes from methane saturated sediments

Transport of reduced biogenic gases from anoxic sediments and soils to the atmosphere can be quantitatively studied through measurement of radon-222/radium-226 disequilibrium. In previous work, seasonal variations in biogenic gas transport mechanisms, net fluxes and overall composition were documented. Now presented are direct field measurements of radon-222 activity in gases exiting organic rich sediments which show their usefulness for tracing of the stripping of dissolved biogenic gases from within the sediment column and transport via bubble ebullition. Methane is depleted in deuterium during the summer as compared with winter months and is in general lighter than in most marine sediments signaling the probable importance of acetate as an important precursor molecule. The significant seasonal isotopic variations observed illustrate the importance of understanding mechanisms and rates of biogenic gas production in order to interpret observed tropospheric isotopic data.

Martens, Christopher S.↗

Tracing Carbon Metabolism with Stable Isotope Metabolomics Reveals the Legacy of Diverse Carbon Sources in Soil

Tracking the metabolic activity of whole soil communities can improve our understanding of the transformation and fate of carbon in soils. For this work, we used stable isotope metabolomics to trace 13 C from nine labeled carbon sources into the water-soluble metabolite pool of an agricultural soil over time. Soil was amended with a mixture of all nine sources, with one source isotopically labeled in each treatment. We compared changes in the 13 C enrichment of metabolites with respect to carbon source and time over a 48-day incubation and contrasted differences between soluble sources (glucose, xylose, amino acids, etc.) and insoluble sources (cellulose and palmitic acid). Whole soil metabolite profiles varied singularly by time, while the composition of 13 C-labeled metabolites differed primarily by carbon source (R 2 = 0.68) rather than time (R 2 = 0.07), with source-specific differences persisting throughout incubations. The 13 C labeling of metabolites from insoluble carbon sources occurred slower than that from soluble sources but yielded a higher average atom percent (atom%) 13 C in metabolite markers of biomass (amino acids and nucleic acids). The 13 C enrichment of metabolite markers of biomass stabilized between 5 and 15 atom% 13 C by the end of incubations. Temporal patterns in the 13 C enrichment of tricarboxylic acid cycle intermediates, nucleobases (uracil and thymine), and by-products of DNA salvage (allantoin) closely tracked microbial activity. Our results demonstrate that metabolite production in soils is driven by the carbon source supplied to the community and that the fate of carbon in metabolites do not generally converge over time as a result of ongoing microbial processing and recycling.

59 BASIC BIOLOGICAL SCIENCES↗

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

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.

Zare, Richard N.↗

Petrogenesis of Challis volcanics from central and southwestern Idaho - Trace element and Pb isotopic evidence

An analysis of the lava flows and ash-flow tuffs in Idaho is conducted to determine the composition of the volcanics in terms of major and trace elements and Pb isotopic substances. Al2O3 is found to be low, MgO content is high, and the concentration of K2O is higher or equal to that of Na2O with respect to the lavas of mafic to intermediate composition. Trace elements and element ratios are compatible with the crustal component, and the Pb isotopic compositions suggest a lack of assimilation during crystallization. The evidence does not support the notion of a magma system related to subduction, and the data regarding Pb isotopes and trace elements point to a connection with the lithosphere. A model is proposed for the Challis volcanics in which they resulted from completely melting within the lithosphere and then extending during the late Mesozoic and early Cenozoic compression.

Norman, Marc D.↗

Trace elements and their isotopes in streams and rivers

The occurrence and speciation of trace elements in streams and rivers are controlled by interconnected hydrogeological, biogeochemical, and anthropogenic factors that include rock weathering, climate, vegetation, and land use within the watershed. This chapter provides a broad overview of trace element abundance, speciation, and mobility in streams and rivers, including an assessment of how trace elements are partitioned into dissolved, colloidal, and particulate phases. We also discuss how trace elements are mobilized into stream networks and transformed during transport. Select isotopic systems are reviewed to provide examples of how isotopic analyses can be used to understand geochemical and anthropogenic processes.

Herndon, Elizabeth [ORNL] (ORCID:0000000291945493)↗

Atmospheric Trace Gas Abundances and Stable Isotope Ratios via IR-LIF

We propose to develop new technologies with support provided by PIDDP that will enable the in situ measurements of abundances and stable isotope ratios in important radiatively and biogenically active gases such as carbon dioxide, carbon monoxide, water, methane, nitrous oxide, and hydrogen sulfide to very high precision (0.1 per mil or better for the isotopic ratios, for example). Such measurements, impossible at present, could provide pivotal new constraints on the global (bio)geochemical budgets of these critical species, and could also be used to examine the dynamics of atmospheric transport on Mars, Titan, and other solar system bodies. We believe the combination of solid state light sources with imaging of the IR laser induced fluorescence (IR-LIF) via newly available detector arrays will make such in situ measurements possible for the first time. Even under ambient terrestrial conditions, the LIF yield from vibrational excitation of species such as water and carbon dioxide should produce emission measures well in excess of ten billion photons/sec from samples volumes of order 1 c.c. These count rates can, in principle, yield detection limits into the sub-ppt range that are required for the in situ isotopic study of atmospheric trace gases. While promising, such technologies are relatively immature, but developing rapidly, and there are a great many uncertainties regarding their applicability to in situ IR-LIF planetary studies. We therefore feel PIDDP support will be critical to developing these new tools, and propose a three-year program to combine microchip near-IR lasers with low background detection axes and state-of-the-art HgCdTe detectors developed for astronomical spectroscopy to investigate the sensitivity of IR-LIF under realistic planetary conditions, to optimize the optical pumping and filtering schemes for important species, and to apply the spectrometer to the non-destructive measurement of stable isotopes in a variety of test samples. These studies form the necessary precursors to the development of compact, lightweight stable isotope/trace gas sensors for future planetary missions.

Blake, Geoffrey A.↗

Development of Chemical Procedures for Isotope Harvesting: Separation of Trace Hafnium from Tungsten

The separation of trace hafnium from bulk tungsten alloys is of interest for isotope harvesting at the National Superconducting Cyclotron Laboratory and the Facility for Rare Ion Beams because 172 Hf, the parent of 172 Lu, accumulates in tungsten alloy beam blockers at these facilities. In this work, a procedure for the separation of trace hafnium from a bulk tungsten alloy (454 g) was established using tracer isotopes ( 175 Hf, 88 Zr, 173 Lu, and 88 Y). Here, the procedure employed dissolution in an HF–HNO 3 solution followed by a calcium fluoride precipitation, and then extraction chromatography was used for more selective separation steps. Two stages of column separations using LN resin (HDEHP based) and TRU resin (CMPO based) were performed. Gamma-ray spectroscopy and mass spectrometry were used to analyze the final hafnium sample and follow the steps in the chemical processing. Furthermore, the final recovery of hafnium was high (90 ± 8)%, and the mass of tungsten and other transition metals was reduced to near background levels (as determined by ICP-MS of the blank acid solutions). Zirconium follows hafnium quantitatively in this procedure; there was no detectable 173 Lu in the final hafnium sample.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Isotopic Fractionation and Kinetic Isotope Effects of a Purified Bacterial Nitric Oxide Reductase (NOR)

Nitrous oxide (N 2 O) is a serious concern due to its role in global warming and ozone destruction. Agricultural practices account for ~80% of all anthropogenic N 2 O produced in the US, due in large part to the stimulation of microbial denitrification. Stable isotopes are uniquely suited to examine both microbial N 2 O sources and the mechanism of N 2 O biosynthesis through the use of 2 Site Preference (δ 15 N SP ; the difference in δ 15 N between the central and outer N atoms in N 2 O) and kinetic isotope effects (KIEs), respectively. Using trace gas isotope ratio mass spectrometry (TG-IRMS), we determined the δ 15 N, δ 15 N α , δ 15 N β , and δ 18 O of N 2 O produced by a purified cytochrome c nitric oxide reductase (cNOR) from Paracoccus denitrificans. We also calculated δ 15 N SP , the KIEs, and associated isotopic enrichment factors (ε) for N bulk , N α , and N β . A normal isotope effect was observed for bulk 15 N, with a KIE value of 1.0086 ± 0.0009 (ε = -8.6 ± 0.9‰). The isotope effects for both 15 N α and 15 N β were also normal, with position-specific KIEs of 1.0072 ± 0.0010 (ε = -7.2 ± 1.0‰) and 1.0100 ± 0.0010 (ε = -9.9 ± 1.0‰), respectively, and δ 15 N SP values ranged from 0.5 to 8.7‰ with no significant trend as the reaction proceeded. Values of δ 18 O increased with N 2 O production (slope of δ 18 O against [-flnf/(1-f)] = -19.9 ± 1.9‰). We present implications for the mechanism of N 2 O production from cNOR based on our data.

Rivett, Elise D. [Michigan State Univ., East Lansi↗

A new highly enriched 233 U reference material for improved simultaneous determination of uranium amount and isotope amount ratios in trace level samples

A highly-enriched 233 U reference material (>0.99987 n( 233 U)/n(U)) has been prepared and characterized for use as an isotope dilution mass spectrometry spike. An ion exchange separation was performed on 1 g of high purity 233 U to further reduce trace amounts of contaminant Pu in the material. The purified 233 U was then prepared as a master solution which was analyzed for molality of uranium by modified Davies and Gray titration. A portion of the master solution was quantitatively diluted and dispensed for reference material units. Selected units were analyzed for verification of uranium amount and to characterize uranium isotope amount ratios by multi-collector inductively couple plasma mass spectrometry. Furthermore, modelling of spike-corrected isotopic data show that the new spike will enable simultaneous measurements of uranium amount and isotope amount ratios with resulting uncertainties that are substantially less sensitive to over spiking than widely used 233 U certified reference materials.

233U↗

An Evolutionary System of Mineralogy. Part I: Stellar Mineralogy (>13 to 4.6 Ga)

Minerals preserve records of the physical, chemical, and biological histories of their origins and subsequent alteration, and thus provide a vivid narrative of the evolution of Earth and other worlds through billions of years of cosmic history. Mineral properties, including trace and minor elements, ratios of isotopes, solid and fluid inclusions, external morphologies, and other idiosyncratic attributes, represent information that points to specific modes of formation and subsequent environmental histories—information essential to understanding the co-evolving geosphere and biosphere. This perspective suggests an opportunity to amplify the existing system of mineral classification, by which minerals are defined solely on idealized end-member chemical compositions and crystal structures. Here we present the first in a series of contributions to explore a complementary evolutionary system of mineralogy—a classification scheme that links mineral species to their paragenetic modes. The earliest stage of mineral evolution commenced with the appearance of the first crystals in the universe at >13 Ga and continues today in the expanding, cooling atmospheres of countless evolved stars, which host the high-temperature (T > 1000 K), low-pressure (P < 10-2 atm) condensation of refractory minerals and amorphous phases. Most stardust is thought to originate in three distinct processes in carbon- and/or oxygen-rich mineral-forming stars: (1) condensation in the cooling, expanding atmospheres of asymptotic giant branch stars; (2) during the catastrophic explosions of supernovae, most commonly core collapse (Type II) supernovae; and (3) classical novae explosions, the consequence of runaway fusion reactions at the surface of a binary white dwarf star. Each stellar environment imparts distinctive isotopic and trace element signatures to the micro- and nanoscale stardust grains that are recovered from meteorites and micrometeorites collected on Earth’s surface, by atmospheric sampling, and from asteroids and comets. Although our understanding of the diverse mineral-forming environments of stars is as yet incomplete, we present a preliminary catalog of 41 distinct natural kinds of stellar minerals, representing 22 official International Mineralogical Association (IMA) mineral species, as well as 2 as yet unapproved crystalline phases and 3 kinds of non-crystalline condensed phases not codified by the IMA.

Robert M. Hazen↗