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The composition of heavy ions in solar energetic particle events

Recent advances in determining the elemental, charge state, and isotopic composition of or approximate to 1 to or approximate to 20 MeV per nucleon ions in solar energetic particle (SEP) events and outline our current understanding of the nature of solar and interplanetary processes which may explain the observations. Average values of relative abundances measured in a large number of SEP events were found to be roughly energy independent in the approx. 1 to approx. 20 MeV per nucleon range, and showed a systematic deviation from photospheric abundances which seems to be organized in terms of the first ionization potential of the ion. Direct measurements of the charge states of SEPs revealed the surprisingly common presence of energetic He(+) along with heavy ion with typically coronal ionization states. High resolution measurements of isotopic abundance ratios in a small number of SEP events showed these to be consistent with the universal composition except for the puzzling overabundance of the SEP(22)Ne/(20)Ne relative to this isotopes ratio in the solar wind. The broad spectrum of observed elemental abundance variations, which in their extreme result in composition anomalies characteristic of (3)He rich, heavy ion rich and carbon poor SEP events, along with direct measurements of the ionization states of SEPs provided essential information on the physical characteristics of, and conditions in the source regions, as well as important constraints to possible models for SEP production.

Fan, C. Y.↗

The composition of heavy ions in solar energetic particle events

Recent advances in determining the elemental, charge state, and isotopic composition of or approximate to 1 to or approximate to 20 MeV per nucleon ions in solar energetic particle (SEP) events and outline our current understanding of the nature of solar and interplanetary processes which may explain the observations. Average values of relative abundances measured in a large number of SEP events were found to be roughly energy independent in the approx. 1 to approx. 20 MeV per nucleon range, and showed a systematic deviation from photospheric abundances which seems to be organized in terms of the first ionization potential of the ion. Direct measurements of the charge states of SEPs revealed the surprisingly common presence of energetic He(+) along with heavy ion with typically coronal ionization states. High resolution measurements of isotopic abundance ratios in a small number of SEP events showed these to be consistent with the universal composition except for the puzzling overabundance of the SEP(22)Ne/(20)Ne relative to this isotopes ratio in the solar wind. The broad spectrum of observed elemental abundance variations, which in their extreme result in composition anomalies characteristic of (3)He rich, heavy ion rich and carbon poor SEP events, along with direct measurements of the ionization states of SEPs provided essential information on the physical characteristics of, and conditions in the source regions, as well as important constraints to possible models for SEP production. Previously announced in STAR as N83-20886

Fan, C. Y.↗

Chemical abundance of comets

Observations of NH2, (OI) and molecular ion spectra in comets represent virtually all of the volatile fraction of a comet nucleus. Their study leads to the N2, NH3, H2O, CO2, CO content of the nucleus, and thus to important constraints on models of comet formation and chemical processing in the primitive solar nebula. The observations of Comet Halley provide the opportunity for the first comprehensive determination of the abundances in a comet nucleus. The carbon isotope abundance ratio 12 C/13 C = 65 plus or minus 8 has been determined for Comet Halley from resolved rotational line structure in the CN B-X (0,0) band. The ratio is approximately 30 pct lower than the solar system value, 89, indicating either an enhancement of 13CN or a depletion of 12CN in the comet. Scenarios consistent with the observed carbon isotope ratio are: (1) formation of the comet at the periphery of the solar nebula in a fractionation-enriched 13CN region, or hidden from 12CN enrichment sources, and (2) capture of an interestellar comet. Long-slit charge coupled device (CCD) spectra obtained at the time of the spacecraft encounter of Comet Halley have also been analyzed. Scale lengths, production rates and column densities of CH, CN, C2 and NH2 were determined.

Wyckoff, Susan↗

The isotropic condition of energetic particles emitted from a large solar flare

Isotope abundance ratios for 5 to 50 MeV/nuc nuclei from a large solar flare were measured. The measurements were made by the heavy isotope spectrometer telescope (HIST) on the ISEE-3 satellite orbiting the Sun near an Earth-Sun liberation point approximately one million miles sunward of the Earth. Finite values for the isotope abundance ratios C-13/C-12, N-15/N-14, O-18/O-16, Ne-22/Ne-20, Mg-25/Mg-24, and Mg-26/Mg-24, and upper limits for the isotope abundance ratios He-3/He-4, C-14/C-12, O-17/O-16 and Ne-21/Ne-20 were reported. Element abundances and spectra were measured to compare the flare with other reported flares. The flare is a typical large flare with low Fe/O abundance or = to 0.1). For C-13/C-12, N-15/N-14, O-18/O-16, Mg-25/Mg-24 and Mg-26/Mg-24 isotope abundance ratios agree with the solar system abundance ratios. Measurement for Ne-22/Ne-20 agree with the isotopic composition of the meteoritic component neon-A.

Spalding, J.↗

In-Lab Rapid Analytical Detection of Lunar Volatiles By Universal Gas Analyzer With Comparison to GC-MS System

Introduction: The curation of permanently shadowed regions (PSRs) [1] on the lunar surface is centered around studies based upon the observed volatiles from the LCROSS mission [2]. The rapid detection of important volatile gases and vapors present in planetary bodies and Astromaterials by a standalone analytical device is an area of intense research interest in our group and Planetary Exploration & Astromaterials Research Laboratory (PEARL) facility and this work is relevant to the future preparation of viable lunar simulants for testing curation efforts down the road. The groundbreaking results obtained from the LCROSS Mission [2] open the requirements for the direct detection of volatiles present in regolith materials collected from the lunar surface. The mass spectrometry of volatile chemicals is a general technique that utilizes a set of instruments that creates charged ions from a gaseous chemical species and measures the intensities vs. mass-to-charge ratio (m/z) [3]. In this context, we discuss in-lab experimental results and procedures for rapid qualitative analysis of main LCROSS volatiles (water, H2S, NH3, CO2, and CH3OH) by a Universal Gas Analyzer (UGA) instrument. Additionally, the instrument performance was evaluated by measuring the isotopic abundance ratio of atmospheric Ar-40 to Ar-36 present in room air since, argon is a relevant gas in planetary studies as it can provide an insight and reference point to isotope studies [4]. Additional, cross comparisons were attempted and made between the two instruments to develop a robust analytical technique by comparing mass spectral data for H2S headspace samples with a Trace-1310/ ISQ 7000 (ThermoFisher Scientific.) GC-MS system. Background: The benchtop UGA System is equipped with an SRS UGA 300 quadrupole mass spectrometer designed and built by Stanford Research Systems [5]. This system can be configured for several types of gaseous chemical analysis. The inlet line continuously samples gases at low flow rates (several milliliters per minute) through a capillary limiting the intake pressure making the instrument ideal for online analysis of select gases and/or room atmosphere. Moreover, in our current UGA system, a change in composition at the inlet can be detected in about 200 milliseconds and a complete spectrum is acquired (for a range of 1-100 amu) in under 45 sec with masses measured at rates up to 25 msec per point [5]. This system provides a quick upstream analytical data that we can then compare to results obtained by our GC-MS system. Sample Preparation: Small volume (2-4 mL) of analyte sample was taken in a 10 mL glass vial and sealed with a crimped cap and purged with pure Ar or N2 gas to displace air from the top. The headspace sample was scanned by the UGA instrument at analog, histogram, and pressure vs. time modes. The isotopic abundance ratio for 40Ar-to-36Ar was estimated by measuring partial pressure vs. time scans and setting the mass at 40 and 36 respectively. Results and Discussions: In this work, we have investigated the applicability of the UGA system by qualitative analysis of a series of LCROSS volatiles measured individually. Fig. 1 demonstrates a set of vertically offset spectra for the partial pressures measured as a function of mass-to-charge (m/z) ratios. The average acquisition time for each spectrum was less than a minute suggesting that the UGA system is ideal for quick analysis of geochemical volatiles. For the cross-comparison, we analyzed an H2S headspace sample by a Trace-1310/ISQ-7000 system and compared mass spectral data with previously measured UGA histogram scan data (Fig. 2). In both cases, major peak positions are the same, however, the intensities of fragment ions ([1H132S]+ and [32S]+) are higher for UGA suggesting that the fragment ionization process is stronger in UGA compared to that of GC-MS. To investigate how the integrated area under each chromatogram varies with the headspace sample volume, a set of five H2S headspace samples with increasing volumes was analyzed by the GC-MS system (Fig. 3, inset). A small volume (e.g., 200 to 1000 µL) of H2S/H2O vapor was withdrawn from a 20 mL stock sample vial containing ~5 mL of 0.4% H2S in water by a gas-tight syringe and added to another 20 mL vial filled with argon and analyzed by the GC-MS system. Finally, the UGA detector sensitivity was evaluated by calculating the atmospheric 40Ar-to-36Ar isotopic abundance ratio in room air by running a partial pressure vs. time scan with setting the atomic mass at 40, and 36. Fig. 4(a) shows a ~25 min duration “P vs. time” scan for 40Ar (plot for 36Ar is not shown). The partial pressure values (~100 points) were corrected by subtracting the corresponding background pressure value for 37Ar and utilized to calculate 40Ar-to-36Ar isotopic abundance ratios as shown by Fig. 4b. The average isotopic abundance ratio is ~306 with a 2*STDEV ~13. This abundance ratio is significantly close to the previously reported value of 298.56 [6] and the ratio obtained by our GC-MS system (303 for a UHP grade Ar sample). Conclusions: Our study strongly evidenced that the benchtop UGA system is a valuable analytical tool for the detection of major LCROSS volatiles. The rapid scanning capability, the inexpensiveness of the whole system, and impressive detection sensitivity prove its worthiness as an essential device for advanced geochemical applications. Moreover, cross comparisons with the GC-MS provide important bridges into advanced curatorial efforts into the future. References: [1] Bickel, V.T., et al. (2021) Nat Commun 12, 5607. [2] Colaprete, A., et al. (2010) Science, 330, 463-468. [3] Glavin, D. P. et al. (2012) 2012 IEEE Aerospace Conference, 1-11. [4] Willett, C. D., et al. (2022) Geochimica et Cosmochimica Acta 329, 119-134. [5] Operation Manual and Programming Reference. (2018) Universal gas Analyzers, Stanford Research Systems. [6] Lee, J. Y., et al. (2006) Geochimica et Cosmochimica Acta 70, 4507–4512. Notes: (4 figures are attached with text as shown by the attached file)

Curation↗

The production and escape of nitrogen atoms on Mars

The lack of agreement between our previously computed values and those measured by Viking of the N-15:N-14 isotope enhancement ratio has led us to reevaluate our model of the Martian ionosphere. In previous models, we were unable to reproduce the ion profiles measured by the RPA on Viking using electron temperatures that were higher that the ion temperatures. When we increased the electron temperatures to 2500-3000 K and with a zero flux upper boundary condition, the ion densities at high altitudes exceeded the measured values by a large factor. We found that we can better fit the observed profiles if we impose a loss process at the upper boundary of our model. If the horizontal fluxes of ions do not constitute a net loss of ions, then the escape of N due to dissociative recombination is also inhibited and better agreement with the measured isotope ratio is found. The production of escaping nitrogen atoms is closely related to the production of thermospheric odd nitrogen; therefore, the densities of NO measured by Viking provide a convenient check on our nitrogen escape model. Our standard model NO densities are less that the measured values by a factor of 2-3, as are those of previous models. We find that reasonable agreement can be obtained by assuming that the rate coefficient for loss of odd nitrogen in the reaction of N with NO is smaller at temperatures that prevail in the lower Martian thermosphere than the standard value, which applies to temperatures of 200-400 K. Other aspects of this investigation are presented.

Fox, J. L.↗

Rb-Sr, Sm-Nd, K-Ca, O, and H isotopic study of Cretaceous-Tertiary boundary sediments, Caravaca, Spain Evidence for an oceanic impact site

The results of isotopic and trace-element-abundance analyses of Ir-enriched Cretaceous-Tertiary-boundary clay sediments from Caravaca, Spain, and of adjacent carbonate and marl layers, are presented. Acetic-acid and HCl leachates and residues were analyzed by isotope dilution to determine K, Rb, Sr, Sm, and Nd concentrations and Sr-87/Sr-86 and Nd-143/Nd-144 ratios. The stable isotope ratios delta-D, delta-(C-13), and delta-(0-18) were also determined. The results are presented in tables and graphs and compared with published data on the Caravaca sediments and on samples from other locations. The boundary clay is found to be distinguished from the adjacent layers by its isotopic ratios and to be of mainly terrestrial, lithospheric (deeper than 3-km) origin. Although submarine-weathering effects are evident and difficult to quantify, the degree of variation in Ni, Ir, Sr, and REE concentrations is considered too large to be attributed to postdepositional processes alone. These findings are seen as evidence for the ocean impact of a large single asteroid producing a worldwide blanket of ejecta, a large injection of water vapor into the atmosphere, and perhaps a gigantic tsunami, at the end of the Cretaceous period.

Depaolo, D. J.↗

Stable Isotope Laser Spectrometer for Exploration of Mars

On Earth, measurements of the ratios of stable carbon isotopes have providet much information about geological and biological processes. For example, fractionation of carbon occur in biotic processes and the retention of a distinctive 2-4% contrast in C-13/C-12 between organic carbon and carbonates in rocks as old as 3.8 billion years constitutes some of the firmest evidence for the antiquity of life on the Earth. We have developed a prototype tunable diode laser spectrometer which demonstrates the feasibility of making accurate in situ isotopic ratio measurements on Mars. This miniaturized instrument, with an optical path length of 10 cm should be capable of making accurate C-13/C-12 and N-15/N-14 measurements. Gas samples for measurement are to be produced by pyrolysis using soil samples as small as 50 mg. Measurements of C-13/C-12, O-18/O-16 and N-15/N-14 have been made to a precision of better than 0.1%, and various other isotopes are feasible. This laser technique, which relies on the extremely narrow emission linewidth of tunable diode lasers (less than 0.001/ cm),has favorable features in comparison to mass spectrometry, the standard method of accurate isotopic ratio measurement. The miniature instrument could be ready to deploy c 2003 or other Mars lander missions.

Sauke, Todd B.↗

Martian stable isotopes: volatile evolution, climate change and exobiological implications

Measurements of the ratios of stable isotopes in the martian atmosphere and crust provide fundamental information about the evolution of the martian volatile and climate system. Current best estimates of the isotope ratios indicate that there has been substantial loss of gases to space and exchange of gases between the atmosphere and the crust throughout geologic time; exchange may have occurred through circulation of water in hydrothermal systems. Processes of volatile evolution and exchange will fractionate the isotopes in a manner that complicates the possible interpretation of isotopic data in terms of any fractionation that may have been caused by martian biota, and must be understood first. Key measurements are suggested that will enhance our understanding of the non-biological fractionation of the isotopes and of the evolution of the martian volatile system.

Review, Tutorial↗

Mass spectrometric study of the mercury isotopes in the Allende meteorite

Isotopic abundance ratios for mercury were determined by mass spectrometry in six samples of bulk material and in one sample of chondrules from the Allende meteorite. A primary purpose of the work was to attempt to verify the anomalous ratios reported for Hg-196/Hg-202 by neutron activation. Measurements were made on the mercury released at temperatures of 250, 450, 600 C, and in some cases, higher temperatures. The precision of the measurements was such that if an anomaly of the magnitude reported exists, it should have been seen. The isotopic abundance ratios for the other mercury isotopes were also measured. Within the errors of measurement these agreed with normal terrestrial values.

Nier, A. O.↗

Determination of the isotopic composition of atmospheric methane and its application in the Antarctic

A procedure for establishing the C-13/C-12 ratio and the C-14 abundance in the atmospheric methane is discussed. The method involves air sample collection, measurement of the methane mixing ratio by gas chromotography followed by quantitative conversion of the methane in the air samples to CO2 and H2O, and analysis of the resulting CO2 for the C-13/C-12 ratio by stable isotope ratio mass spectrometry and measurement of C-14 content by accelerator mass spectrometry. The carbon isotropic composition of methane in air collected at Baring Head, New Zealand, and in air collected on aircraft flights between New Zealand and Antarctica is determined by the method, and no gradient in the composition between Baring Head and the South Pole station is found. As the technique is refined, and more data is gathered, small seasonal and long-term variations in C-13 are expected to be resolved.

Lowe, David C.↗

Isotopes of titanium in cool stars

A program of stellar Ti isotopic-abundance determinations is described and related to changes that may have occurred in the Ti isotopic abundance ratios during the chemical evolution of the Galaxy, and to whether the abundance ratios are perturbed in the S and MS stars having atmospheres with enhanced abundances of s-process nuclei resulting from convective mixing after internal exposure to neutrons. High-resolution (0.07 A) Reticon spectra of portions of the TiO gamma (0,0), gamma (0,1), and delta (0,0) bands were the source material, and particular emphasis was placed on the definition of the continuum level. The isotopic abundance ratios are terrestrial in all of the sample, and errors in the (Ti-i)/(Ti-48) ratio are typically plus or minus 25% for the dwarfs and plus or minus 50% for the giants. The observations show that the magic nucleus Ti-50 is not enhanced in S and MS stars.

Clegg, R. E. S.↗

The C-12/C-13 ratio in stellar atmospheres. II - CN and CO in alpha Orionis

The isotopic abundance ratio C-12/C-13 for the M supergiant alpha Orionis is derived from photoelectric high-resolution scans of the CN 2-0 red system and high-resolution interferometric spectra of the CO second-overtone bands. The two molecules yield consistent results and the final value for the C-12/C-13 ratio is 7.0 plus or minus 1.5. Rationale is offered for the causes contributing to an earlier suggestion that C-12/C-13 ratios from CO and CN were in disagreement.

Lambert, D. L.↗

Identification of Martian Regolith Sulfur Components in Shergottites Using Sulfur K Xanes and Fe/S Ratios

Based on isotopic anomalies in Kr and Sm, Sr-isotopes, S-isotopes, XANES results on S-speciation, Fe/S ratios in sulfide immiscible melts [5], and major element correlations with S determined in impact glasses in EET79001 Lith A & Lith B and Tissint, we have provided very strong evidence for the occurrence of a Martian regolith component in some impact melt glasses in shergottites. Using REE measurements by LA-ICP-MS in shergottite impact glasses, Barrat and co-workers have recently reported conflicting conclusions about the occurrence of Martian regolith components: (a) Positive evidence was reported for a Tissint impact melt, but (b) Negative evidence for impact melt in EET79001 and another impact melt in Tissint. Here, we address some specific issues related to sulfur speciation and their relevance to identifying Martian regolith components in impact glasses in EET79001 and Tissint using sulfur K XANES and Fe/S ratios in sulfide immiscible melts. XANES and FE-SEM measurements in approx. 5 micron size individual sulfur blebs in EET79001 and Tissint glasses are carried out by us using sub-micron size beams, whereas Barrat and coworkers used approx. 90 micron size laser spots for LA- ICP-MS to determine REE abundances in bulk samples of the impact melt glasses. We contend that Martian regolith components in some shergottite impact glasses are present locally, and that studying impact melts in various shergottites can give evidence both for and against regolith components because of sample heterogeneity.

Sutton, S. R.↗

Observation of J = 1-0 emission from H/N-15/C

Emission from the J = 1-0 transition of H(N-15)C has been detected in the direction of DR21(OH). The transition frequency of 88,865.69 MHz was measured in the laboratory by microwave absorption spectroscopy. The computed N-15/C-13 isotopic abundance ratio of 1.01 for DR21(OH) is larger than those calculated from isotopes of HCN in other interstellar clouds, perhaps implying a localized enrichment in N-15 in DR21(OH).

Brown, R. D.↗

An investigation of techniques for the measurement and interpretation of cosmic ray isotopic abundances

An instrument, the Caltech High Energy Isotope Spectrometer Telescope was developed to measure isotopic abundances of cosmic ray nuclei by employing an energy loss - residual energy technique. A detailed analysis was made of the mass resolution capabilities of this instrument. A formalism, based on the leaky box model of cosmic ray propagation, was developed for obtaining isotopic abundance ratios at the cosmic ray sources from abundances measured in local interstellar space for elements having three or more stable isotopes, one of which is believed to be absent at the cosmic ray sources. It was shown that the dominant sources of uncertainty in the derived source ratios are uncorrelated errors in the fragmentation cross sections and statistical uncertainties in measuring local interstellar abundances. These results were applied to estimate the extent to which uncertainties must be reduced in order to distinguish between cosmic ray production in a solar-like environment and in various environments with greater neutron enrichments.

Wiedenbeck, M. E.↗

Lower limit to the interstellar C 12/C 13 ratio in the direction of 20 Tauri.

Results of photoelectric scanning of the spectrum of 20 Tau in the vicinity of 4232 A of interstellar CH(+). From the observed absence of the isotopically shifted line of super 13CH(+) it is deduced that the C 12/C 13 isotopic abundance ratio in this direction is greater than 33, and hence consistent with the terrestrial value.

Vanden Bout, P.↗