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Evidence in meteorites for an active early sun

High-sensitivity noble gas mass-spectrometric analyses of meteorite grains having solar flare heavy ion tracks show large enrichments of spallation-produced Ne-21 and Ar-38 when compared to nonirradiated grains from the same meteorite. The enhanced spallation effects in the irradiated grains are due to irradiation by energetic protons early in the history of the solar system, before compaction of the host meteorite. They require a proton fluence (E greater than 10 MeV) of 10 to the 16th to 10 to the 18th/cu cm. These results are best explained by solar flare irradiation in the early solar system with a proton flux several orders of magnitude higher than contemporary solar flares. The Ne isotopic structure suggests a harder energy spectrum than is characteristic of contemporary flares. These observations provide direct evidence for an active early (T Tauri) sun.

Caffee, M. W.

An intercomparison of aircraft instrumentation for tropospheric measurements of sulfur dioxide

As part of the NASA Tropospheric Chemistry Program, a series of field intercomparisons have been conducted to evaluate the state-of-the art for measuring key tropospheric species. One of the objectives of the third intercomparison campaign in this series, Chemical Instrumentation Test and Evaluation 3 (CITE 3), was to evaluate instrumentation for making reliable tropospheric aircraft measurements of sulfur dioxide, dimethyl sulfide, hydrogen sulfide, carbon disulfide, and carbonyl sulfide. This paper reports the results of the intercomparisons of five sulfur dioxide measurement methods ranging from filter techniques, in which samples collected in flight are returned to the laboratory for analyses (chemiluminescent or ion chromatographic), to near real-time, in-flight measurements via gas chromatographic, mass spectrometric, and chemiluminescent techniques. All techniques showed some tendency to track sizeable changes in ambient SO2 such as those associated with altitude changes. For SO2 mixing ratios in the range of 200 pptv to a few ppbv, agreement among the techniques varies from about 30% to several orders of magnitude, depending upon the pair of measurements intercompared. For SO2 mixing ratios less than 200 pptv, measurements from the techniques are uncorrelated. In general, observed differences in the measurement of standards do not account for the flight results. The CITE 3 results do not unambiguously identify one or more of the measurement techniques as providing valid or invalid SO2 measurements, but identify the range of 'potential' uncertainty in SO2 measurements reported by currently available instrumentation and as measured under realistic aircraft environments.

Gregory, Gerald L.

Precompaction irradiation effects: Particles from an early active sun?

Two recent studies have shown that solar flare irradiated grains from Murchison and Kapoeta have excess spallogenic Ne-21 compared to unirradiated grains, indicating large precompaction particle irradiation effects. The quantity of cosmogenic neon in these grains presents serious difficulties for either galactic cosmic ray or normal solar flare sources. In the first study it was suggested that the effect might be the result of exposure to an early active sun. The more recent experiment both confirms the earlier results and provides constraints on the characteristic energy spectrum on the irradiation. The first results were obtained from Murchison olivines and Kapoeta pyroxenes by mass spectrometric analysis of sets of grains selected on the basis of the presence or absence of solar flare particle tracks. In the second work plagioclase feldspar grains from Kapoeta were studied.

Caffee, M. W.

Size-dependent femtosecond proton transfer in protonated methanol clusters

Methanol clusters (CH 3 OH) n are prototypical hydrogen-bonded systems that bridge isolated molecules and bulk liquid methanol. Strong-field ionization of these clusters can trigger ultrafast charge migration, proton transfer, and isomerization; however, the onset timescales of these pathways remain largely unexplored despite extensive steady-state mass-spectrometric evidence for protonation and chemical rearrangement. Here we use femtosecond time-resolved strong-field ionization and disruptive probing to directly track the early-time dynamics of methanol clusters. Transient mass spectra yield size-dependent timescales for the formation of protonated clusters H + (CH 3 OH) n (n = 1–3) and an associated CHO˙ + radical cation. We find that both proton-transfer and subsequent stabilization become markedly faster with increasing cluster size. These measurements establish methanol clusters as a complementary benchmark to water for understanding ionization-initiated proton motion and chemical reorganization in hydrogen-bonded liquids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Tensioned metastable fluid detector sensing technology for multifarious-multiscale applications in the nuclear fuel cycle

The nuclear fuel cycle presents formidable 10 30+ multiscale challenges for high-efficiency spectroscopic sensing of alpha-neutron-fission radiation signatures amidst extreme gamma-beta radiation backgrounds at various stages of the cycle; it involves diverse arenas ranging from continuous/pulsed power production, security/safeguards, spent fuel, environmental remediation, and personnel health-dosimetry. This paper discusses the novel tensioned metastable fluid detector (TMFD) sensor technology. It discusses the results of studies demonstrating extreme (10 4 Sv/h) gamma-beta field blind high intrinsic efficiencies (80–100%) for neutron-alpha-fission radiation spectrometric detection. Example studies discussed in this paper include Neutron detection with spectroscopy; H*10 neutron radiation dosimetry upwards from ultra-low10 −2 µSv/h levels; Air and/or liquid-borne trace (10 –3 Bq/mL) quantity, 1 keV energy resolved alpha/fission spectroscopy for Rn/Po/U/Pu/Am environmental isotope assays at 106:1 (β:α) ratios; Directional-position enabled extended standoff tracking of neutron emitting (shielded/unshielded) special nuclear materials while stationary or moving at highway speeds; and, U.S. Department of Energy nuclear complex wide nuclear waste reprocessing, criticality safety, health physics, and environmental applications.

Alpha-fission-neutron spectrometry

Mass Spectrometric Determination of Site-Specific O -Acetylation in Rhamnogalacturonan I Oligomers

O-acetylation, a common modification in rhamnogalacturonan I (RG-I), is critical for various biological processes, including plant growth, stress responses, and pathogen defense. Precise determination of the degree and specific positions of acetylation is therefore essential. To date, nuclear magnetic resonance (NMR) and tandem mass spectrometry have been employed to identify O-acetyl positions in pectin oligosaccharides. Although NMR is effective, it requires pure, high-concentration samples. Tandem mass spectrometry (MS), which uses smaller sample amounts, faces challenges due to O-acetyl migration between monosaccharide positions. The multiple steps in pectin sample analysis can further promote O-acetyl migration, especially near free hydroxyl groups. Moreover, during tandem MS, O-acetyl groups may detach, complicating the accurate tracking. This study presents an approach to lock O-acetyl groups by introducing trideuteroacetyl and propionyl substituents onto free hydroxyls of RG-I or partially acetylated RG-I. By combining matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) MS and electrospray ionization (ESI) MS with MS/MS or tandem mass spectrometry (MSn), we devised a way to determine the monosaccharide sequence in the oligomer and the precise positions of O-acetyl groups in partially acetylated RG-I. This method enables the study of the regiospecificity of recombinant pectin O-acetyltransferases and can be applied to other oligosaccharides to determine acyl positions.

O-acetylation

Synthesis and characterization of isotopically barcoded nickel, molybdenum, and tungsten taggants for intentional nuclear forensics

Intentional nuclear forensics is a concept wherein the deliberate addition of benign and persistent material signatures to nuclear material can be used to reduce the time between the discovery of material outside of regulatory control and determination of its original provenance. One concept within intentional nuclear forensics involves the use of perturbed stable isotopes to generate unique isotope ratio “barcodes” to encode information (e.g., production batch, location, etc.) and track material throughout the nuclear fuel cycle. Synthesis of taggant species of nickel (Ni), molybdenum (Mo), and tungsten (W) was undertaken via a double-spike mechanism, wherein two highly enriched isotopes of interest per elemental taggant were mixed to form an enriched “double-spike” which was subsequently isotopically diluted with bulk material having a natural isotopic composition. Two taggant species perturbing isotopic ratios, alpha (α) and beta (β), for each of Ni, Mo, and W were synthesized. Independent measurements of double spikes and alpha and beta taggant species agreed within uncertainty and are clearly resolvable from natural compositions. High-precision analyses were independently performed by MC-ICP-MS at two U.S. National Laboratories, with consensus values and uncertainties calculated for all samples. Observed isotopic perturbations in the final taggant species measured on the order of hundreds to thousands of permille (‰) with respect to natural for isotope ratios of interest (e.g., 60 Ni/ 58 Ni, 100 Mo/ 98 Mo, 186 W/ 183 W). Discrepancies between modeled and measured isotopic compositions were observed and are largely attributed to imprecise vendor assay values for starting materials. Using measured starting material compositions as inputs for the mixing model improved the level of agreement between predicted and measured α and β taggant isotope ratios. Overall, characterization of all taggant species demonstrates that this “barcode” concept could have viability for use in nuclear forensics. Finally, it is expected that for any two-isotope mixing array dozens of isotopic barcodes could be encoded into a material system and subsequently resolved utilizing modern mass spectrometric methods.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P