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Comment on 'Heavy ozone in the stratosphere'

It is suggested that the factor-of-two difference in ozone formation rate constants derived by Bates (1986) can also be explained by the omission of standard correction factors from the rate expression. Proper accounting for the fact that isotope exchange and recombination reactions share a common energized collision complex (which can decay by dissociation to products isotopically distinct from the original reactants) eliminates the anomalous dependence of the rate constant on the isotopic composition of the reactants and products through their symmetry numbers. In a reply, Bates argues that symmetry effects in association do not lead to enhancement of the total heavy ozone abundance.

Anderson, Stuart M.↗

Al-26-Mg-26 ages of iron meteorites

An exposure age for an iron meteorite can be calculated from measurements of a radioactive nuclide and a stable nuclide that are produced by similar sets of nuclear reactions, provided that the stable nuclide is present with low initial abundance. The standard methods rely on either K-40 (t(sub 1/2) = 1.26 Gy), K-39, and K-41 or on a shorter-lived radionuclide and a stable, noble gas isotope. Widely used pairs of this type include Cl-36/Ar-36 and Al-26/Ne-21. Other pairs that may serve the purpose for iron meteorites contain many stable isotopes besides those of K and the noble gases that are produced partly by cosmic rays. We consider here the calculation of exposure ages, t(sub 26), from measurements of Al-26 (t(sub 1/2) = 0.7 My) and (stable) Mg-26. Ages based on Al-26/Mg-26 ratios, like those based on Cl-36/Ar-36 ratios, are 'buffered' against changes in relative production rates due to shielding because decay of the radioactive nuclide accounts for a good part of the inventory of the stable nuclide.

Herzog, G. F.↗

Mineralogy of Stardust Track 112 Particle: Relation to Amoeboid Olivine Aggregates

The successful analysis of comet 81P/Wild 2 particles returned by the Stardust mission has revealed that the Wild 2 dust contains abundant silicate grains that are much larger than interstellar grains and appear to have formed in the inner regions of the solar nebula [1]. Wild 2 particles include minerals which are isotopically and mineralogically similar to CAIs [e.g., 2, 3] and chondrules [e.g., 4] in chondrites. In addition, particles similar to amoeboid olivine aggregates (AOAs) also have been discovered [5, 6,7]. C2067,2,112,1 is a terminal particle recovered from track #112 (T112). Nakamura-Messenger et al. [7] showed that the forsterite grain in T112 has O-16 enrichment of approximately 40 0/00 (vs. SMOW) and possibly formed together with AOAs. In this study, we have examined the mineralogy of the T112 particle and compared the possible relationships between T112 and AOAs in primitive meteorites.

Komatsu, M.↗

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↗

Noble gas isotopes and halogens in volatile-rich inclusions in diamonds

Application of the (40)Ar-(39)Ar method and noble gas studies to diamonds has increased our understanding of their age relationships to the host kimberlite or lamproite, and of the source and composition of volatile-rich fluids in the upper mantle. The properties of diamond (inert, high mechanical strength and low gas diffusivities) means they are especially useful samples for studying gases trapped deep within the earth (less than 150 km) as they are unlikely to have undergone loss or exchange of entrapped material since formation. Volatile-rich fluids (H2O-CO2) are important agents for metasomatic processes in the upper mantle, and the noble gases and halogens preferentially partition into this phase leading to a strong geochemical coherence between these groups of elements. The abundances of the halogens in the major reservoirs of the Earth shows a marked progression from chlorine, concentrated in the oceans, through to iodine which, through its affinity to organic material, is concentrated mainly in sediments. Abundances in the upper mantle are low. This is particularly true for iodine which is of special interest in view of its potential significance as an indicator of sediment recycling and by way of its link to (129)Xe amomalies in the mantle through the low extinct isotope (129)I. Extensions of the (40)Ar-(39)Ar technique enable measurements of halogens and other elements (K, Ca, Ba, U) by production of noble gas isotopes from these species during neutron irradiation. Samples analyzed in this way include 15 coated stones from an unknown source in Zaire, 3 boarts from the Jwaneng and 1 boart from the Orapa kimberlites, both in Botswana.

Burgess, Raymond↗

Unraveling the convoluted and dynamic interphasial mechanisms on Li metal anode

Accurate understanding of the chemistry of solid-electrolyte interphase (SEI) is key to developing new electrolytes for high-energy batteries using lithium metal (Li-0) anodes(1). SEI is generally believed to be formed by the reactions between Li-0 and electrolyte(2,3). However, our new study shows this is not the whole story. Through synchrotron-based X-ray diffraction and pair distribution function analysis, we reveal a much more convoluted formation mechanism of SEI, which receives considerable contributions from electrolyte, cathode, moisture and native surface species on Li-0, with highly dynamic nature during cycling. Using isotope labelling, we traced the origin of LiH to electrolyte solvent, moisture and a new source: the native surface species (LiOH) on pristine Li-0. When lithium accessibility is very limited as in the case of anode-free cells, LiOH develops into plate-shaped large crystals during cycling. Alternatively, when the lithium source is abundant, as in the case of Li||NMC811 cells, LiOH reacts with Li-0 to form LiH and Li2O. While the desired anion-derived LiF-rich SEI is typically found in the concentrated electrolytes or their derivatives, we found it can also be formed in low-concentration electrolyte via the crosstalk effect, emphasizing the importance of formation cycle protocol and opening up opportunities for low-cost electrolyte development.

Polzin, Bryant J.↗

Coordinated Chemical and Isotopic Studies of GEMS in IDPS

Cometary IDPs contain a record of the building blocks of the solar system including presolar grains, molecular cloud material, and materials formed in the early solar nebula [1]. Following their accretion, these materials have remained relatively unaltered because of the lack of parent body hydrothermal alteration. We are using coordinated transmission electron microscope (TEM) and ion microprobe studies to establish the origins of the various components within cometary IDPs. Of particular interest is the nature and abundance of presolar silicates in these IDPs because astronomical observations suggest that crystalline and amorphous silicates are the dominant grain types produced in young main sequence stars and evolved O-rich stars [e.g. 2]. Amorphous silicates (in the form of GEMS grains) are a major component of cometary IDPs and so a major objective of this work is to elucidate their origins. In rare cases, GEMS grains have highly anomalous O isotopic compositions that establish their origins as circumstellar condensates [3]. Here we present data on a systematic study of the silicate components within a primitive IDP.

Keller, L. P.↗

Carbon, nitrogen and sulfur in Apollo 15, 16 and 17 rocks

Carbon, nitrogen and sulfur contents, as well as carbon isotopic compositions, were determined for seven lunar rocks from the Apollo 15, 16 and 17 missions. Sequential combustion at three temperatures was used to resolve terrestrial contamination from indigenous lunar volatiles. Nitrogen abundances averaged 0.4 micrograms/gram in the samples. The results of the sequential combustion analysis suggested that all the samples contained variable amounts of terrestrial carbon contamination prior to examination. Indigenous lunar carbon abundances ranging from 2.5 to 6 micrograms/gram were found. Thus the moon appears to be substantially depleted in nitrogen and carbon relative to the earth and C and H meteorites.

Des Marais, D. J.↗

Noble gases in meteorites and terrestrial planets

Terrestrial planets and chondrites have noble gas platforms that are sufficiently alike, especially Ne/Ar, that they may have acquired their noble gases by similar processes. Meteorites presumably obtained their noble gases during formation in the solar nebula. Adsorption onto C - the major gas carrier in chondrites - is the likely mechanism for trapping noble gases; recent laboratory simulations support this hypothesis. The story is more complex for planets. An attractive possibility is that the planets acquired their noble gases in a late accreting veneer of chondritic material. In chondrites, noble gases correlate with C, N, H, and volatile metals; by Occam's Razor, we would expect a similar coupling in planets. Indeed, the Earth's crust and mantle contain chondritic like trace volatiles and PL group metals, respectively and the Earth's oceans resemble C chondrites in their enrichment of D (8X vs 8-10X of the galactic D/H ratio). Models have been proposed to explain some of the specific noble gas patterns in planets. These include: (1) noble gases may have been directly trapped by preplanetary material instead of arriving in a veneer; (2) for Venus, irradiation of preplanetary material, followed by diffusive loss of Ne, could explain the high concentration of AR-36; (3) the Earth and Venus may have initially had similar abundances of noble gases, but the Earth lost its share during the Moon forming event; (4) noble gases could have been captured by planetestimals, possibly leading to gravitational fractionation, particularly of Xe isotopes and (5) noble gases may have been dissolved in the hot outer portion of the Earth during contact with a primordial atmosphere.

Wacker, J. F.↗

Proximal Cretaceous-Tertiary boundary impact deposits in the Caribbean

Trace element, isotopic, and mineralogic studies indicate that the proposed impact at the Cretaceous-Tertiary boundary occurred in an ocean basin, although a minor component of continental material is required. The size and abundance of shocked minerals and the restricted geographic occurrence of the ejecta layer and impact-wave deposits suggest an impact between the Americas. Coarse boundary sediments at sites 151 and 153 in the Colombian Basin and 5- to 450-meter-thick boundary sediments in Cuba may be deposits of a giant wave produced by a nearby oceanic impact.

Hildebrand, Alan R.↗

In Situ Measurements of Meteoric Ions

Extraterrestrial material is the source of metal ions in the Earth's atmosphere, Each year approx. 10(exp 8) kg of material is intercepted by the Earth. The origin of this material is predominantly solar orbiting interplanetary debris from comets or asteroids that crosses the Earth's orbit. It contains a very small amount of interstellar material. On occasion the Earth passes through enhanced amounts of debris associated with the orbit of a decaying comet. This leads to enhanced meteor shower displays for up to several days. The number flux of shower material is typically several times the average sporadic background influx of material. Meteoric material is some of the earliest material formed in the solar system. By studying the relative elemental abundances of atmospheric metal ions, information can be gained on the chemical composition of cometary debris and the chemical makeup of the early solar system. Using in situ sampling with rocket-borne ion mass spectrometers; there have been approximately 50 flights that made measurements of the metal ion abundances at attitudes between 80 and 130 km. It is this altitude range where incoming meteoric particles am ablated, the larger ones giving rise to visible meteor. displays. In several rocket measurements isotopic ratios of different atomic ion mass components and metal molecular ion concentrations have been determined and used to identify unambiguously the measured species and to investigate the processes controlling the metal ion distributions The composition of the Earth's ionosphere was first sampled by an ion mass spectrometer flown an a rocket in 1956. In 1958 a rocket-borne ion spectrometer identified, fbr the first time, a layer of metal ions near 95 km. These data were interpreted as evidence of an extraterrestrial rather than a terrestrial source. Istomin predicted: "It seems probable that with some improvement in the method that analysis of the ion composition in the E-region may be used for determining the chemical composition of those meteors which do not reach the ground. Particularly, we hope to get information about the composition difference between particles of different meteor showers and also sporadic and shower meteoroids". These visions categorized the aims of many subsequent rocket-borne ion mass spectrometer experiments in the lower ionosphere, Although the use such measurements to deduce the composition of different classes of meteoroids has not been successful, the past four decades of rocket observations have provided po%erful sets of data for advancing our understanding of meteor ablation, meteoric composition, metal neutral and ion chemistry as well as ionospheric dynamics.

Grebowsky, Joseph M.↗

The Deuterium to Hydrogen Ratio in the Water that Formed the Yellowknife Bay Mudstones in Gale Crater

A suite of isotope ratios of light elements in the present martian atmosphere (13C/12C, 15N/14N, 18O/16O, 38Ar/36Ar, and D/H) are all substantially enriched in the heavy element suggesting atmospheric loss to space over the past billions of years with preferential loss of the lighter isotope from each pair. In situ measurements from MSL's Sample Analysis at Mars (SAM) instrument [e.g. 1,2,3] have considerably refined previous measurements from the Viking mass spectrometers [e.g. 4], from remote spectroscopic observations [e.g. 5,6], and from martian meteorite studies [e.g. 7,8]. The persistence of habitable environments such as the ancient Yellowknife Bay lake recently revealed by measurements from the Curiosity rover [9] depends on the surface temperatures and the duration of an atmosphere thicker than that at present. Current and planned measurements from orbit with the Mars Express and MAVEN missions respectively intend to study the processes of atmospheric escape including solar wind interaction, sputtering, thermal escape, and dissociative recombination, and determine or refine the current rate of atmospheric loss caused by these and other mechanisms. The goal of these programs is to understand the physical processes sufficiently well so that robust extrapolations over the past billions of years can be made D/H is measured by both the Tunable Laser Spectrometer (TLS) and the Quadrupole Mass Spectrometer (QMS) of the SAM suite. to predict the atmospheric and surface conditions on early Mars. However, the study of the history of martian atmospheric evolution will be greatly facilitated if we are able to also directly measure the isotopic composition of volatiles captured in rocks that are representative of the ancient atmosphere. To date, D/H is one of the most promising candidates for this study since water is the most abundant volatile thermally released from the Yellowknife Bay phylosilicates discovered by the SAM and CheMin experiments of MSL and its

Yellowknife Bay↗

A D- and N-15-Rich Micrometer-Sized Aggregate of Organic Matter in a Xenolithic Clast from the Zag Ordinary Chondrite

The nature and origin of extraterrestrial organic matter are still under debate despite the significant progress in the analyses and experimental approaches in this field over the last five decades. Xenolithic clasts are often found in a wide variety of meteorite groups, some of which contain exotic organic matter (OM). The Zag meteorite is a thermally-metamorphosed H ordinary chondrite. It contains a primitive xenolithic clast that has been proposed to have originated from Ceres, which was accreted to the Zag host asteroid after metamorphism. The cm-sized clast contains abundant large carbon-rich (mostly organic) grains or aggregates up to 20 microns. Such large OM grains are unique among astromaterials with respect to the size. Here we report organic and isotope analyses of a large (approx.10 microns) aggregate of solid OM in the Zag clast. The X-ray micro-spectroscopic technique revealed that the OM has sp2 bonded carbon with no other functional groups nor graphitic feature (1s-sigma exciton), and thus it is distinguished from most of the OM in carbonaceous meteorites. The apparent absence of functional groups in the OM suggests that it is composed of hydrocarbon networks with less heteroatoms, and therefore the OM aggregate is similar to hydrogenated amorphous carbon (HAC). The OM aggregate has high D/H and 15N/14N ratios, suggesting that it originated in a very cold environment such as the interstellar medium or outer region of the solar nebula, while the OM is embedded in carbonate-bearing matrix resulting from aqueous activities. Thus the high D/H ratio must have survived the extensive late-stage aqueous processing. It is not in the case for OM in carbonaceous chondrites of which the D/H ratio was reduced by the alteration via the D-H exchange of water. It indicates that both the OM precursors and the water had high D/H ratios, similar to the water in Enceladus. Our results support the idea that the clast originated from Ceres, or at least, a hydrovolcanically active body similar to Ceres, and further imply that Ceres originally formed in the outer Solar System and migrated to the main belt asteroid region as suggested by the "Grand tack" scenario.

Kebukawa, Yoko↗

Incorporation of 16 O-rich anhydrous silicates in the protolith of highly hydrated asteroid Ryugu

The abundant phyllosilicate and carbonate minerals characterizing most of the returned particles from asteroid Ryugu suggest a history of extensive aqueous alteration on its parent body, similar to the rare mineralogically altered, but chemically primitive, CI (Ivuna-type) chondrite meteorites. Particle C0009 differs mineralogically from other Ryugu particles examined so far by containing anhydrous silicates at a level of ~0.5 vol%, and thus can help shed light on the unaltered original materials that constituted Ryugu’s protolith. In situ oxygen isotope measurements of the most Mg-rich olivine and pyroxene in C0009 reveal two populations of Δ 17 O: –25‰ to –15‰ and –8‰ to –3‰. The former and the latter populations correlate well with silicate morphologies similar to those seen in amoeboid olivine aggregates and chondrule phenocrysts, respectively, both of which are abundant in less aqueously altered carbonaceous chondrites. Here, this result also highlights the presence of olivine with Δ 17 O close to the solar value in either a CI chondrite or an asteroid with CI-chondrite characteristics, and provides strong evidence that amoeboid olivine aggregates and Mg-rich chondrules accreted into Ryugu’s protolith. Our data also raise the possibility that the protoliths of CI and other carbonaceous chondrites incorporated similar anhydrous silicates.

58 GEOSCIENCES↗

Associative nitrogen fixation linked with three perennial bioenergy grasses in field and greenhouse experiments

Abstract Associative nitrogen (N 2 )‐fixation (ANF) by bacteria in the root‐zone of perennial bioenergy grasses has the potential to replace or supplement N fertilizer and support sustainable production of biomass, but its application in marginal ecosystems requires further evaluation. In this study, we first combined both greenhouse and field experiments, to explore the N 2 fixation effects of three temperate feedstocks Miscanthus × giganteus (giant miscanthus, Freedom), Panicum virgatum (switchgrass, Alamo), and Saccharum sp. (energycane, Ho 02‐147). In field studies across three growing seasons, plant and soil pools of candidate feedstocks were partially composed of N derived from the atmosphere (Ndfa). Energycane, giant miscanthus, and switchgrass were estimated to derive >30%, %Ndfa. Greenhouse studies were also performed to trace isotopically labeled 15 N 2 into plant biomass and soil pools. Evidence for Ndfa was detected in all three feedstock grasses (using reference 15 N of soil, chicory, and sorghum, δ 15 N~+7.0). Isotopically labeled 15 N 2 was traced into biomass (during grass elongation stage) and soil pools. Extrapolation of rates during the 24 hr labeling period to 50 days estimated 30%–55% of plant Ndfa, with the greatest Ndfa for energycane. The findings of the field natural abundance and greenhouse 15 N 2 feeding experiments provided complementary evidence that perennial bioenergy grasses have the potential to support relatively high rates of ANF, and accumulate diazotroph‐derived N into biomass when grown on non‐fertilized soil.

09 BIOMASS FUELS↗

Carbon and Sulfur Isotopic Composition of Yellowknife Bay Sediments: Measurements by the Sample Analysis at Mars (SAM) Quadrupole Mass Spectrometer

Since landing at Gale Crater in Au-gust 2012, the Sample Analysis at Mars (SAM) instru-ment suite on the Mars Science Laboratory (MSL) “Curiosity” rover has analyzed solid samples from the martian regolith in three locations, beginning with a scoop of aeolian deposits from the Rocknest (RN) sand shadow. Curiosity subsequently traveled to Yellowknife Bay, where SAM analyzed samples from two separate holes drilled into the Sheepbed Mudstone, designated John Klein (JK) and Cumberland (CB). Evolved gas analysis (EGA) of all samples revealed the presence of H2O as well as O-, C- and S-bearing phas-es, in most cases at abundances below the detection limit of the CheMin instrument. In the absence of definitive mineralogical identification by CheMin, SAM EGA data can help provide clues to the mineralogy of volatile-bearing phases through examination of tem-peratures at which gases are evolved from solid sam-ples. In addition, the isotopic composition of these gas-es may be used to identify possible formation scenarios and relationships between phases. Here we report C and S isotope ratios for CO2 and SO2 evolved from the JK and CB mudstone samples as measured with SAM’s quadrupole mass spectrometer (QMS) and draw com-parisons to RN.

Franz, H. B.↗

Plutonium isotope ratio measurements by total evaporation-thermal ionization mass spectrometry (TE-TIMS): an evaluation of uncertainties using traceable standards from the New Brunswick Laboratory

The accuracy and precision of isotope amount ratio measurements using thermal ionization mass spectrometry (TIMS) instrumentation are described, and the measurement of Pu materials is emphasized. The mass fractionation observed for Am, Ga, Pu, and U for isotope amount ratio measurements using the total evaporation (TE) technique is compared with theoretical estimates to demonstrate the advantage of the TE methodology and to investigate systematic biases in the major isotope amount ratios of U and Pu certified reference material (CRM) standards from the U.S. provider of CRMs. The quality of the Pu isotopic data generated by TIMS instruments in an analytical laboratory is demonstrated by the application of the double ratio technique to estimate the 241 Pu half-life. Analytical data on traceable Pu CRMs from the New Brunswick Laboratory (NBL), generated as part of routine measurements supporting various programs, are used for this half-life estimation. Although the 241 Pu abundances in CRMs of 136, 137, 138, and 126-A are approximately 200–2000× smaller than those in the 241 Pu material used in the previous Institute for Reference Materials and Measurements (IRMM) evaluation of the 241 Pu half-life, the half-life value estimated in this work shows excellent agreement with the currently accepted value from the IRMM. This agreement also demonstrates the pedigree of the Pu isotopic standards from the NBL and the quality of the isotope amount ratio measurements using TIMS instrumentation. For both the major and minor Pu isotope amount ratios, this report describes the relative importance of the factors affecting the uncertainty of TIMS measurements, which are considered the gold standard in isotope ratio measurements (LA-UR-24-29199).

07 ISOTOPE AND RADIATION SOURCES↗

Carbon Isotopic Heterogeneity of Graphite in the San Juan Mass of the Campo Del Cielo IAB Iron Meteorite

The origin of IAB iron meteorites is still a matter of debate. It is generally believed that iron meteorites originated from molten cores in small planetesimals because the fractionation trend of trace elements (e.g., Ir, Ge, Ga, etc. vs. Ni) for most iron meteorites can be more or less explained by fractional crystallization from metal melts. However, this process cannot produce trace element characteristics of the IAB (and other) iron meteorites. To explain these trace element abundance patterns, several models have been proposed. Although most of these models require a high temperature, clear evidence has recently been obtained for a sub-solidus formation of IAB iron meteorites from noble gas analyses. Moreover, heterogeneous distributions of some trace elements in metal and other phases also suggest a low temperature origin of at least some IAB iron meteorites. Here we use the carbon isotopic compositions of graphite to constrain the origin of IAB iron meteorites. Our data confirm a possible low temperature origin of IAB iron meteorites.

Maruoka, T.↗