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Trace element geochemistry of Archean volcanic rocks

The K, Rb, Sr, Ba and rare-earth-element contents of some Archean volcanic rocks from the Vermilion greenstone belt, northeast Minnesota, were determined by the isotopic dilution method. The characteristics of trace element abundances, supported by the field occurrences and major element chemistry, suggest that these volcanic rocks were formed in an ancient island arc system.

Jahn, B.-M.↗

Grains of anomalous isotopic composition from novae

The effects of grain formation in nova ejecta are studied in order to model the optical and infrared luminosities schematically and to identify the anomalies of isotopic composition that should be present in large abundance in these grains. The large carbon concentration makes rapid and efficient grain formation possible and accounts for the peculiar luminosities observed in Nova Serpentis 1970. In the anticipated range of nova conditions, rapid addition of hot protons during the outburst produces large overabundances of C-13, O-18, Na-22, Al-26, Si-30, and perhaps others. Anomalous C-14 is expected subsequent to the C-13(alpha, n)O-16 reaction, and will be trapped in grains formed by subsequent atmospheric loss. Each of these anomalies may have been detected on the moon (due to accretion of interstellar dust) or in carbonaceous chondrites. Perhaps nova grains are responsible.

Clayton, D. D.↗

Sulfur abundances and distributions in mare basalts and their source magmas

An inverse correlation between metallic iron content and total sulfur abundances was observed by Gibson and Moore (1974) for five Apollo 17 and six Apollo 15 basalts. An investigation was conducted with the objective to distinguish between two processes leading to the inverse metallic iron and total sulfur correlation. The investigation included analyses of ten Apollo 15 and five Apollo 17 basalts for their sulfur and metallic iron abundances along with carbon and hydrogen. The sulfur isotopic compositions were measured for a possible identification of the fractionation processes which might have occurred during volatilization of the basalts.

Gibson, E. K., Jr.↗

Boundary conditions for the paleoenvironment: Chemical and Physical Processes in dense interstellar clouds

The present research includes searches for important new interstellar constituents; observations relevant to differentiating between different models for the chemical processes that are important in the interstellar environment; and coordinated studies of the chemistry, physics, and dynamics of molecular clouds which are the sites or possible future sites of star formation. Recent research has included the detection and study of four new interstellar molecules; searches which have placed upper limits on the abundance of several other potential constituents of interstellar clouds; quantitative studies of comparative molecular abundances in different types of interstellar clouds; investigation of reaction pathways for astrochemistry from a comparison of theory and the observed abundance of related species such as isomers and isotopic variants; studies of possible tracers of energenic events related to star formation, including silicon and sulfur containing molecules; and mapping of physical, chemical, and dynamical properties over extended regions of nearby cold molecular clouds.

Irvine, W. M.↗

The chemical state of dense interstellar clouds - An overview

The currently known interstellar molecules and isotopes are listed, procedures for determining relative chemical abundances in molecular clouds are discussed, and current best estimates for such abundances in regions of differing physical properties are presented. Among the results are a general chemical similarity across a range of density and temperature for quiescent clouds, and some striking differences among regions which are not easily related to such physical parameters and may instead reflect cloud history and evolution. The possibility of constraining chemical models via measurements of relative abundances for the isomeric pairs HNC/HCN, CH3NC/CH3CN, and HOC(+)/HCO(+) is discussed in detail.

Irvine, W. M.↗

Observations of the H2S toward OMC-1

Observations of the 1(10) - 1(01) transition of interstellar H2S and its isotopes toward OMC-1 are reported. The fractional abundance of H2S in the quiescent regions of OMC-1 seems difficult to explain by currently known ion-molecular reactions. The fractional abundance of H2S relative to H2 is enhanced by a factor of 1000 in the hot core and the plateau relative to the quiescent clouds. The (HDS)/(H2S) abundance ratio in the hot core is estimated at 0.02 or less.

Minh, Y. C.↗

Production Rates of Noble Gases in the Near-Surface Layers of Europa by Energetic Charged Particles and the Potential for Determining Exposure Ages

The surface of Europa is expected to be extremely active, undergoing tectonic and/or tidal geological activity and sputtering/ deposition, as well as impact cratering. Determination of the actual age of the surface at one or more places would greatly simplify trying to sort out what processes are occurring, and at what rate. If there is K present, as the spectral and compositional modeling discussed predict, it should be possible, in principle, to determine K-Ar crystallization ages. Whether or not there is K present, a consideration of the environment suggests we can determine an energetic particle exposure age if we can make in situ measurements of the abundances of major elements and of noble gas isotopes. This requires instrumentation that is within reach of current technology. In this paper, we calculate production rates for noble-gas isotopes in a simplified Europan surface, to quantify the amount of light noble gases produced by exposure to energetic particles.

Swindle, T. D.↗

Discovery of Presolar Corundum (and SiC?) in an Interplanetary Dust Particle

This work is part of an ongoing investigation [1-3] of isotopically anomalous phases in interplanetary dust particles (IDPs) on a scale of 100 nm. Previously, such NanoSIMS studies have found sub-micrometer sized, isotopically distinct presolar grains in IDPs at higher abundances than in primitive meteorites [1-5], which demonstrates the unique and primitive nature of IDPs. Although not all presolar grains found so far in IDPs have been chemically or petrographically characterized, the majority appear to be silicate stardust. Conspicuously absent from the presolar grain inventory in IDPs have been other grain types, which are commonly found in primitive meteorites, such as SiC and corundum (Al2O3).

Stadermann, F. J.↗

Sm-Nd, Rb-Sr, and Mn-Cr Ages of Yamato 74013

Yamato 74013 is one of 29 paired diogenites having granoblastic textures. The Ar-39 - Ar-40 age of Y-74097 is approximately 1100 Ma. Rb-Sr and Sm-Nd analyses of Y-74013, -74037, -74097, and -74136 suggested that multiple young metamorphic events disturbed their isotopic systems. Masuda et al. reported that REE abundances were heterogeneous even within the same sample (Y-74010) for sample sizes less than approximately 2 g. Both they and Nyquist et al. reported data for some samples showing significant LREE enrichment. In addition to its granoblastic texture, Y-74013 is characterized by large, isolated clots of chromite up to 5 mm in diameter. Takeda et al. suggested that these diogenites originally represented a single or very small number of coarse orthopyroxene crystals that were recrystallized by shock processes. They further suggested that initial crystallization may have occurred very early within the deep crust of the HED parent body. Here we report the chronology of Y-74013 as recorded in chronometers based on long-lived Rb-87 and Sm-147, intermediate- lived Sm-146, and short-lived Mn-53.

Nyquist, L. E.↗

Review of melt inclusions in lunar rocks: constraints on melt and mantle composition and magmatic processes

Mineral-hosted melt inclusions provide a window into magmatic processes and pre-eruptive liquid compositions. Because melt inclusions are small (typically < 100 µm), the study of lunar melt inclusions is enabled by advancements of microbeam instrumental techniques. In the 1970s immediately following the Apollo and Luna missions, major and minor oxide concentrations of lunar melt inclusions were measured using electron microprobes. The data were used to understand magma evolution, and they revealed the immiscibility of two silicate liquids in the late stage of lunar magma evolution. More recently, the development of secondary ion mass spectrometry as well as laser ablation–inductively coupled plasma–mass spectrometry has enabled the measurement of key volatile elements and other trace elements in lunar melt inclusions, down to about the 0.1 ppm level. The applications of these instruments have ushered in a new wave of lunar melt inclusion studies. Recent advances have gone hand in hand with improved understanding of post-entrapment loss of volatiles. These studies have provided deep insights into pre-eruptive volatiles in lunar basalts, the abundance of volatiles in the lunar mantle, the isotopic ratios of some volatile elements, and the partition of trace elements between host olivine and melt inclusions. The recent studies of lunar melt inclusions have played a critical role in establishing a new paradigm of a fairly wet Moon with about 100 ppm H2O in the bulk silicate Moon (rather than a “bone-dry” Moon) and have been instrumental in developing an improved understanding of the origin and evolution of the Moon.

Youxue Zhang↗

The charge and isotopic composition of Z = 6-14 cosmic ray nuclei at their source

Using data from a cosmic ray charge-isotope telescope flown on balloons, both the charge and isotopic composition are determined of Z = 6-14 cosmic ray nuclei. A low abundance for the elements N and Ne in the cosmic ray source relative to solar cosmic rays is observed. For the isotopes, a cosmic ray source ratio Ne-22/Ne-20 is found that is 3.52 plus or minus 0.67 times the solar ratio, this enhancement being due in part to an enhancement of Ne-22 and in part to an underabundance of Ne-20. Also observed are possible enhancements of the Mg-26/Mg-24 ratio, which is 1.40 plus or minus 0.24 times the solar t ratio, and the C-13/C-12 ratio, which is 2.90 plus or minus 0.93 times the solar ratio. For Ne, the underabundance of this element, coupled with the overabundnace of the isotope Ne-22, is seen as providing an important new clue to the nucleosynthesis processes producing these differences.

Webber, W. R.↗

Bimodal abundances in the energetic particles of solar and interplanetary origin

This letter reports the first results from an examination of the daily-averaged abundances of the elements from H through Fe as well as electrons and isotopes of He in energetic particles observed in interplanetary space by the ISEE 3 spacecraft over an 8.5 yr period. The abundances of heavy elements such as Fe/O show, for the first time, clear evidence of the presence of two distinct populations of particles. Earlier observations could be interpreted as extreme variations within a single population. The population with enhanced Fe/O shows correlated enhancements in He-3/He-4, p/e, and He/H. This population is consistent with material that has been processed to high temperatures in the impulsively heated regions of solar flares. The second population, with more normal abundances, is probably accelerated from ambient material by coronal and interplanetary shocks.

Reames, Donald V.↗

Alfven wave scattering and the secondary to primary ratio

The cosmic ray abundances have traditionally been used to determine the elemental and isotopic nature of galactic ray sources and average measures of propagation conditions. Detailed studies of the physics of propagation are usually paired with relatively straightforward estimates of the secondary-to-primary (S/P) ratios. In the work reported here, calculations of elemental abundances are paired with a more careful treatment of the propagation process. It is shown that the physics of propagation does indeed leave specific traces of Galactic structure in cosmic ray abundances.

Bretthorst, G. L.↗

On the origin and evolution of isotopes of carbon, nitrogen, and oxygen

Calculations of CNO processing in stellar envelopes, based on theoretical nucleosynthesis rather than empirical abundances in evolving stars, are presented and used in two models for the chemical evolution of the solar neighborhood. Seven stable isotopes are considered: C-12, C-13, N-14, N-15, O-16, O-17, and O-18. The two models ('infall' and 'initial-burst') represent extremes of types consistent with general constraints and include theoretical estimates of other nucleosynthesis sites and yields for CNO isotopes. The results obtained are found to predict that all CNO isotopes are produced mainly by stars with lifetimes much less than the age of the Galaxy (even at the present time when low-mass stars have the greatest death rate), so that isotopic ratios evolve very slowly after the first few billion years. Consequences of these slow changes are that the isotopic ratios cannot be employed to test between alternative hypotheses and that galactic evolution does not seem to be able to account for the apparent difference between the C-13/C-12 ratio in the solar system and in molecular clouds. The predicted envelope processing is shown to lead to approximately the solar-system values for the C-13/C-12 and O-17/O-16 abundance ratios but to a N-14/C-12 ratio that is too small by at least a factor of 2.

Dearborn, D.↗

Constraining Inputs to Realistic Kilonova Simulations through Comparison to Observed r -process Abundances

Kilonovae, one source of electromagnetic emission associated with neutron star mergers, are powered by the decay of radioactive isotopes in the neutron-rich merger ejecta. Models for kilonova emission consistent with the electromagnetic counterpart to GW170817 predict characteristic abundance patterns, determined by the relative balance of different types of material in the outflow. Assuming that the observed source is prototypical, this inferred abundance pattern in turn must match r -process abundances deduced by other means, such as what is observed in the solar system. We report on analysis comparing the input mass-weighted elemental compositions adopted in our radiative transfer simulations to the mass fractions of elements in the Sun, as a practical prototype for the potentially universal abundance signature from neutron star mergers. We characterize the extent to which our parameter inference results depend on our assumed composition for the dynamical and wind ejecta and examine how the new results compare to previous work. We find that a dynamical ejecta composition calculated using the FRDM2012 nuclear mass and FRLDM fission models with extremely neutron-rich ejecta ($Y_e$ = 0.035) along with moderately neutron-rich ($Y_e$ = 0.27) wind ejecta composition yields a wind-to-dynamical mass ratio of $M_w$/$M_d$ = 0.47, which best matches the observed AT2017gfo kilonova light curves while also producing the bestmatching abundance of neutron capture elements in the solar system, though, allowing for systematics, the ratio may be as high as of order unity.

79 ASTRONOMY AND ASTROPHYSICS↗

Shock Experiments on Basalt - Ferric Sulfate Mixes at 21 GPa & 49 GPa and their Relevance to Martian Meteorite Impact Glasses

Large abundance of Martian atmospheric gases and neutron-induced isotopic excesses as well as Rb-Sr isotopic variations determined in some impact glasses in basaltic shergottites (e.g., Shergotty #DBS, Zagami #H1 and EET79001 #27, #8 and #104) provide definitive evidence for the occurrence of a Martian regolith component in their constituent mineral assemblages. Some of these glass-es, known as gas-rich impact-melts (GRIM), contain numerous micron-sized iron sulfide blebs along with minor amounts of iron sulfate particulates. As these GRIM glasses contain a Martian regolith component and as iron sulfates (but not sulfides) are found to occur abundantly on the Mars surface, we suggested that the sulfide blebs in GRIMs were likely generated by shock-reduction of the parental iron sulfate bearing regolith material that had been incorporated into the cavities/crevices of basaltic host rock prior to the impact event on Mars. To test whether the sulfates could be reduced to sulfides by impact shock, we carried out laboratory shock experiments on a basalt plus ferric sulfate mixture at 49 GPa at the Caltech Shock Wave Laboratory and at 21 GPa at Johnson Space Center (JSC) Experimental Impact Laboratory. The experimental details and the preliminary results for the Caltech 49 GPa experiment were presented at LPSC last year. Here, we report the results for the 21 GPa experiment at JSC and compare these results to obtain further insight into the mechanism of the bleb formation in the GRIM glasses.

Rao, M. N.↗

Precision Oxygen Isotope Measurements of Two C-Rich Hydrated Interplanetary Dust Particles

Introduction: Chondritic-smooth IDPs (Interplanetary Dust Particles) are low porosity objects whose mineralogy is dominated by aqueous alteration products such as Mg-rich phyllosilicates (smectite and serpentine group) and Mg-Fe carbonate minerals. Their hydrated mineralogy combined with low atmospheric entry velocities have been used to infer an origin largely from asteroidal sources. Spectroscopic studies show that the types and abundance of organic matter in CS IDPs is similar to that in CP IDPs. Although CS IDPs show broad similarities to primitive carbonaceous chondrites, only a few particles have been directly linked to specific meteorite groups such as CM and CI chondrites based on the presence of diagnostic minerals. Many CS IDPs however, have carbon contents that greatly exceed that of known meteorite groups suggesting that they either may derive from comets or represent samples of more primitive parent bodies than do meteorites. It is now recognized that many large, dark primitive asteroids in the outer main belt, as well as some trans-Neptunian objects, show spectroscopic evidence for aqueous alteration products on their surfaces. Some CS IDPs exhibit large bulk D enrichments similar to those observed in the cometary CP IDPs. While hydrated minerals in comets have not been unambiguously identified to date, the presence of the smectite group mineral nontronite has been inferred from infrared spectra obtained from the ejecta from comet 9P/Tempel 1 during the Deep Impact mission. Recent observations of low temperature sulfide minerals in Stardust mission samples suggest that limited aqueous activity occurred on comet Wild-2. All of these observations, taken together, suggest that the high-carbon hydrated IDPs are abundant and important samples of primitive solar system objects not represented in meteorite collections. Oxygen isotopic compositions of chondrites reflect mixing between a 16O-rich reservoir and a 17O,18O-rich reservoir produced via mass-independent fractionation. The composition of the 16O-rich reservoir is well constrained but material representing the 17O,18O-rich end-member is rare. Self-shielding models predict that cometary water, presumed to represent this reservoir, should be enriched in 17O and 18O by greater than 200 per mille. The high-carbon hydrated IDPs may be among the best materials available to search for preserved "cometary" H2O signatures. In order to better understand the origin and evolution of these particles, we have obtained 10 hydrated interplanetary dust particles for coordinated mineralogical, isotopic and organic analyses. We have previously reported the results of mineralogical and O isotopic measurements of two hydrated IDPs; here we present results of O isotopic measurements of three additional IDPs. Samples and Methods: Three interplanetary dust particles (L2079C35, L2083D46 and L2083E46) were embedded in S and partially ultramicrotomed into approximately 70 nanometer sections for analysis via transmission electron microscopy (TEM). The remainders of the unsliced particles were removed from S and pressed into high purity Au foil that was cleaned with HF acid and annealed at 800 degrees Centigrade. The pressed IDPs were analyzed via electron microprobe analysis (EPMA) for quantitative bulk chemical analysis. After EPMA analysis, the IDPs were subjected to precision O isotope analysis with the UCLA Cameca IMS-1270 ion probe. A 20 kiloelectronvolt, 0.5 nanoangstrom Cs+ primary beam of approximately 15 micrometers diameter was used for each measurement. Small particles of San Carlos olivine and Burma spinel were pressed into the Au foil for use as standards to correct for instrumental mass fractionation. The detection system was configured for multicollection, with 16O measured on a Faraday cup, and 17O and 18O measured on electron multipliers (EMs). Individual analyses consisted of 15 cycles of 10 seconds per cycle. Additionally, two microtome thin sections were measured for H isotopic compositions with the JSC NanoSIMS 50L ion probe. An 8 picoangstrom, 16 kiloelectronvolt Cs plus primary beam was used. Measurements consisted of H, C, 12C, 16O, and 18O collected with EMs in multicollection. Terrestrial biotite and kerogen were used for isotopic standards. A significant challenge in O isotope measurement of hydrated minerals is the interference from 16OH at mass 17O. We ensured that the 17O and 16OH peaks were fully resolved by using a mass resolution of greater than 7000 and by careful analyses of San Carlos olivine, Burma spinel and chlorite hydrated mineral standards. The hydride was further suppressed with a cold finger attached to an LN2 dewar to trap volatiles in the sample chamber. All sputtered ions were counted (i.e. presputtering was not used); after applying background, yield and deadtime corrections, we performed a change-point analysis on our data via R in order to determine when the sample reached sputtering equilibrium; data points collected prior to the change point were excluded. Change-point analysis was also used to determine whether the IDP had completely sputtered. Results: Mineralogy. IDPs C35 and E46 exhibited hydrated mineralogies, Fe-Ni sulfide grains, nanoglobules and occasional enstatite grains distributed throughout a fine-grained Mg-Fe saponite matrix. C35 also contained breunnerite (Mg,Fe)CO3; solar flare tracks were observed in enstatite, indicating minimal atmospheric entry heating. The mineralogy of D46 is dominated by a large FeS grain with a minor component of adhering silicate material. D46 was strongly heated during atmorpheric entry as evidenced by a well-developed magnetite rim. EPMA analyses show that both C35 and E46 have high carbon contents of 20 weight percentage (approximately 6X CI). D46 contains approximately 6 wt.weight percentage C. A significant amount of the carbon is present as carbon nanoglobules. Results: Hydrogen isotopes: Although the bulk delta D values of both sections of L2079C35 were within error of SMOW (minus 33 plus or minus 19 per mille, 1 plus or minus 14 per mille 1 sigma), several delta D-rich hotspots were also identified, reaching 2000 per mille. As shown in Fig. 1, these hotspots are clearly associated with discrete carbonaceous inclusions that are akin to nanoglobules found in many meteorites and other IDPs. Oxygen Isotopes. Results of the oxygen isotope measurements are shown in Figure 1. The oxygen isotope composition for L2079C35 was delta 18O equals plus11.6 plus or minus 1.9per mille, delta 17O equals plus 7.9 plus or minus 1.9per mille (2 standard errors). The oxygen isotope composition for L2083D46 was delta 18O equals minus 8.1 plus or minus 1.9 per mille, delta 17O equals minus 6.4 plus or minus 3.1 per mille (2 standard errors). The oxygen isotope composition for L2083E46 was delta 18O equals plus 12.0 plus or minus 1.9 per mille, delta 17O equals plus 9.2 plus or minus 2.0 per mille (2 standard errors). Discussion: Despite mineralogical similarities to highly aqueously altered carbonaceous chondrites, the hydrated IDPs we analyzed have oxygen isotopic compositions that are distinct from matrix materials in the CI, CM, and CR chondrites. The IDPs plot along the Young-Russell line, with delta 17O values for C35 and E46 suggestive of interaction with a 16O-poor reservoir. However, we have thus far not observed evidence of extreme 16O-poor reservoirs expected from self-shielding models and observed in Acfer 094 simplectite. The high carbon contents of the IDPs also set them apart from known meteoritic samples. The lack of atmospheric entry heating effects are consistent with low encounter velocities and suggest either an asteroidal source, or a low inclination, low eccentricity cometary origin. Conclusions: The unusual oxygen isotopic compositions, high carbon contents, and the abundance of Drich nanoglobules, together, suggest that the high-carbon, hydrated IDPs are derived from a primitive source that is not yet represented in meteorite collections.

Snead, C. J.↗

Methane-cycling microbial communities from Amazon floodplains and upland forests respond differently to simulated climate change scenarios

Seasonal floodplains in the Amazon basin are important sources of methane (CH 4 ), while upland forests are known for their sink capacity. Climate change effects, including shifts in rainfall patterns and rising temperatures, may alter the functionality of soil microbial communities, leading to uncertain changes in CH 4 cycling dynamics. To investigate the microbial feedback under climate change scenarios, we performed a microcosm experiment using soils from two floodplains (i.e., Amazonas and Tapajós rivers) and one upland forest. We employed a two-factorial experimental design comprising flooding (with non-flooded control) and temperature (at 27 °C and 30 °C, representing a 3 °C increase) as variables. We assessed prokaryotic community dynamics over 30 days using 16S rRNA gene sequencing and qPCR. These data were integrated with chemical properties, CH 4 fluxes, and isotopic values and signatures. In the floodplains, temperature changes did not significantly affect the overall microbial composition and CH 4 fluxes. CH 4 emissions and uptake in response to flooding and non-flooding conditions, respectively, were observed in the floodplain soils. By contrast, in the upland forest, the higher temperature caused a sink-to-source shift under flooding conditions and reduced CH 4 sink capability under dry conditions. The upland soil microbial communities also changed in response to increased temperature, with a higher percentage of specialist microbes observed. Floodplains showed higher total and relative abundances of methanogenic and methanotrophic microbes compared to forest soils. Isotopic data from some flooded samples from the Amazonas river floodplain indicated CH 4 oxidation metabolism. This floodplain also showed a high relative abundance of aerobic and anaerobic CH 4 oxidizing Bacteria and Archaea. Taken together, our data indicate that CH 4 cycle dynamics and microbial communities in Amazonian floodplain and upland forest soils may respond differently to climate change effects. We also highlight the potential role of CH 4 oxidation pathways in mitigating CH 4 emissions in Amazonian floodplains.

16S rRNA sequencing↗