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At least 325 records · Page 18

Sulfur and Hydrogen Isotope Anomalies in Meteorite Sulfonic Acids

Intramolecular carbon, hydrogen, and sulfur isotope ratios were measured on a homologous series of organic sulfonic acids discovered in the Murchison meteorite. Mass-independent sulfur isotope fractionations were observed along with high deuterium/hydrogen ratios. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low-temperature environment that is consistent with that of interstellar clouds. Sulfur-33 enrichments observed in methanesulfonic acid could have resulted from gas-phase ultraviolet irradiation of a precursor, carbon disulfide. The source of the sulfonic acid precursors may have been the reactive interstellar molecule carbon monosulfide.

Cooper, George W.↗

Remote isotope detection and quantification using femtosecond filament-laser ablation molecular isotopic spectrometry

We demonstrate the detection and quantification of isotopes from solid samples remotely at a distance of 36 m. This was accomplished through the combination of femtosecond filaments and laser ablation molecular isotopic spectrometry (F 2 -LAMIS). Isotopically enriched graphite samples with varying 13 C concentration were used and the F 2 -LAMIS emission was measured remotely using a portable spectrometer system. A standardless quantification approach was used to determine the corresponding isotopic ratios. The use of F 2 -LAMIS for the detection and quantification of isotopes at atmospheric pressure without the use of calibration standards opens the possibility to implement this technology for remote sensing of isotopes in field applications

07 ISOTOPE AND RADIATION SOURCES↗

Al-26, Pu-244, Ti-50, REE, and trace element abundances in hibonite grains from CM and CV meteorites

Hibonites from the CM meteorites Murchison, Murray, and Cold Bokkeveld, and hibonites and Ti-rich pyroxene from the CV chondrite Allende are studied. Electron microprobe measurements of major element concentrations and track and ion probe measurements of Mg and Ti isotopic ratios, rare earth elements (REEs), and trace element abundances are analyzed. Correlations between isotopic anomalies in Ti, Al-26, Pu-244, and Mg-26(asterisk) are examined. Ti isotopic anomalies are compared with REE and trace element abundance patterns. Reasons for the lack of Al-26 in the hibonites are investigated and discussed. It is observed that there is no correlation between the Ti isotopic compositions, and the presence of Mg-26(asterisk), Pu-244, and REE and trace element patterns in individual hibonite samples. The data reveal that hibonites are not interstellar dust grains but formed on a short time scale and in localized regions of the early solar system.

Fahey, A. J.↗

Systematic study of sulfur isotopic composition in iron meteorites and the occurrence of excess S-33 and S-36

The paper concentrates on isotopic measurements of sulfur in different sulfur-carrier phases: troilite inclusions, Fe-Ni alloy, and schreibersite (possibly including daubreelite). Variations in S-34 isotope ratio are observed in some troilite inclusions, and no evidence of nucleosynthetic sulfur isotopic anomalies are found in the troilite inclusions. Excesses of S-33 and S-36 are observed in both FeNi alloy and schreibersite of Grant, Santa Clara, Tlacotepec, and Gibeon, with schreibersite possessing the greater magnitude of presumably spallogenic S-33 and S-36. It is concluded that the magnitude of the observed fractionation is consistent with troilite dissociation and/or vaporization following a collisional impact.

Gao, Xia↗

The use of mineral crystals as bio-markers in the search for life on Mars

It is proposed that minerals resulting from biologically controlled mineralization processes be utilized as biomarkers because of their favorable qualities. Universal signatures of life (biomarkers) are discussed in terms of their terrestrial forms and hypothetical Martian counterparts including organics, suites of specific inorganic and organic compounds, and isotopic ratios. It is emphasized that minerals produced under biologic control have morphological and isotopic compositions that are not found in their abiotic counterparts. Other biomarkers are not necessarily indicative of biological origin and are therefore unreliable resources for scientific study. Mineral crystals are also stable over long geological periods, and the minerals from Martian fluvial features can therefore be employed to search for fossils and biomarkers of early biological activity.

Schwartz, D. E.↗

Interferometric Imaging of Titan's HC3N, H(13)CCCN, and HCCC(15)N

We present the first maps of cyanoacetylene isotopologues in Titan's atmosphere, including H(13)CCCN and HCCC(15)N, detected in the 0.9 mm band using the Atacama Large Millimeter/submillimeter array (ALMA) around the time of Titan's (southern winter) solstice in 2017 May. The first high-resolution map of HC3N in its v(sub 7) = 1 vibrationally excited state is also presented, revealing a unique snapshot of the global HC3N distribution, free from the strong optical depth effects that adversely impact the ground-state (v = 0) map. The HC3N emission is found to be strongly enhanced over Titan's south pole (by a factor of 5.7 compared to the north pole), consistent with rapid photochemical loss of HC3N from the summer hemisphere combined with production and transport to the winter pole since the 2015 April ALMA observations. The H(13)CCCN/HCCC(15)N flux ratio is derived at the southern HC3N peak, and implies an HC3N/HCCC(15)N ratio of 67 +/- 14. This represents a significant enrichment in 15N compared with Titan's main molecular nitrogen reservoir, which has a N-14/N-15 ratio of 167, and confirms the importance of photochemistry in determining the nitrogen isotopic ratio in Titan's organic inventory.

Cordiner, M. A.↗

The interstellar (C-12)N/(C-13)N ratio toward Zeta Persei

High-resolution, high signal-to-noise observations of interstellar CN toward Zeta Per are performed to determine the C-12/C-13 isotope ratio in this line of sight. Observations of (C-12)N/(C-13)N in several diffuse clouds are performed to assess whether CN suffers from isotope-selective effects. Values are obtained which are higher than the value toward Zeta Oph determined by Crane and Hegyi (1988) and lower than the results toward the more reddened stars HD 21483 obtained by Meyer et al. (1989) and Palazzi et al. (1990). Theory and observations indicate the existence of a spatial C-12/C-13 gradient which decreases toward the Galactic center at an approximate rate of 12 percent/kpc at the distance of the solar radius. It is argued that since a gradient of this character cannot explain the CN results, isotope-selective effects provide a more likely explanation for the large range in (C-12)N/(C-13)N ratios.

Kaiser, Mary E.↗

The incorporation of environmentally derived 87 Sr / 86 Sr and Sr/Ca in early otolith formation of Chinook salmon

Abstract Effective species management often requires understanding patterns of movement and habitat use. A common approach in identifying where individuals reside relies upon chemical tracers from the environment that are incorporated into an individual's tissues. For fish, isotopes in their otoliths, specifically the portion of their otolith formed during their larval stage, have been used to identify the natal origin. Complicating this work, however, is the fact that during this life stage, there is a shift in the source of isotopes deposited onto the growing otolith from maternally to environmentally derived. The objective of this study was to identify the portion of the otolith representing this transition to environmentally derived isotopes so as to accurately investigate questions of natal origin for a threatened population of fall Chinook salmon ( Oncorhynchus tshawytscha ). We exposed developing larvae to four treatments that differed in terms of their water strontium isotope ratio ( 87 Sr/ 86 Sr) and used change‐point analysis of otolith 87 Sr/ 86 Sr and strontium to calcium ratio (Sr/Ca) to identify the otolith radius corresponding to the transition to environmentally derived isotopes. Our results indicated this transition occurred, on average, at 132 μm ( 87 Sr/ 86 Sr; ±50 μm standard deviation) and 127 μm (Sr/Ca; ±29 μm) from the otolith core, which corresponded to the developmental time between hatching and exogenous feeding. A substantial proportion of our otoliths (i.e., 61%) did not show convergence between otolith and water 87 Sr/ 86 Sr by the end of the 113‐day experiment, which was likely due to the dietary contribution of marine‐based feed. Therefore, we were unable to recommend an otolith radius to target for the purposes of reconstructing natal origin apart from being beyond approximately 130 μm.

Chittaro, Paul↗

Isotopic and chemical investigations on Angra dos Reis

Isotope ratios and chemical abundance measurements for a variety of elements are reported for total meteorite and mineral separates of the Angra dos Reis achondrite. U-Pb, Th-Pb, and Pb-Pb ages are concordant at 4.54 eons for the total meteorite and for high-purity whitlockite, which indicates that Angra dos Reis is an early planetary differentiate that has not been disturbed for these systems since 4.54 eons ago. The implications of different ratios of Sr-87 and Sr-86 found in different components are discussed. Xe isotopic measurements show that Pu-244 was enriched in the whitlockite relative to the pyroxene by a factor of about 18. Chemical enrichment factors between the whitlockite and the fassaitic pyroxene in Angra dos Reis are presented

Wasserburg, G. J.↗

The Galileo probe mass spectrometer: composition of Jupiter's atmosphere

The composition of the jovian atmosphere from 0.5 to 21 bars along the descent trajectory was determined by a quadrupole mass spectrometer on the Galileo probe. The mixing ratio of He (helium) to H2 (hydrogen), 0.156, is close to the solar ratio. The abundances of methane, water, argon, neon, and hydrogen sulfide were measured; krypton and xenon were detected. As measured in the jovian atmosphere, the amount of carbon is 2.9 times the solar abundance relative to H2, the amount of sulfur is greater than the solar abundance, and the amount of oxygen is much less than the solar abundance. The neon abundance compared with that of hydrogen is about an order of magnitude less than the solar abundance. Isotopic ratios of carbon and the noble gases are consistent with solar values. The measured ratio of deuterium to hydrogen (D/H) of (5 +/- 2) x 10(-5) indicates that this ratio is greater in solar-system hydrogen than in local interstellar hydrogen, and the 3He/4He ratio of (1.1 +/- 0.2) x 10(-4) provides a new value for protosolar (solar nebula) helium isotopes. Together, the D/H and 3He/4He ratios are consistent with conversion in the sun of protosolar deuterium to present-day 3He.

NASA Discipline Number 52-10↗

Single particle – MC-ICP-MS for isotopic analysis of uranium particles

Single particle – multi-collector – inductively coupled plasma – mass spectrometry (SP-MC-ICP-MS) was employed to measure a suspension of 1 µm U3O8 particles (∼1.3 pg total U/particle) to determine their individual isotopic compositions of 234U/238U, 235U/238U, and 236U/238U. The effects of different detector combinations for 235U and 238U, including secondary electron multipliers (SEM) and Faraday detectors (1011 and 1013 Ω amplifiers), were explored for accuracy and precision optimization on the observed 235U/238U. The minor isotopic ratios (i.e., 234U/238U and 236U/238U) were analyzed such that the 234U and 236U were monitored on SEM detectors and the 238U was monitored on a Faraday (1011 Ω) detector. Various integration times (5, 10, 25, and 50 ms) were investigated in all detector configurations to gain a better understanding of their impact on sensitivity, accuracy, and precision. For 235U/238U ratios of 1 µm U3O8 particles, a dual Faraday detector measurement with 1011 Ω was the optimal choice; measurement of 1021 particles yielded an average 235U/238U ratio of 0.00170 (14), a −1.8% relative difference (% RD) from the reference value. The minor isotopic compositions were determined to be 0.0000070 (14) and 0.0000758 (48) for the 234U/238U and 236U/238U, respectively. These measurements correspond to <8% and <1% RD from their reference value for the 234U/238U and 236U/238U, respectively. SP-MC-ICP-MS was also able to provide insight into measurement sensitivity. In these individual particles, merely 15 and 165 atto-grams (ag) of 234U and 236U were present (calculated). Initial limits of detection for SP-MC-ICP-MS were determined to be ∼1.0 ag (when measured via SEM detectors). This valuable approach is applicable to areas including nuclear forensics, nuclear safeguards, and geochemical analysis, which require high-precision measurements of uranium within micron-sized particles.

Manard, Benjamin [ORNL] (ORCID:0000000207400627)↗

U-Th-Pb and Rb-Sr measurements on some Apollo 14 lunar samples.

The concentrations of selected elements and elemental ratios in some Apollo 14 samples are presented in a table. Another table shows the isotopic composition of lead and strontium in some Apollo 14 samples. Graphs are provided with lead isotope ratio plots and a strontium evolution diagram. Rb-Sr ages are discussed together with isochron age methods of U-Th-Pb, a primary Pb-Pb isochron, a secondary Pb-Pb isochron, U-Pb concordia age relations, and U-Th-Pb concordia relations. Breccias and some soil samples as well as a basalt sample give evidence of significant enrichment of lead relative to uranium and thorium billions of years ago at the Fra Mauro site.

Tatsumoto, M.↗

Inter- and intra-crystalline oxygen isotope distribution of fassaites in Allende CAI

Calcium, aluminum-rich inclusions (CAI's) from carbonaceous chondrite are believed to be among the first solids to have formed in the early solar system and thus to preserve a record of conditions and processes that prevailed early in the solar nebula. We have measured inter- and intra- crystalline oxygen isotope distribution of fassaite in Type B1 CAI of Allende meteorite. Secondary ion mass spectrometry (SIMS) using negative Au primary ion was applied to in situ oxygen isotope ratio analysis on a polished thin section of the CAI. Present data indicate that O isotope composition is homogeneous inside of fassaite grains as well as among grains in the HN3-1 CAI, and that the delta(exp 18) O value (-24.14 percent relative to SMOW) determined previously could be applied to most fassaite grains. The results suggest that most fassaite grains are preexisting solids like spinel grains.

Yurimoto, Hisayoshi↗

Ti Isotopes: Echoes of Grain-Scale Heterogenaity in the Protoplanetary Disk

Calcium-aluminum-rich inclusions (CAIs) are the oldest surviving solids to have formed in the Solar System. Their chemical and isotopic compositions provide a record of the conditions present in the protoplanetary disk where they formed and can aid our understanding of how solids formed in the solar nebula, an important step in the eventual process of planet building. The isotopic compositions of CAIs are primarily controlled by volatility. Evaporation/sublimation are well understood through both theory and experimental work to produce an enrichment in the heavy isotopes of an element, but less is understood about the effects of condensation. Mass-dependent fractionation can potentially provide a record of nebular condensation. Ti is not likely to experience evaporation due to its refractory nature, making it a useful tool for assessing the effects of condensation. We have undertaken a study of the stable isotope fractionation of Ti isotopes as a tracer of processes that predate the last evaporation events affecting CAIs. We compare the 49Ti/47Ti stable isotope ratio with excess 50Ti common in CAIs. We have collected Ti, Mg, Si, and Ca isotope data for a suite of CAIs in order to search for heterogeneity in each of these isotope systems, and for potential correlations among them. We compare our results to expectations for condensation.

Jordan, M. K.↗

Evidence From Hydrogen Isotopes in Meteorites for a Martian Permafrost

Fluvial landforms on Mars suggest that it was once warm enough to maintain persistent liquid water on its surface. The transition to the present cold and dry Mars is closely linked to the history of surface water, yet the evolution of surficial water is poorly constrained. We have investigated the evolution of surface water/ ice and its interaction with the atmosphere by measurements of hydrogen isotope ratios (D/H: deuterium/ hydrogen) of martian meteorites. Hydrogen is a major component of water (H2O) and its isotopes fractionate significantly during hydrological cycling between the atmosphere, surface waters, ground ice, and polar cap ice. Based on in situ ion microprobe analyses of three geochemically different shergottites, we reported that there is a water/ice reservoir with an intermediate D/H ratio (delta D = 1,000‒2500 %) on Mars. Here we present the possibility that this water/ice reservoir represents a ground-ice/permafrost that has existed relatively intact over geologic time.

Usui, T.↗

In-Situ Reaction Monitoring for Lunar Applications Utilizing a Single Quadrupole Residual Gas Analyzer

With a revived focus to create a permeant presence on the moon and in preparation for future Mars exploration, it is imperative that all re-sources are utilized to their fullest potential. In-Situ Resource Utilization (ISRU) will be critical for future mission success as it would enable independent operation of missions while minimally relying on the complex supply chain created between the Earth, moon and Mars. One of the most critical resources that have been identified for ISRU is the creation of liquid oxygen (O2) for not only breathable air, but also for rocket fuel. On the moon and potentially Mars, one of the most O2 rich resources is in the presence of regolith. Although there are numerous minerals within regolith and various processes to extract O2, this is not the scope of this paper. Since the O2 extraction method can vary, a critical standardized analytical method is needed to verify O2 (or oxygenated precursor compounds) for extraction efficiency and purity. Our group utilizes a modified consumer off-the-shelf (COTS), Residual Gas Analyzer (RGA) Single Quadrupole Mass Spectrometer (QMS). Due to the current field mission requirements, the gas analysis module will need to rely only on mass-to-charge ratios (m/z) and peak intensities to differentiate and quantitate targeted gas-phase reactants or products, i.e. carbon monoxide (CO), carbon dioxide (CO2), methane (CH4) and hydrogen (H2). However, due to solar wind implanted volatiles and various other compounds present in lunar regolith, such as nitrogen (N2), helium (He), and deuterium (D2), deconvolution and quantification of isobaric compounds becomes quite difficult. Specifically, the presence of N2 makes quantification of CO, an oxygenated precursor, difficult due to both compounds having a peak at m/z 28. Approaches to differentiate isobaric components: Initially, the solution to overcome isobaric overlap was to use isotopic ratios, particularly be-tween carbon-13 and nitrogen-15. Although limited literature discuss isotopic composition and attempt to quantify the ratios, variation is particularly high and limited to a few lunar regolith samples. The following were identified as potential approaches to quantify isobaric species, N2 and CO, using our RGA. Threshold Ionization. CO and N2 both have peaks at m/z 28, but only N2 is capable of producing a peak at m/z 7. While a N2 peak at m/z 7 is generally rare, instrument parameters can be optimized in order to maximize the peak intensity. Typically a standard ionization energy of 70 eV is used to monitor a batch process and would produce reliable results for a majority of the reactants or products that we are interested in quantifying. However, to analyze the rare molecular fragment of N2 (N2+ at m/z 7), a different ionization energy may be beneficial. Threshold Ionization Mass Spectrometry (TIMS) will be explored to optimize the N2+ peak at m/z 7 by varying parameters such as ionization energy and pressure. Therefore, a quantitative value at m/z 7 will be used to determine the product gas concentration of N2, which will be subtracted from the total concentration determined at m/z 28 enabling us to approximate the amount of CO. Secondary Detector (infrared gas detector, IR). Another approach to quantitate and differentiate be-tween isobaric components is to leverage alternative modes of detection. Unlike mass spectrometry, which generally uses a separation step prior to analysis (i.e. gas chromatography), IR produces energy that is specifically absorbed depending on the bond and configuration of the molecule. This technique could be leveraged since it is generally only active on non-symmetric molecules, i.e. CO. Utilizing concentrations of CO determined from another detector could help correct concentrations of CO obtained from the QMS. However, the inclusion of another detector adds additional mission requirements, such as power, software changes and avionics updates that add additional cost and schedule requirements.

mass spectrometry↗

Round Robin Analysis of Uranium Isotopics on Cotton Swipes Measured Using Microextraction-Based Sampling Versus Conventional Bulk Analysis

A comparison of microextraction sampling methods to directly analyze uranium isotopics on cotton swipes was performed concurrently with traditional bulk-processing methods. For the microextraction sampling approach, two different detection platforms were evaluated, a quadrupole-based inductively coupled plasma mass spectrometer (ICP-MS) and the liquid sampling-atmospheric pressure glow discharge (LS-APGD) coupled to an Orbitrap mass spectrometer. Results presented from this innovative sampling approach (i.e., microextraction) are compared with a more traditional approach employed for analysis of cotton-based environmental swipes, namely bulk ashing/digestion, separation, and subsequent analysis by high-precision multi-collector ICP-MS. Overall, the microextraction approach proved to be a reliable and accurate means to determine isotopic ratios of uranium collected on cotton swipes. The ICP-MS-based detection had relative standard deviations of <0.65% for the major isotopic determinations, whereas the LS-APGD-Orbitrap method had relative standard deviations of <3%. The percent relative difference for the 235 U/ 238 U ratios, in comparison to the expected values, was <1% for ICP-MS and <4% for the microplasma-Orbitrap method. Additionally, the microextraction ICP-MS accurately (<2%) and precisely (<5%) determined the minor isotopic compositions (i.e., 234 U/ 238 U and 236 U/ 238 U).

ICP-MS↗

Using an Isotope Enabled Mass Balance to Evaluate Existing Land Surface Models

Abstract Land surface models (LSMs) play a crucial role in elucidating water and carbon cycles by simulating processes such as plant transpiration and evaporation from bare soil, yet calibration often relies on comparing LSM outputs of landscape total evapotranspiration ( ET ) and discharge with measured bulk fluxes. Discrepancies in partitioning into component fluxes predicted by various LSMs have been noted, prompting the need for improved evaluation methods. Stable water isotopes serve as effective tracers of component hydrologic fluxes, but data and model integration challenges have hindered their widespread application. Leveraging National Ecological Observation Network measurements of water isotope ratios at 16 US sites over 3 years combined with LSM‐modeled fluxes, we employed an isotope‐enabled mass balance framework to simulate ET isotope values ( δET ) within three operational LSMs (Mosaic, Noah, and VIC) to evaluate their partitioning. Models simulating δET values consistent with observations were deemed more reflective of water cycling in these ecosystems. Mosaic exhibited the best overall performance (Kling‐Gupta Efficiency of 0.28). For both Mosaic and Noah there were robust correlations between bare soil evaporation fraction and error (negative) as well as transpiration fraction and error (positive). We found the point at which errors are smallest ( x ‐intercept of the multi‐site regression) is at a higher transpiration fraction than is currently specified in the models. Which means that transpiration fraction is underestimated on average. Stable isotope tracers offer an additional tool for model evaluation and identifying areas for improvement, potentially enhancing LSM simulations and our understanding of land‐surface hydrologic processes.

58 GEOSCIENCES↗