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NASA NTRS2015

Evidence of Metasomatism in the Lowest Petrographic Types Inferred from A Na(-), K, Rich Rim Around A LEW 86018 (L3.1) Chondrule

Ordinary chondrites (OCs) represent the most abundant extraterrestrial materials and also record the widest range of alteration of primary, pristine minerals of early Solar system material available for study. Relatively few investigations, however, address: (1) the role of fluid alteration, and (2) the relationship between thermal metamorphism and metasomatism in OCs, issues that have been extensively studied in many other meteorite groups e.g., CV, CO, CR, and enstatite chondrites. Detailed elemental abundances profiles across individual chondrules, and mineralogical studies of Lewis Hills (LEW) 86018 (L3.1), an unequilibrated ordinary chondrite (UOC) of low petrographic type of 3.1 returned from Antarctica, provide evidence of extensive alteration of primary minerals. Some chondrules have Na(-), K(-), rich rims surrounded by nepheline, albite, and sodalite-like Na(-), Cl(-), Al-rich secondary minerals in the near vicinity within the matrices. Although, limited evidences of low temperature (approximately 250 C) fluid-assisted alteration of primary minerals to phyllosilicates, ferroanolivine, magnetite, and scapolite have been reported in the lowest grades (less than 3.2) Semarkona (LL3.00) and Bishunpur (LL3.10), alkali-rich secondary mineralization has previously only been seen in higher grade greater than 3.4 UOCs. This preliminary result suggests highly localized metamorphism in UOCs and widens the range of alteration in UOCs and complicates classification of petrographic type and extent of thermal metamorphism or metasomatism. The work in progress will document the micro-textures, geochemistry (Ba, Ca, REE), and isotopic composition (oxygen, Al(-)- 26 Mg-26) of mineral phases in chondrules and adjoining objects to help us understand the formation scenario and delineate possible modes of metamorphism in UOCs.

Mishra, Ritesh Kumar↗

NASA NTRS2012

Predicting the Sources and Formation Mechanisms of Evolved Lunar Crust by Linking K/Ca Ratios of Lunar Granites to Analogous Terrestrial Igneous Rocks

Although silicic rocks (i.e. granites and rhyolites) comprise a minor component of the sampled portion of the lunar crust, recent remote sensing studies [e.g., 1-4] indicate that several un-sampled regions of the Moon have significantly higher concentrations of silicic material (also high in [K], [U], and [Th]) than sampled regions. Within these areas are morphological features that are best explained by the existence of chemically evolved volcanic rocks. Observations of silicic domes [e.g., 1-5] suggest that sizable networks of silicic melt were present during crust formation. Isotopic data indicate that silicic melts were generated over a prolonged timespan from 4.3 to 3.9 Ga [e.g., 6-8]. The protracted age range and broad distribution of silicic rocks on the Moon indicate that their petrogenesis was an important mechanism for secondary crust formation. Understanding the origin and evolution of such silicic magmas is critical to determining the composition of the lunar crustal highlands and will help to distinguish between opposing ideas for the Moon's bulk composition and differentiation. The two main hypotheses for generating silicic melts on Earth are fractional crystallization or partial melting. On the Moon silicic melts are thought to have been generated during extreme fractional crystallization involving end-stage silicate liquid immiscibility (SLI) [e.g. 9, 10]. However, SLI cannot account for the production of significant volumes of silicic melt and its wide distribution, as reported by the remote global surveys [1, 2, 3]. In addition, experimental and natural products of SLI show that U and Th, which are abundant in the lunar granites and seen in the remote sensing data of the domes, are preferentially partitioned into the depolymerized ferrobasaltic magma and not the silicic portion [11, 12]. If SLI is not the mechanism that generated silicic magmas on the Moon then alternative processes such as fractional crystallization (only crystal-liquid separation) or partial melting should be considered as viable possibilities to be tested.

Mills, R. D.↗

DOE OSTI2021

Volatile Element Evidence of Local MORB Mantle Heterogeneity Beneath the Southwest Indian Ridge, 48°–51°E

Abstract The mantle source beneath the Southwest Indian Ridge (SWIR) reflects a complex history of contamination. Magmatic volatile contents are vital tracers of these kinds of heterogeneities, which may fractionate otherwise constant volatile/non‐volatile elemental ratios, such as the H 2 O/Ce ratio. Although several studies have recently used trace element and isotopic data to address mantle source heterogeneity and magmatic processes at SWIR 48°–51°E region, volatile element constraints provide a valuable test of models for the origins of mantle heterogeneities in this region. Here, we present new data for nine rare basaltic glass samples from the 48°–51°E region, which enable careful assessment of the effects of primary versus secondary processes on the glass volatile contents. These samples are strongly affected by variable extents of carbon degassing, and shallow assimilation of Cl‐rich fluid, but also reveal consistently high H 2 O/Ce ratios (458.8 ± 14.9), among the highest in MORBs, that cannot be explained by late‐stage secondary processes, crustal assimilation, or simple melting of peridotite mantle at variable depths. Instead, the high H 2 O/Ce ratios are features of the mantle source composition. The 48°–51°E region is notably more depleted in highly incompatible trace elements relative to other regions of the SWIR, although this depletion is not apparent in H 2 O, which is similarly abundant throughout the SWIR. We link the high H 2 O/Ce ratios in these glasses with other trace element characteristics diagnostic of subduction and fluid addition, suggesting that the mantle source reflects signatures of a refractory mantle residue that previously melted within a subduction zone.

Wang, Wei↗

DOE OSTI2021

Inelastic scattering in isotopologues of O 2 –Ar: the effects of mass, symmetry, and density of states

The two species considered here, O 2 (oxygen molecule) and Ar (argon-atom), are both abundant components of Earth's atmosphere and hence familiar collision partners in this medium. O 2 is quite reactive and extensively involved in atmospheric chemistry, including Chapman's cycle of the formation and destruction of ozone; while Ar, like N 2 , typically plays the nevertheless crucial role of inert collider. Inert species can provide stabilization to metastable encounter-complexes through the energy transfer associated with inelastic collisions. The interplay of collision frequency and energy transfer efficiency, with state lifetimes and species concentrations, contributes to the rich and varied chemistry and dynamics found in diverse environments ranging from planetary atmospheres to the interstellar and circumstellar media. The nature and density of bound and resonance states, coupled electronic states, symmetry, and nuclear spin-statistics can all play a role. Here, we systematically investigate some of those factors by looking at the O 2 –Ar system, comparing rigorous quantum-scattering calculations for the 16 O 16 O– 40 Ar, 18 O 16 O– 40 Ar, and 18 O 18 O– 40 Ar isotope combinations. A new accurate potential energy surface was constructed for this purpose holding the O 2 bond distance at its vibrationally averaged distance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2003

Strangelove Ocean and Deposition of Unusual Shallow-Water Carbonates After the End-Permian Mass Extinction

The severe mass extinction of marine and terrestrial organisms at the end of the Permian Period (approx. 251 Ma) was accompanied by a rapid negative excursion of approx. 3 to 4 per mil in the carbon-isotope ratio of the global surface oceans and atmosphere that persisted for some 500,000 into the Early Triassic. Simulations with an ocean-atmosphere/carbon-cycle model suggest that the isotope excursion can be explained by collapse of ocean primary productivity (a Strangelove Ocean) and changes in the delivery and cycling of carbon in the ocean and on land. Model results also suggest that perturbations of the global carbon cycle resulting from the extinctions led to short-term fluctuations in atmospheric pCO2 and ocean carbonate deposition, and to a long-term (>1 Ma) decrease in sedimentary burial of organic carbon in the Triassic. Deposition of calcium carbonate is a major sink of river-derived ocean alkalinity and for CO2 from the ocean/atmosphere system. The end of the Permian was marked by extinction of most calcium carbonate secreting organisms. Therefore, the reduction of carbonate accumulation made the oceans vulnerable to a build-up of alkalinity and related fluctuations in atmospheric CO2. Our model results suggest that an increase in ocean carbonate-ion concentration should cause increased carbonate accumulation rates in shallow-water settings. After the end-Permian extinctions, early Triassic shallow-water sediments show an abundance of abiogenic and microbial carbonates that removed CaCO3 from the ocean and may have prevented a full 'ocean-alkalinity crisis' from developing.

Rampino, Michael R.↗

NASA NTRS2014

Noble Gases in Two Fragments of Different Lithologies from the Almahata Sitta Meteorite

The Almahata Sitta meteorite, whose preat-mospheric body was the asteroid 2008 TC3, fell on October 7, 2008 in the Nubian Desert in northern Sudan [e.g., 1, 2]. Numer-ous fragments have been recovered during several expeditions organized from December 2008 [2]. The meteorite was classified as an anomalous polymict ureilite with several different kinds of chondritic fragments [e.g., 3-5]. Noble gas studies performed on several fragments from the meteorite showed cosmic-ray expo-sure ages of about 20 My [e.g., 6-8], although slightly shorter ages were also reported in [9, 10]. Concentrations of trapped heavy noble gases are variable among the fragments of different lithologies [9, 10]. We report noble gas data on two samples from the #1 and #47 fragments [2], which were the same as those re-ported by Ott et al. [9]. Experimental Procedure: Weights of bulk samples #1 and #47 used in this work were 16.1 mg and 17.6 mg, respectively. Noble gases were extracted by stepwise heating at the tempera-tures of 800, 1200 and 1800˚C for #1 and 600, 800, 1000, 1200, 1400, 1600 and 1800˚C for #47. Concentrations and isotopic ra-tios of noble gases were measured with a modified-VG5400/MS-III at the Geochemical Research Center, University of Tokyo. Results and Discussion: Cosmogenic He and Ne are domi-nant in both #1 and #47, but trapped Ar, Kr and Xe concentra-tions are much higher in #47 than in #1, showing that noble gas compositions in #47 are similar to those of ureilites. 3He/21Ne and 22Ne/21Ne of cosmogenic He and Ne are 4.8 and 1.12 for #1 and 3.6 and 1.06 for #47, respectively, both of which plot on a Bern line [11]. This indicates negligible loss of cosmogenic 3He from #1 in our sample, unlike the low 3He/21Ne of 3.1 for #1 by Ott et al. [9]. Concentrations of cosmogenic 3He and 21Ne (10-8 cc/g) are 30 and 6.3 for #1 and 32 and 9.0 for #47, respectively, which are higher than those in [9] and give cosmic-ray exposure ages of ca. 20 My depending on assumed production rates. Rela-tive abundances of trapped 36Ar, 84Kr and 132Xe for #1 resemble those of Q-component, which is a dominant trapped noble gas component in chondrites. In contrast to #1, #47 plots below a trend for ureilites [12] as well as Q, which implies a partial loss of trapped 36Ar from the lithology of #47.

Nagao, K.↗

DOE OSTI2024

Evaluation of material accountancy techniques for 233 Pa from thorium nuclear fuels

Thorium is a promising alternative to uranium as nuclear fuel with advantages such as higher abundance, lower production of long-lived transuranic elements, and potentially better proliferation resistance. However, thorium presents a potential pathway for proliferation where produced 233 Pa can be diverted for the clandestine production of safeguarded 233 U. To prevent this, the ability to detect and measure 233 Pa must be assessed. This paper reviews several nuclear material accountancy techniques to determine their suitability for detecting 233 Pa extracted from irradiated thorium fuel. Hybrid K-edge densitometry and passive gamma spectroscopy have been found to be the best options based on technology maturity, cost, accuracy, and acquisition time. Thorium can be used in various reactor designs such as pressurized water reactors (PWRs), Canada deuterium uranium (CANDU) reactors, and molten salt reactors (MSRs). Therefore, thorium-uranium oxide fueling was modeled for three representative reactors (PWR, CANDU, MSR), burning the fuel to 47 GWd/MTHM for PWR, 19 GWd/MTHM for CANDU, and at a steady power of 52.711 MW/MTHM for MSR. Within each model, the protactinium element in the used fuel was extracted and its isotopic content analyzed. Simulated results indicated that 233 Pa can be detected using passive gamma spectroscopy in each fuel type at all decay times (0–300 days) following separation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

NASA NTRS1997

A survey of the chemical properties of the M17 and Cepheus A cloud cores

We present the results of a systematic survey of the chemical properties of two giant molecular cloud (GMC) cores in M17 and Cepheus A. In all, we have mapped the emission from 32 molecular transitions of 13 molecules and seven isotopic variants over a 4' x 5' region in each core. Each map includes known sites of massive star formation, as well as the more extended quiescent material. In M17 most molecules have emission peaks away from the H II region/molecular cloud interface, while two species, HC3N and CH3C2H, deviate from this structure with sharp maxima closer to this interface. In Cepheus A the core is influenced by a compact high-velocity molecular outflow and a more extended low-velocity flow. The molecular emission distributions in this source are generally quite similar, with most molecules peaking near the center of the core to the east of the compact H II region HW 2. A few molecules, SO, CH3OH, H13CN, and C18O, have more extended emission. Only two molecules, CO and HCO+, appear to trace the high- and low-velocity outflows; all other species are tracing the quiescent core. We have used the results of previous studies of the density and temperature of the dense gas in the same cloud cores to derive accurate abundances relative to CO for several positions in each core. The principal result is that the chemical composition of all the cores we have surveyed (which include OMC-1 as well as M17 and Cepheus A) show remarkable similarity, both within a given core and among the cores. This suggests that the chemical processes are similar in quiescent GMC core material. In M17 the lack of variation of molecular abundances is remarkable because the radiation field and the gas temperature are known to vary appreciably throughout the surveyed region, suggesting that the bulk of the emission arises from gas that is well shielded from radiation.

Non-NASA Center↗

NASA NTRSDate not supplied

Tin-Essako 001: A Metal-Rich Ureilite?

Introduction: Metal-rich achondrites include a variety of types, and likely have a variety of origins. Models range from gravitational mixing at the core-mantle boundaries of differentatiated asteroids, to complex impact mixing scenarios. We describe a new type of metal-rich achondrite that might be the first metal-rich ureilite. Sample: Tin-Essako (TE) 001 (~4.3 g) was found in Mali in 2020 and purchased by Jay Piatek in 2021. It was classified as a metal-rich ungrouped achondrite, with olivine and oxygen isotope (d18O=8.2810‰, d17O=3.718‰, avg. 3) compositions suggesting affinity to ureilites [1]. We studied one polished section (~187.7 mm2) of TE 001. Petrography: TE 001 consists of ~60% metal and 40% silicates, heterogeneously distributed. The metal is largely fresh, but iron oxides (presumably terrestrial) occur along one edge and in some patches and veins in the interior. The silicates are dominantly olivine (≥90%), with melt-textured areas of plagioclase + Si-rich glass. Minor phases include chromite and carbon. Olivine occurs as rounded grains (up to ~2.5 mm) in metal, commonly with rims of melt-textured plagioclase + glass. Olivine also occurs in more massive areas having a “honeycomb” texture, with rounded olivine “cells” surrounded by an interstitial network of reduced olivine riddled with tiny metal grains, plus melt-textured plagioclase + Si-rich glass. Chromite occurs as subhedral to rounded grains; smaller grains (30-250 mm) are included in olivine and a few larger grains (400-500 mm) are isolated within metal. A carbon phase occurs as lacy-textured rims around olivine grains in metal, or small patches within metal. Mineral Compositions: The olivine (excluding interstitial areas) is Fo 73.9±0.5, with 0.25±0.02 wt.% CaO, 0.31±0.01 wt% Cr2O3, 0.01 wt.% NiO, and molar Fe/Mn=49.8±2.2 (53 analyses). Olivine in interstitial areas has Fo up to at least 91. Smaller chromite grains have Fe# (molar Fe/[Fe+Mg]) = 0.54±0.01, Cr# (molar Cr/[Cr+Al]) = 0.52±0.01, 0.52±0.02 wt.% V2O3 and 0.21±0.04 wt% ZnO (28 analyses). One larger grain is zoned from Fe# = 0.45, Cr# =0.52 to Fe# = 0.40, Cr# =0.57, and contains thin Al-rich lamellae not resolved by EMPA. One irregularly shaped patch of chromite included in olivine has Fe# =0.26 and contains no ZnO. Plagioclase laths are An ~53-60, with ≤0.01 wt.% K2O. Glass contains 75-76 wt% SiO2 and ~16 wt% Al2O3. The metal contains 5.2±0.2 wt% Ni, 0.46±0.02 wt.% Co, and 0.01±0.01 wt.% Cr, with Si and P below detection (168 analyses). Discussion: The olivine + chromite assemblage in TE 001 is similar to the most ferroan ureilites (Fo ~75-79 [2]), as are the oxygen isotopes [1]. The presence of a carbon phase supports this, although the identity of this phase (graphite as in ureilites?) remains to be determined. The “honeycomb” textured areas, in particular, the presence of olivine “reduction rims,” resemble shock-smelted olivine areas in ureilites [3], but interstitial melt-textured plagioclase laths + glass like those in TE 001 have not been reported in such (or any) ureilites. Olivine in TE 001 is marginally more ferroan than in the most FeO-rich ureilite, with Fe-Mg-Mn composition offset from the trend of olivine + low-Ca pyroxene ureilites similar to augite-bearing ureilites [4]. CaO and Cr2O3 contents are in the range of those in ureilite olivine [ ] , though Cr2O3 is at the extreme low end of the range [5]. Chromites (except the unusual one) have similar Fe# to the most ferroan primary chromites in ureilites [2], but distinctly lower Cr# (0.52 vs. 0.71). Metal compositions are with the range for metal in ureilites [7]. The absence of pyroxene and sulfide, and the high abundance of metal in TE 001, are unlike ureilites. One possibility is that a ferroan, chromite-bearing, pyroxene-poor ureilite was invaded (possibly due to impact) by a metallic liquid (low S content suggests very high temperature), resulting in complete melting of pyroxene and smelting of olivine, with rapid recrystallization of melted silicate as plagioclase + glass. Alternatively, a pre-existing metal-rich ureilite assemblage may have been impact melted. Additional types of data will be obtained to evaluate these hypotheses (i.e., is the metal indigenous?) and assess affinity to ureilites.

olivine↗

NASA NTRSDate not supplied

A Combined Al-Mg/Pb-Pb Age of the Solar System

Astrophysical models of planet formation and protoplanetary disk evolution demand precise and accurate timing of the sequence of events in the solar nebula, relative to a time t=0, usually taken to be during the short epoch of CAI (Ca-rich, Al-rich inclusion) formation. Most CAIs formed withlive26Al (mean-life τ26= 1.034 Myr [1]), with an abundance 26Al/27Al ≈ (26Al/27Al)SS= 5.23 × 10-5[2]. We adopt this as the widespread level of 26Al in the solar nebula at t=0. Assuming spatial homogeneity of 26Al, an inclusion that had less 26Al, (26Al/27Al)0, formed a time Δt26= τ26ln[(26Al/27Al)SS/ (26Al/27Al)0] after t=0.These ages are typical precise to within ±0.1 Myr. Igneous bulk meteorites and inclusions can be relatively dated by the Al-Mg chronometer, but only ifΔt26<6 Myr. The Pb-Pb system is useful as a longer relative chronometer. It yields absolute ages tPb using 207Pb/206Pb, 206Pb/204Pb, and 238U/235U ratios measured indifferent portions of a sample, assuming certain half-lives [4]. These absolute ages are uncertain to within ±9 Myr due to uncertainties in the 235U half-life[3], but times of formation ΔtPb= tCAI–tPb relative to t=0, are more precise(±0.5Myr),iftCAI can be found. Here, tCAI means the Pb-Pb age that would be measured in CAIs using the half-lives the community typically uses, if they achieved isotopic closure at t=0. Unfortunately, direct Pb-Pb dating of CAIs has not definitively determined tCAI. Based on four CAIs with canonical (26Al/27Al)0,[5,6] found tPb= 4567.30 ± 0.16 Myr. No other CAI ages with measured 238U/235U have been reported in the refereed literature, but there are hints of other CAIs with ages tPb= 4568.0 ± 0.2 Myr [7] and tPb= 4568.3 ± 0.2 Myr [8].It is unclear whether anyof these igneous type B CAIs isotopically closed at t=0 or represents tCAI. Instead of measurements, we advocate finding tCAI by minimizing the discrepancies between the Al-Mg and Pb-Pb chronometers. Assuming Δt26=ΔtPb, we find the implied t’CAI= tPb+Δt26, then define t*CAIas the weighted mean of the t’CAI. t*CAIis the best guess for the Pb-Pb age of t=0; the assumption of homogeneity is justified if the t’CAI cluster within errors around t*CAI. This statistical approach is similar to, but improves on, that of[9]. We find t*CAI= 4568.73 ± 0.16 Myr. Below we discuss our methodology and the implications of this age for CAIs, 1.4 Myr older than the reported and typically used age 4567.30±0.16 Myr. Methods: We base our estimate of t*CAIon five achondrites for which published (26Al/27Al)0and Pb-Pb ages exist: the quenched angrites D’Orbigny, Sahara 99555 (SAH 99555), and Northwest Africa (NWA) 1670; the pseudo-eucrite Asuka 881394; and the inner disk achondrite. All are “NC” (non-carbonaceous) achondrites that likely cooled quickly enough that the Al-Mg and Pb-Pb systems achieved isotopic closure simultaneously. We also considered the “CC” (carbonaceous chondrite-like) achondrites NWA 2796 and NWA 6704, butdo not include them in our fit. Al-Mg and Pb-Pb seem not to have closed simultaneously, possibly because formation in the outer disk from volatile-rich composition led to slower cooling. Of the 8 chondrules from NWA 5697 measured by [20,21], we also consider the 4 for which 238U/235U was measured: 2-C1, 5-C2, 3-C5, 11-C1.Depending on their post-formation thermal histories, the Al-Mg and Pb-Pb systems in chondrules may or may not have closed simultaneously. Table 1: (26Al/27Al)0, Pb-Pb ages of selected samplesSample(26Al/27Al)0/ 10-6RefPb-PbRefD’Orbigny3.98±0.15104563.43±0.19♮10-12SAH 995553.64±0.18104563.88±0.2712NWA16705.92±0.59104564.39±0.24*10Asuka 88139413.1±0.5613-154564.98±0.1715NWA 73253.03±0.14164563.4±2.616NWA 27963.94±0.16174562.89±0.5917NWA 67043.03±0.14184562.76±0.26192-C17.56±1.53204567.57±0.56*215-C27.04±1.51204567.54±0.52*213-C58.85±1.83204566.20±0.63*2111-C15.55±1.84204565.84±0.72*21*regression based on one subset of data points ♮weighted mean of two datasets Pb-Pb ages are proportional to the intercept of the line formed by linear regression of 207Pb/206Pb vs. 206Pb/204Pb data from various washes, leachates and residues of acid dissolution of a sample. Because contamination by terrestrial or primordial Pb is pervasive, some fractions must be excluded from regressions to ensure a fit with acceptable mean squares weighted deviation (MSWD). Usually points are excluded based on low [Pb], or low 206Pb/204Pb ratio(low radiogenic component), with single outliers identified [11,12,15,16,17]. In the starred examples (Table 1)and the case of 3 CAI Pb-Pb ages [5], up to half the points were excluded solely because did not fit a pre-determined line. This approach is vulnerable to confirmation bias and produces fits with low MSWD and too-low Pb-Pb age uncertainty. Regressing the same data points as [10], were produce the Pb-Pb age of NWA 1670 of 4564.39±0.24 Myr. But selecting other combinations of data points, other, equally valid, isochrons yield ages from 4563.77±0.21 Myr to 4564.64±0.23 Myr. Similar arguments apply to the Pb-Pb isochrons built by [21] for chondrules 2-C1 (we find 4567.33±0.44 to 4567.85±0.46 Myr), 5-C2 (4566.84±0.53 to 4567.70±0.44 Myr), 3-C5 (4565.84±0.54to 4567.04±0.54)and 11-C1 (4565.36±0.51 to 4565.74±0.45 Myr). Our adopted ages for these and NWA 1670 are listed in Table 2.Table 2. tCAI estimated from various components, using our regressions for the chondrules & NWA 1670.SampleΔt26(Myr)tPb(Myr)t’CAI(Myr)D’Orbigny5.05±0.044563.43±0.194568.48±0.19SAH 995555.14±0.054563.88±0.274569.02±0.27NWA16704.64±0.104564.21±0.634568.85±0.67Asuka 8813943.81±0.044564.98±0.174568.79±0.17NWA 73255.33±0.054563.4±2.64568.7±2.6NWA 27965.06±0.044562.89±0.594567.95±0.59NWA 67045.29±0.134562.76±0.264568.05±0.292-C12.00±0.214567.59±0.704569.59±0.725-C22.07±0.224567.23±0.914569.30±0.933-C51.84±0.214566.44±1.124568.28±1.1411-C12.32±0.344565.52±0.664567.84±0.73achondrite4568.72±0.16chondrules4568.76±0.58combined4568.73±0.16A weighted average of the five NC achondrites(or just D’Orbigny, SAH 99555 and Asuka 881394)yields t*CAI= 4568.72 ± 0.16Myr. All are consistent with this value to within 1.8σ, and MSWD=1.5. Including the 4 U-corrected chondrules, t*CAI= 4568.73± 0.16Myrwith MSWD=1.66, which is statistically significant. All chondrules and NC achondrites are consistent with this to within 1.8σ, (Figure 1).Figure 1. Al-Mg formation times after t=0 vs. Pb-Pb ages. The five NC achondrites and four chondrules are consistent with a Pb-Pb age of t=0 of 4568.7 Myr. Discussion: The data from achondrites and chondrules are consistent with a single Pb-Pb age at t=0, justifying the assumption of 26Al homogeneity. The age, 4568.7 Myr, is ≈1.4 Myr older than the commonly accepted Pb-Pb age of CAIs that formed with canonical 26Al/27Al at t=0 [3]. Others have interpreted the discrepancy to signify 26Al heterogeneity in the CAI-forming region[5,21]. We suggest instead that CAIs were exposed to transient heating events that reset the Pb-Pb system without disturbing the Al-Mg system. Notably, chondrules typically experienced transient heating at these times in the nebula [22]. If so, direct measurements of CAIs will not yield as reliable a Pb-Pb age of t=0 as statistical approaches like this and that of [9].References:[1] Auer et al. 2009. [2] Jacobsen, B et al. 2008, EPSL 272, 353-364. [3] Tissot, Fet al. 2017, GCA 213, 593-617.[4] Villa, I et al. 2016, GCA 172, 387-392.[5] Amelin, Y et al. 2010, EPSL 300, 343-350.[6] Connelly, Jet al. 2012, Science 338, 651.[7] Bouvier, Aet al. 2011, LPICo 1639, 9054. [8] Bouvier, Aand Wadhwa, M2010, Nat Geosci 3, 637-641.[9] Nyquist, Let al. 2009, GCA 73, 5115-5136.[10] Schiller et al. 2015. [11] Wadhwa & Brennecka 2012. [12] Tissot et al. 2017. [13] Nyquist et al. 2003. [14] Wadhwa et al. 2009. [15] Wimpenny et al. 2019, GCA 244, 478-501.[16] Koefoed et al. 2016, GCA 183, 31-45. [17] Bouvier, A et al. 2011, GCA 75, 5310-5323. [18] Sanborn, Met al. 2019, GCA 245, 577-596. [19] Amelin, Yet al. 2019, GCA 245, 628-642.[20] Bollard, Jet al. 2017, Sci Adv 3 ,e1700407. [21] Bollard, Jet al. 2019, GCA 260, 62-83.[22] Villeneuve, J et al. 2009, Science 325, 985

S. J. Desch↗

NASA NTRS2022

Sample Materials Considerations for Curating and Processing Pristine MSR Samples

The perseverance rover is collecting and caching samples of Mars as part of the Mars 2020 mission, which represents the first leg of a multi-mission Mars Sample Return Campaign. The MSR Campaign is an international partnership that will result in delivery of the first martian samples to Earth that were not delivered through meteoritic infall. All meteorites, regardless of how they were handled from recovery to curation, have experienced uncontrolled entry and exposure to the terrestrial environment. Whilst meteorite deliveries are serendipitous, they are also unplanned events that require reactionary responses for recovery and curation. However, with the direct return of pristine astromaterials from another body, we are afforded the ability to design a facility in advance of sample delivery to keep those samples in a pristine (i.e., as returned) state for an indefinite period of time. Given that the curation and processing infrastructure needs to be made out of something, it is important to choose materials for the pristine curation environment that will optimize between the need to effectively process samples and the need to minimize contamination of the samples. The Johnson Space Center (JSC) has an optimized list of materials that have been used in previous sample return missions that includes 304/316 Stainless Steel, Teflon, and T6061 Aluminum (1). This set of materials are compatible with inorganic, organic, and biological cleanliness requirements and protocols. Furthermore, only these materials are permitted to come in contact with pristine samples. We note that JSC uses Neoprene and Hypalon for the gloves on their gloveboxes, but the glove material never comes in direct contact with the samples, only the approved materials. The MSR sample tubes will be made of Ti, so Ti may be an acceptable material for making tools, but the minor and trace element abundances of 304 and 316 stainless steel are well known and do not inhibit scientific investigations of metals, including HSE (2). More work is needed to determine whether the same is true for Ti alloys. In addition to defining the materials in the pristine environment, one must also choose whether the pristine environment will be under vacuum or under a specific atmospheric composition and pressure. Although JAXA has successfully implemented pristine curation vacuum chambers for their Hayabusa and Hayabusa2 samples (3), a vacuum environment is not appropriate for martian samples because it may drive deliquescence of mineral phases in the samples that are sensitive to pressure and relative humidity (4). Consequently, the pristine environment for the martian samples should be under an inert gas. It will be crucial to minimize the number of gases that come into direct contact with samples and these gases will need to be high purity and consistent throughout the pristine isolators. Samples at JSC are stored under high purity gaseous nitrogen (1). Dry N2 gas has not been a problem for N isotope studies for high-T release phases, but an additional inert atmosphere like Ar may be needed for samples where there is a particular concern about low-T release of N from bulk sample analysis. References: (1) McCubbin FM, et al. (2019) Space Science Reviews, 215, 1-81. (2) Day JMD, et al. (2018) Meteorit. Planet. Sci. 53:1283-1291. (3) Yada, T., et al., (2014). Meteorit. Planet. Sci. 49, 135-153. (4) Tosca NJ, et al. (2021). Astrobiology, in press, doi:10.1089/ast.2021.0115.

F M McCubbin↗

DOE OSTI2021

Soil organic matter is principally root derived in an Ultisol under oak forest

To a large degree, the sources and stability of soil organic carbon remain poorly constrained. A clear understanding of links among the components of the soil C cycle is hampered by the complexity of the system as well as challenges associated with partitioning bulk soil C into meaningful fractions. A large accidental 14 CO 2 release at the Oak Ridge Reservation in Tennessee, USA provided a strong label pulse into adjacent, well-studied oak forests, resulting in highly elevated Δ 14 C values in leaf litter (~1000‰) and roots (~260–450‰). A four-year manipulative study was conducted to determine the relative contribution of litter versus roots to the bulk mineral soil C pool, as well as to free light, occluded light and heavy fractions. The heavy fraction was further split into fractions with densities of 1.7–2.4 g cm –3 and >2.4 g cm –3 to test the homogeneity of the mineral-associated fraction of C. Substantial concentrations of label were detected in all soil fractions within a year of the 14 CO 2 release, indicating rapid incorporation of newly fixed photosynthates in all fractions of soil organic C, regardless of differences in stability inferred by previous work. This rapid incorporation of label occurred only in treatments where roots were labeled, indicating that roots are the major source of inputs to mineral soil C stocks at these sites. Separation of the heavy fraction into subfractions of intermediate (1.7–2.4 g cm –3 ) and high (>2.4 g cm –3 ) density indicated that both subfractions incorporated label at similar rates, despite significant differences in degree of microbial processing. In general, the rate of label incorporation suggested a much faster turnover for all fractions than indicated by natural radiocarbon abundance values. This study suggests that within each soil fraction there are portions of slow-cycling and fast-cycling materials, and the determination of an average turnover time or mean age is dependent on experimental approach. The rapid incorporation of label into all fractions within a year regardless of inferred stability implies a high degree of heterogeneity in all fractions regardless of how finely the soils are partitioned. Further refinement of the nature and drivers of this heterogeneity could yield important insights into the soil C cycle.

58 GEOSCIENCES↗

DOE OSTI2023

Statistical chronometry of Meteorites: II. Initial abundances and homogeneity of short-lived radionuclides

Astrophysical models of planet formation require accurate radiometric dating of meteoritic components by short-lived (Al-Mg, Mn-Cr, Hf-W) and long-lived (U-Pb) chronometers, to develop a timeline of such events in the solar nebula as formation of Ca-rich, Al-rich Inclusions (CAIs), chondrules, planetesimals, etc. CAIs formed mostly around a time (“t=0”) when the short-lived radionuclide 26 Al (t 1/2 = 0.72 Myr) was present and presumably homogeneously distributed at a known level we define as ( 26 Al/ 27 Al) SS = 5.23 × 10 -5 . The time of formation after t=0 of another object can be found by determining its initial ( 26 Al/ 27 Al) 0 ratio and comparing it to ( 26 Al/ 27 Al) SS . Dating of meteoritic objects using the Mn-Cr or Hf-W systems is hindered because the abundances ( 53 Mn/ 55 Mn) SS and ( 182 Hf/ 180 Hf) SS at t=0 are not known precisely. To constrain these quantities, we compile literature Al-Mg, Mn-Cr, Hf-W and Pb-Pb data for 13 achondrites and use novel statistical techniques to minimize the discrepancies between their times of formation across these systems. We find that for ( 53 Mn/ 55 Mn) SS = (7.80±0.36)×10 -6 , ( 182 Hf/ 180 Hf) SS = (10.41 ± 0.12) × 10-5, t SS = 4568.65 ± 0.10 Myr, and a 53 Mn half-life of 3.98 ± 0.22 Myr, these four free parameters make concordant 18 formation times recorded by the different systems in all six known volcanic achondrites (the quenched angrites D’Orbigny, Sahara 99555, Northwest Africa 1670; the psuedo-eucrites Asuka 881394 and Ibitira; and the basaltic achondrite Northwest Africa 7325). These parameters also make concordant the ages derived for chondrules from CB/CH achondrites, formed simultaneously in an impact. The other seven achondrites are not quite concordant, but are plutonic angrites or ‘carbonaceous achondrites’ for which simultaneous closure of the isotopic systems might not be expected. Our findings provide very strong support for homogeneity of 26 Al, 53 Mn, and 182 Hf in the solar nebula, and our approach offers a path for more precise chronometry

79 ASTRONOMY AND ASTROPHYSICS↗

NASA NTRS1988

The early archaean crustal history of West Greenland as recorded by detrital zircons

The isotope systematics of some of the oldest samples on Earth from both Greenland and Australia was discussed. The antiquity was confirmed of the 4.1 to 4.2 Ga zircons from Western Australia; the model Lu-Hf age of these zircons, as measured with the ANU ion probe is 4.14 + or - 0.24 Ga, although the oldest preserved rock units there are anorthosites with a Lu-Hf model age of about 3.73 Ga. U-Pb ion probe ages of detrital zircons ranging between 2.87 and 3.89 Ga from an Akilia association quartzite was reported, whose age of deposition is probably around 3.8 Ga. It was argued that the younger age in this range are discordant because of late Pb-loss, probably associated with a high grade metamorphic event at about 3.6 Ga. It was also argued that the earliest crust in West Greenland and elsewhere is about 3.9 Ga, but in some places, such as Western Australia, crustal evolution took place much earlier, perhaps starting as far back as 4.3 Ga. This would account for the presence in that terrane of abundant K rich granitoid, the paucity of tonalitic and trondhjemitic materials, and the existence of Eu anomalies in early Archean sediments.

Kinny, P. D.↗

NASA NTRS1994

Alkali element depletion by core formation and vaporization on the early Earth

The depletion of Na, K, Rb, and Cs in the Earth's upper mantle and crust relative to their abundances in chondrites is a long standing problem in geochemistry. Here we consider two commonly invoked mechanisms, namely core formation, and vaporization, for producing the observed depletions. Our models predict that a significant percentage of the Earth's bulk alkali element inventory is in the core (30 percent for Na, 52 percent for K, 74 percent for Rb, and 92 percent for Cs). These predictions agree with independent estimates from nebular volatility trends and (for K) from terrestrial heat flow data. Our models also predict that vaporization and thermal escape during planetary accretion are unlikely to produce the observed alkali element depletion pattern. However, loss during the putative giant impact which formed the Moon cannot be ruled out. Experimental, observational, and theoretical tests of our predictions are also described. Alkali element partitioning into the Earth's core was modeled by assuming that alkali element partitioning during core formation on the aubrite parent body (APB) is analogous to that on the early Earth. The analogy is reasonable for three reasons. First, the enstatite meteorites are the only known meteorites with the same oxygen isotope systematics as the Earth-Moon system. Second, the large core size of the Earth and the V depletion in the mantle requires accretion from planetesimals as reduced as the enstatite chondrites. Third, experimental studies of K partitioning between silicate and metal plus sulfide show that more K goes into the metal plus sulfide at higher pressures than at one atmosphere pressure. Thus partitioning in the relatively low pressure natural laboratory of the APB is a good guide to alkali elemental partitioning during the growth of the Earth.

Lodders, K.↗

DOE OSTI2022

Quantifying fish otolith mineralogy for trace-element chemistry studies

Otoliths are frequently used to infer environmental conditions or fish life history events based on trace-element concentrations. However, otoliths can be comprised of any one or combination of the three most common polymorphs of calcium carbonate - aragonite, calcite, and vaterite - which can affect the ecological interpretation of otolith trace-element results. Previous studies have reported heterogeneous calcium carbonate compositions between left and right otoliths but did not provide quantitative assessments of polymorph abundances. In this study, neutron diffraction and Raman spectroscopy were used to identify and quantify mineralogical compositions of Chinook salmon Oncorhynchus tshawytscha otolith pairs. We found mineralogical compositions frequently differed between otoliths in a pair and accurate calcium carbonate polymorph identification was rarely possible by visual inspection alone. The prevalence of multiple polymorphs in otoliths is not well-understood, and future research should focus on identifying otolith compositions and investigate how variations in mineralogy affect trace-element incorporation and potentially bias environmental interpretations.

60 APPLIED LIFE SCIENCES↗

NASA NTRS1995

Measurements of the H2(13)CO ortho/para ratio in cold dark molecular clouds

H2(13)CO has been detected for the first time toward cold dark molecular clouds using the NRAO 12 m telescope. The H2(13)CO ortho/para abundance ratio R for B335, which we report as R approximately 1.7, suggests equilibrium at the local kinetic temperature and appears to be distinctly different from that for both TMC-1 and L134N, where R is close to or higher than the statistical value 3. Since only B335 among the observed positions includes an imbedded IR source, this difference may result from heating of the grain surfaces, providing the energy necessary for desorption of formaldehyde formed on the grains.

NASA Discipline Exobiology↗

NASA NTRS2015

On Infrared Excesses Associated with Li-Rich K Giants

Infrared (IR) excesses around K-type red giants (RGs) have previously been discovered using Infrared Astronomy Satellite (IRAS) data, and past studies have suggested a link between RGs with overabundant lithium and IR excesses, implying the ejection of circumstellar shells or disks. We revisit the question of IR excesses around RGs using higher spatial resolution IR data, primarily from the Wide-field Infrared Survey Explorer. Our goal was to elucidate the link between three unusual RG properties: fast rotation, enriched lithium, and IR excess. Our sample of RGs includes those with previous IR detections, a sample with well-defined rotation and lithium abundance measurements with no previous IR measurements, and a large sample of RGs asserted to be lithium-rich in the literature; we have 316 targets thought to be K giants, about 40% of which we take to be Li-rich. In 24 cases with previous detections of IR excess at low spatial resolution, we believe that source confusion is playing a role, in that either (a) the source that is bright in the optical is not responsible for the IR flux, or (b) there is more than one source responsible for the IR flux as measured in IRAS. We looked for IR excesses in the remaining sources, identifying 28 that have significant IR excesses by approximately 20 micrometers (with possible excesses for 2 additional sources). There appears to be an intriguing correlation in that the largest IR excesses are all in Li-rich K giants, though very few lithium-rich K giants have IR excesses (large or small). These largest IR excesses also tend to be found in the fastest rotators. There is no correlation of IR excess with the carbon isotopic ratio, 12C/13C. IR excesses by 20 micrometers, though relatively rare, are at least twice as common among our sample of lithium-rich K giants. If dust shell production is a common by-product of Li enrichment mechanisms, these observations suggest that the IR excess stage is very short-lived, which is supported by theoretical calculations. Conversely, the lithium-enrichment mechanism may only occasionally produce dust, and an additional parameter (e.g., rotation) may control whether or not a shell is ejected.

Li-rich↗