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Publications and source records attributed to P Mane.
Constraining the initial abundances of short-lived radionuclides in planetary materials helps determine the spatial and temporal distribution of interstellar material added during the initial stages of Solar System formation.
A population study of the high temperature early-formed solid particles in the MIL 090019 CO3 carbonaceous chondrite, when compared to similar studies conducted on other chondritic meteorites, will provide insights into the accretion processes of early formed chondritic parent bodies.
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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
Introduction: Calcium-aluminum-rich inclusions (CAIs) are an important component of chondritic meteorites. They can contain materials that are thermodynamically predicted and isotopically age dated to be among the first-formed solids in our solar system [1-5]. Observed in some CAIs are micron to sub-micron sized inclusions rich in Fe, Ni, and high-Z elements such as Pt, Os, Ir and W, in the form of refractory metal nuggets (RMNs), fremdlinges, and ‘nugget like objects’ (NLOs) [1,6]. Refractory siderophile elements such as Os, Ir and Ru are thermodynamically predicted to condense at temperatures well in excess of the major CAI phases such as melilite, perovskite, spinel and hibonite [2,7-9]. These refractory metal inclusions in CAIs can therefore serve as probes into the thermodynamic landscape of the early solar protoplanetary disk. Here we report on a refractory grain identified in a CAI of the Leoville CV3 chondrite. This work is part of an ongoing effort to gain insight into the thermochemistry of the early solar system through systematic analyses of the structure and chemistry of various components in CAIs [10-13]. Sample and Analytical Techniques: A fluffy type A CAI (Fig. 1A) was identified in a section of the Leoville, CV3 chondrite (Center for Meteorite Studies, Arizona State University collection, #821_C_3) using a JOEL-JXA 8530F electron microprobe at Arizona State University. Backscattered electron (BSE) imaging and energy-dispersive X-ray spectroscopy (EDS) were used to identify refractory metal grains in the CAI using a Thermo Fisher (formerly FEI) Helios NanoLab 660 G3 focused-ion-beam scanning-electron microscope (FIBSEM) located at the Kuiper Materials Imaging and Characterization Facility (KMICF) at the Lunar and Planetary Laboratory, University of Arizona. The FIB is equipped with an EDAX EDS system. We selected one of the larger (micron-sized) refractory metal grains, designated as ‘Spud’ (Fig. 1B) for further analysis. ‘Spud’ was extracted and thinned to electron transparency (<100 nm) using the FIB-SEM located in KMICF, following methods described by [14- 15]. The FIB section was analyzed using a 200 keV Hitachi HF5000 scanning transmission electron microscope (S/TEM) located at KMICF. The HF5000 is equipped with cold-field emission gun, 3rd-order spherical aberration corrector for STEM imaging, and an Oxford Instruments X-Max N 100 TLE energydispersive spectroscopy (EDS) system with dual 100 mm2 windowless silicon-drift detectors (Ω = 2.0 sr). Selected-area electron-diffraction (SAED) patterns were acquired to aid in determination of crystallinity and phase. Results: The mineralogy, texture, and morphology of the CAI are consistent with that of a fluffy type A (FTA) CAI [16]. BSE imaging at high magnifications revealed grains with high contrast, indicative of compositions rich in elements of higher atomic number relative to surrounding material. These high-Z grains have sizes that range from ∼250 nm to 4 µm. EDS analyses confirm that the bright grains are metal-rich inclusions. A minor fraction of the grains are composed of only Fe and Ni, but the majority (∼60%) of the identified inclusions also contained various refractory siderophiles including Os, Ru, Zr, Ir and Mo. EDS analysis on the FIB-SEM of Spud shows that it contains Fe, Ni, Mo and Ru. High-angle annular dark-field (HAAFD) imaging and EDS mapping in the TEM (Fig. 2) show that Spud occurs in melilite (Ca1.9Al1.99Si1.06O7). Spud contains a subhedral to anhedral morphology and is compositionally heterogenous (polyphasic, Fig. 2). Local spatial correlation occurs among Fe, Ni, and Pt, and also among Os, Ru, and Mo. SAED patterns show that the Fe-Ni-Pt, Fe-Os-Mo-Ru and Fe-Pt regions are crystalline. Discussion: CAIs can contain various types of inclusions rich in Fe, Ni and refractory siderophiles such as Os, Ru, W and Pt [1]. RMNs are micron-sized, single phase alloy grains and can contain Os, Ir, Ru and Rh [1,7,17]. NLOs are also micron-sized inclusions, but contain two phases, a refractory metal, and an oxide [6]. Fremdlinge are the largest of such inclusions (tens of microns in size) and are complex aggregates of Fe-Ni alloy, silicates, oxides, and sulfides [1,17]. While the size of Spud matches previous descriptions of RMNs and NLOs, Spud is neither a single-phase alloy like RMNs, nor does it contain one metal phase and one oxide like NLOs. Spud does not match the above described categories of refractory metal inclusions. The presence of refractory siderophiles such as Mo, Os, Ru, and Pt suggests a high-temperature origin. Thermodynamic modelling by [7] indicates condensation temperatures of 1917 K, 1693 K, 1613 K and 1415 K for Os, Mo, Ru and Pt respectively. These models also show that following the initial condensation of a refractory metal, alloying of solutes such as Fe, Ni and W, occurs in levels proportional to their partial pressures in the surrounding gas. Such alloying occurs at temperatures above the condensation temperatures of common CAI phases such as melilite (1529 K), perovskite (1441 K), spinel (197 K) and forsterite (1354 K) [2]. The polyphasic nature of Spud could be the result of such high-temperature alloying, possibly shortly after the condensation of Mo and Ru at 1693 K and 1613 K respectively. That Spud occurs as an inclusion is consistent with it having formed prior to and at temperature above that of its host melilite in this FTA CAI, which is qualitatively consistent with such prior thermodynamic modeling. Further, the polyphasic nature of Spud is similar to refractory grains from a FTA CAI in the Northwest Africa (NWA) 8323, CV3 chondrite [11-13]. These data suggest that such refractory metal grains could have been widespread in the inner and early solar protoplanetary disk and represent some of the earliest formed solids to have condensed. Acknowledgments: Research and instrumentation supported by NASA grants #NNX12AL47G, #NNX15AJ22G and #80NSSC19K0509, and NSF grants #1531243 and #0619599. Fig 2. STEM data on ‘Spud’. HAADF Image (Top) False-color EDS Maps (Bottom) References: [1] MacPherson G. J. (2014) T. of Geochem. Vol I: Met. And Cosmochem. Processes, 139-179. [2] Lodders K. (2003) ApJ, 591, 1220-1247. [3] Ebel D. S. (2006) Met. & the Early S. Sys. II., 253- 277. [4] Amelin Y. (2002) Science, 297, 1678-1683. [5] Connelly J.N. et.al. (2012) Science, 338, 651-655. [6] Schwander D. et al. (2015) GCA, 18, 70-87. [7] Palme H. and Wlotzka F. (1976) EPSL, 33, 45-60. [8] Berg T. et al. (2009) ApJ, 702, 172-176. [9] Liffman K. et al. (2021) Icarus, 221, 89-105. [10] Zega T.J. et al. (2021) PSJ, 2, 115. [11] Ramprasad T. et al. (2020) LPSC LI, Abstract #2472. [12] Ramprasad T. et al. (2021) Microscopy & Microanalysis, S1, 2792-2794. [13] Ramprasad T. et al. (2021) 84th MetSoc, Abstract #6123. [14] Zega T.J. et al. (2007) MAPS, 42, 1373-1386. [15] Ramprasad T. et al. (2022) MAPS, in revision. [16] Grossman L. (1975), GCA, 39, 433-454. [17] El Goresy A. et al. (1978) LPSC IX, Abstract#1100
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Introduction: Primitive meteorites contain Calcium-Aluminum-rich Inclusions (CAIs)that preserve the records of the earliest times in the Solar System. CAIs record O isotopic variations with time and/or location from solar (16O-rich) to planetary (16O-poor) compositions [e.g., 1, 2].However, CAIs were also affected by parent body processing to varying degrees. The goal of this work was to identify the processes that resulted in the fine-scale spatial variations in oxygen isotopic compositions within the most ancient Solar System solids. We report oxygen isotopic composition of CAIs from MIL 090019 CO3.1 carbonaceous chondrite. MIL 090019 contains a high abundance of CAIs showing mineralogical as well as textural variations [3]. Methods: We analyzed 10 CAIs with different mineralogical assemblages, classified as corundum-bearing, grossite-bearing, hibonite-bearing, melilite-bearing, anorthite-bearing inclusions and amoeboid olivine aggregates(AOA’s). The mineralogical and petrological characterization of CAIs was performed using the JOEL Hyperprobe 8530 electron microprobe at NASA JSC. Oxygen isotopic imaging of the CAIs was done using the Cameca NanoSIMS 50L ion microprobe at NASA JSC. We followed the analytical protocol described in [4]. O-isotopic maps of the CAI were acquired by rastering a ~3 pA primary Cs+beam at 16 keVover an area of 20 ×20μm2over a period of ~7 hours. Negative secondary ions of 16O−, 17O−, 18O−, 28Si−, 24Mg16O−, 27Al16O−, and 40Ca16O−were simultaneously acquired using electron multiplier detectors at a mass resolving power sufficient to resolve the 16OH−interference from the 17O−peak, where the contribution of 16OH−was <0.1%.An electron flood gun was used to mitigate sample charging during the analyses. We used San Carlos olivine and Madagascar hibonite as isotopic standards to correct for the instrumental mass fractionation. The O-isotopic ratios were corrected for the quasi simultaneous arrival (QSA) effect and the detector dead time. All reported errors are 1 sigma. Results: The MIL 090019 carbonaceous chondrite hosts refractory inclusions varying in their mineralogies and textures[2, 3]. We found the oxygen isotopic compositions of mineral phases in MIL 090019 CAIs show large variations with Δ17O values varying from -27 to 0‰. A corundum-bearing inclusion records isotopic variations with corundum, melilite, perovskite, and anorthite showing Δ17Ovalues of -20 ±2.5, -10.2 ± 6.5, -10.7 ± 1.3,and -1.2 ± 3.2‰ respectively. A grossite-hibonite-bearing inclusion also records O-isotopic heterogeneity, where grossite, hibonite, Mg-rich spinel, and melilite show -3.7 ± 2.7, -22.9 ± 2.5, -21.4 ± 2.6, and -17.3 ± 2.8‰ respectively, whereas perovskite grains record a heterogenous isotopic composition ranging from -22.6 to -13.9‰. A hibonite-bearing inclusion shows average Δ17Ο values of -17.6 ± 5.3 ‰ and -15.1 ± 4.8 ‰ for hibonite and spinel respectively. The two perovskite grains also show relatively 16O-poor composition (Δ17Ο = -11.8 ± 6.4 ‰ and -8.6 ± 5.2 ‰). Anorthite has ~0.1 wt% Na2O and ~0.52 wt% FeO and a Δ17Ο value of -7.2 ± 5.0 ‰, whereas diopside records a Δ17Ο value of -3.5 ± 5.0 ‰. A hibonite-spinel-rich inclusion contains spinel and hibonite that are16O-rich (Δ17Οvalues -21.3 ± 2.8‰ and -19.4 ± 3.0‰, respectively). Melilite shows heterogenous oxygen isotopic composition, with an inner 16O-rich region and an outer 16O-poor region separated by a sharp boundary, with a bulk Δ17Ο= -16.2 ± 2.1‰, whereas two perovskite grains are relatively 16O-poor (Δ17Ο= -13.2 ± 3.7‰ and -7.1 ± 3.4‰).A spinel-rich inclusion contains perovskite grains with Δ17Οranging from -27.0 to -22.8 ‰and spinel with average Δ17Οvalue of -21.4 ± 2.8 ‰. In a melilite and spinel-rich CAI, perovskite, spinel, diopside, melilite, and Al-Ti-rich pyroxene record Δ17Ο values of-26.9 ± 4.6‰, -22.4 ± 4.3‰,-23.4 ± 4.9, -19.3 ± 3.4, and -19.0 ± 4.3 ‰ respectively. Olivine and spinel components of 2 AOA’s record a 16O-rich composition with Δ17O~-23‰. Discussion: The coexistence of 16O-rich and 16O-poor minerals within CAIs has been attributed to differing degrees of O isotopic exchange, reflecting a wide range of O diffusion rates[5]. However, the O isotopic heterogeneity observed in these CAIs cannot be explained by oxygen diffusion in nebular or parent body settings alone. The isotopic imaging of CAIs from the MIL 090019 meteorite shows variations in the O isotopic composition recorded in their mineral components, suggesting that these CAIs record the oxygen isotopic heterogeneity in the nebular gas from which they condensed. The coexistence of 16O-rich and 16O-poor mineral components in the CAI-forming region suggests that the gas in this region was not well-mixed and consisted of distinct 16O-rich and 16O-poor gaseous reservoirs.
Presolar grains formed in the outflows of dying stars and some have been preserved in primitive meteorites, interplanetary dust particles, and comet Wild 2 samples. Presolar silicates are one of the most abundant presolar phases, but are prone to destruction by parent body hydrothermal alteration. Refractory presolar phases, such as oxides and carbides, are more resistant to such alteration. Samples from asteroid Ryugu returned by JAXA’s Haya-busa2 mission show evidence for extensive aqueous alteration. To constrain the abundance of presolar grains in Ryugu, we conducted NanoSIMS isotopic mapping of fragments of a C0002 grain from Chamber C, perhaps from the asteroid sub-surface.
The samples of Ryugu returned by the Hayabusa2 spacecraft have mineralogy similar to CI chondrites and are dominated by secondary phases(e.g., phyllosilicates, carbonates, magnetite, sulfides) from extensive parent body aqueous alteration. Anhydrous minerals such as olivine, pyroxene, and spinel are rare and exist in phyllosilicate-rich clasts [2-4]. Oxygen isotopic studies of these minerals have shown a bimodal distribution with both 16O-rich and 16O-poor grains. In this study, we conducted NanoSIMS isotopic mapping of a clast found in a fragment of a C0002 grain from Chamber C, which may have derived from the asteroid sub-surface, to characterize small primary minerals
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Samples of C-type asteroid (162173) Ryugu returned by the Hayabusa2 mission of JAXA [1-3] have been found to be mineralogically, chemically, and isotopically similar to CI carbonaceous chondrites [3-6]. The rare CI meteorites have bulk chemical compositions closely matching the solar photosphere in all but the most volatile elements, and so are considered to represent the starting composition of the solar system. Paradoxically, however, all known CI have been extensively altered by aqueous fluids (i.e., they are CI1), so that their primary mineralogy, textures, and oxygen isotope compositions have been obscured. Thus, one of the most exciting discoveries from Ryugu samples is that they contain “less-altered” (CI2) areas, which have substantial abundances of anhydrous silicates (olivine and pyroxene) and Ca-Al-rich phases that may be remnants of primordial CI3 materials [4-11]. This discovery has motivated new investigations of CIs that show higher abundances of anhydrous silicate grains than previously recognized [9,12,13]. Such studies are an important step in the search for unaltered CI-like material, a so-called “holy grail” of meteoriticists [14]. To further this goal, we are studying Ryugu samples in the context of a previously unrecognized, potentially Ryugu-like, population of C2 materials that occur as xenoliths in polymict ureilites.
Introduction: Calcium-aluminum-rich inclusions (CAIs), are the first formed solids that define the age of the Solar System [1,2]. CAIs are thought to have condensed from nebular gas [3,4] within the first <1 Ma of Solar System formation [5,6]. CAIs have experienced numerous early Solar System processes including condensation, evaporation, melting, recrystallization, and aqueous alteration [e.g., 7]. The chemical, mineralogical, and textural diversity among CAIs results from a range of chemical and physical processes recorded during nebular and parent body epoch. This study aims to explore the mineralogical, textural, and chemical compositions of CAIs including the trace elemental abundances in CAI phases to determine the early Solar System processes recorded in them. Samples and Analytical Methods: We analyzed one CAI each from CV3 chondrites Northwest Africa (NWA) 5508 designated as ‘Saguaro’, and Northwest Africa (NWA) 12772 designated as ‘Hoopoe’. Back-scatter electron (BSE) images were collected using a Phenom XL scanning electron microscope (SEM) at the Lunar and Planetary Institute (LPI) and the JEOL JXA-8530F electron probe microanalyzer (EPMA) at Johnson Space Center (JSC)-NASA. Additionally, energy dispersive X-ray spectrometry (EDS) elemental maps of select areas for these samples were collected using a 15.0kV beam energy and a 40µA emission current. Using the EPMA, wavelength-dispersive X-ray spectroscopy (WDS) quantitative data were collected. In-situ trace element measurements for both CAIs were determined at JSC-NASA using a Photon Machines 193nm laser ablation system and a Thermo-Scientific Element-XR inductively coupled plasma mass spectrometer (ICP-MS). Analyses consisted of 30s ablations at 10Hz, spot sizes of 20-25µm, and a fluence of 6.0 J/cm2 for anorthite and melilite, and a 3.5 J/cm2 fluence for all other phases. NIST612 was used to correct for instrument drift, while BHVO-2g was used as a primary calibration standard. BCR-2g and in-house mineral standards were regularly measured as unknowns to ensure accuracy. Results: Saguaro is a coarse-grained CAI, ~11 x 6 mm in dimensions. Saguaro contains spinel, Al-rich pyroxene, anorthite, Mg-rich melilite, and minor perovskite in its interior and is therefore classified as a Type B CAI. Individual melilite grains shows normal compositional zoning with an Ak content ranging from ~24 to 54 with no apparent trend from the core to the edge of the CAI. The spinel appears euhedral and occurs both as clusters and as spinel palisades [8]. Two rim sequences surround most of the sample: the inner rim being a Wark-Lovering (WL) rim (~10-35 µm) containing pyroxene, spinel, and melilite (or anorthite), and the outer rim is a finer-grained, thicker (~100 µm), accretionary rim (Fig. 1). The mineral phases in Saguaro record an overall flat REE pattern with an average negative Eu anomaly in pyroxene, and an average positive Eu anomaly in anorthite and melilite respectively. Anorthite, melilite, and pyroxene have a minor depletion in Tm (Fig. 2). The Hoopoe CAI is a compact, coarse-grained ~6 × 4 mm in size. The major mineralogy includes hibonite, spinel, melilite, anorthite, and perovskite. Therefore, it is classified as a compact transitional type A and B. (?)zoning was observed in some hibonites. Individual melilite grains show both reverse and normal zoning, where the Ak content ranges from ~6- to 28. Melilite shows two distinct textures. One texture consisted of smooth melilite that appeared homogenous, while the second appeared to consist of many fine fractures. The spinel also often appears clustered. The WL-rim sequence surrounding Hoopoe is ~25 µm thick and composed of spinel, perovskite, hibonite, and melilite/anorthite. It is then partially surrounded by an outer accretionary rim (~75µm). Like before, refractory metal nuggets appeared concentrated near the WL rims. Other metal assemblages rich in Fe and Ni were also observed. All major mineral phases in Hoopoe display relatively flat REE patterns, except for varying Eu and Tm between phases (Fig. 2). There is a prominent negative Eu anomaly in perovskite and an average positive Eu anomaly in spinel, anorthite, and hibonite respectively (Fig. 2, 3). The mixed phases along the rim of the CAI also display a negative Eu anomaly, and all phases the CAI were depleted in Pb. Discussion: The CV3 CAIs analyzed in this study were classified based on their mineralogy and textures into Type A versus Type B CAIs [10]. Hibonite appears to be pseudomorphically replacing the spinel, (i.e., is hibonite in composition, but appears in the shape of spinel). Spinel palisades. The presence of spinel palisades present in Saguaro are consistent with the melting and recrystallization experienced by this CAI. Trace elemental analyses. Saguaro and Hoopoe display similar trace element patterns to each other, with both appearing generally flat, with anomalies in Eu, and Tm. Melilite and anorthite display positive Eu anomalies in both CAIs, in addition to the hibonite in Hoopoe (Fig. 2). The phases that are depleted in Eu are pyroxene and perovskite in both Saguaro and Hoopoe, respectively (Fig. 3). Given that Eu is volatile in reducing environments [11], this could possibly indicate reducing conditions at the time anorthite and melilite crystallized, with the gas they formed from containing Eu. As these CAIs continued to form, this gas as a result would become depleted in Eu. This also could be supported by the propensity of anorthite and melilite to take up Eu from its surroundings and incorporate it into their structure [12]. In addition, analyzing the assemblage of the phases in the Saguaro, melilite and anorthite (Eu enriched) often surround the pyroxene (Eu depleted) as they are crystallized. This intergrowth of phases and the proximity of the phases would support that the Eu is being incorporated into some phases, preventing it from incorporating into other. Trace elemental analyses of the CAI rims will be evaluated in more detail, as they are complicated by the transient signal being composed of a mixture of mineral phases. Broadly, however, the patterns in the rims of both CAIs are comparable to each other, and for Hoopoe, to the mixed phase patterns in the core (Fig. 3). Other studies have found that CAI rims can be depleted in Ce and Yb [13], however we did not observe these anomalies in the two CAIs discussed here. Given their similarity, the trace elemental analyses of the mixed interior (i.e. core) and rim phases could be interpreted as forming from similar, if not the same, reservoirs. The REE abundance between the rim and core of Hoopoe are also similar, indicating they may have formed from a gas of the same or similar composition. Acknowledgments: We thank the ASU Center for Meteorite Studies for loaning the samples used in this work and Tabb Prissel for his assistance with the analysis. Mouti Al-Hashimi thanks Sam Crossley and Cyrena Goodrich for their help with the LPI SEM training. This work was supported by the LPI Summer Intern Program in Planetary Science and the LPI Cooperative Agreement. References: [1] Connelly J.N. (2012) Science, 338, 651-655. [2] MacPherson G. J. (2014) Treatise on Geochem., 2, 139-179. [3] Grossman L. (1972) GCA, 36, 597-619. [4] Ebel, D.S. (2006) Meteorites and the Early Solar System II (D. S. Lauretta & H. Y. McSween, Eds.) 253-277. [5] MacPherson G. J. (2012) Earth Planet. Sci. Lett., 331-332, 43-54. [6] MacPherson G.J. (2017) GCA, 201, 65-82. [7] Krot A.N. (1995) Meteoritics & Planet. Sci., 30, 748-775. [8] Wark and Lovering (1982) GCA, 46, 2595-2607. [9] Palme H. and Jones A. (2003) Treatise on Geochemistry (H. D. Holland and K. K. Turekian Eds.), 1, 41-61. [10] Grossman L. (1980) Ann. Rev. Earth Planet. Sci., 8, 559-608. [11] Floss C. et al. (1996) GCA, 60, 1975-1997. [12] Mason B. and Martin P. M. (1974) Earth Planet. Sci. Lett., 22, 141-144. [13] Wark B. and Boynton W. V. (2001) Meteoritics & Planet. Sci., 36, 1135-1166.
CI meteorites have bulk chemical compositions closely matching the solar photosphere (except volatiles) and thus are considered to represent the starting composition of the Solar System. The return of CI-like samples from asteroid (162173) Ryugu by Hayabusa2 has greatly bolstered studies of CI. However, both CI and the Ryugu samples are CI1, i.e., they were extensively altered by aqueous fluids on their parent bodies so the mineralogy, textures, and oxygen isotope compositions of their CI3 precursors have been obscured. Fortunately, they contain rare remnants of primordial minerals in the form of small anhydrous silicate and Ca-Al-rich grains, and detailed petrologic and isotopic studies of these grains have helped elucidate the nature of their precursors. Here, we continue our work on petrologic and isotopic studies of such phases in Ryugu particle C0137.
Introduction: Calcium-aluminum inclusions (CAIs) are cm- to mm-sized intergrowths of refractory phases found in chondritic meteorites [1]. Their mineral compositions closely match the compositions of the solids thought to condense from an extremely hot (>1500K) gas with a bulk solar composition [2-4], suggesting that CAIs were the earliest solids within the Solar System [2-4]. These inclusions provide invaluable insights into the conditions and dynamics of the early Solar System. CAIs must be transported from their formation region near the protosun to the chondrite parent-body accretion region. The nature of their journey could affect how, when, and where the secondary processes recorded in these CAIs occurred [4]. Did these secondary processes occur in the solar nebula or during accretion with the parent body, or both? How were the CAIs affected by varying thermochemical processes? To better answer these questions, we have undertaken an in-depth, textural study of the secondary alteration of select CAI samples. Methods: We chose three CAIs that experienced a range of post-formation processing to gain better understanding of secondary alteration based on previous preliminary examination [5]. Representative CAIs were chosen from NWA 5508 (CV3), NWA 12772 (CV3), and Coolidge (CL4) carbonaceous chondrites. We used scanning electron microscopy (SEM) and electron backscatter diffraction (EBSD) techniques for detailed chemical, mineralogical, and textural analysis of the CAIs. Backscattered electron (BSE) images and X-ray elemental maps were taken of Coolidge and NWA 5508 using the Lunar and Planetary Institute (LPI) Phenom SEM. The JEOL 7900F SEM at NASA Johnson Space Center (JSC) was used to obtain energy dispersive spectroscopy (EDS) chemical maps of all samples. High resolution EBSD analysis identified the mineral phases and textures, providing key information on their nature. Based on the SEM and EBSD data, minerals of interest were selected for quantitative chemical electron probe micro-analysis (EPMA) using the JEOL JXA-8530F at NASA JSC. Results and Discussion: The EDS maps show that the NWA 5508 and NWA 12772 CAIs designated “Saguaro” and “Hoopoe” respectively [5] are enriched in calcium while the Coolidge CAI designated “Cottonwood” is aluminum and magnesium rich. Saguaro. A ~1.5cm diameter igneous Type B CAI with a rounded shape. The dominant phases are melilite, spinel, and Al-Ti pyroxene with minor anorthite. Spinel is subhedral and occurs in clusters. Some of these clusters have a circular geometry which encloses other minerals, known as a palisade structure [6] (Fig. 1). Some palisades form near perfect circles while others are more irregular in shape. Melilite in Saguaro ranges in size from coarse (>250m) to fine-grained (5-7m) and forms intergrown laths. A third of the melilite grains exhibit simple twinning about their <001> axis. The spinel palisades and twinned melilite in Saguaro suggest an igneous history, and the lack of secondary minerals suggests minimal aqueous alteration. At some point in time after the initial condensation of the minerals and formation of the inclusion, the sample was remelted and quickly solidified. The formation of the palisades is still heavily debated. One hypothesis is that the palisades are the rims of smaller CAIs that accreted early on, essentially acting as xenoliths within the larger CAIs [7]. Another hypothesis suggests an igneous origin for palisade structures [6-8] wherein the melt traps gas bubbles, and the spinel nucleates on the surface of this bubble. Based on the WDS spot analyses of 41 melilite grains using EPMA, the data suggest that the composition inside and outside the palisades is nearly identical. This finding indicates that these palisades are likely not exogenous but rather formed from melt-vapor reactions. Our results are consistent with studies by Simon and Grossman,1997 [6] and Zhang et al. (2019) [8]. Hoopoe. A ~0.5cm compact Type A CAI with an irregular shape. The dominant mineral phases are melilite, spinel, and hibonite with minor amounts of anorthite, augite, and perovskite. The melilite ranges in size from ~500 to 50µm. The larger melilite grains have simple twinning along the <001> axis like melilite in Saguaro. Melilite in Hoopoe exhibits crystal-plastic strain with misorientation dominantly about the <010> and <110> axes. Spinel shows subhedral to euhedral morphology and appears in clusters. Hibonite grains are similar to spinel in habit and size but show more plastic strain. The two minerals are often found together with one appearing to replace the other. Perovskite appears in fine grained recrystallized regions alongside fine augite and spinel. The abundant strain and deformation features in the melilite and hibonite suggest that Hoopoe experienced shock. This shock could have occurred in the nebula [9] or from an impact of another body on the parent body asteroid. The appearance of fine-grained (<10m) areas of augite, perovskite, and spinel in the dominantly coarse-grained inclusion suggest recrystallization, possibly due to the sudden increase in pressure and temperature. Cottonwood. This ~0.5cm CAI exhibits distinct mineralogy and textures suggesting a high degree of alteration. It is irregular in shape. The dominant mineral phases are spinel and anorthite with minor amounts of augite and rutile. The two main texture types can be seen in Fig. 2. The first type consists of coarse euhedral to subhedral spinel and anorthite. The second includes fine grained spinel, anorthite, rutile, and iron sulfides. Within these fine-grained regions, the anorthite grains are clustered into domains exhibiting the same crystallographic orientation. Rutile exclusively occurs with fine anorthite indicating a potential relationship between the two. Cottonwood has a clear and unbroken Wark-Lovering [10] rim (Fig. 2) on one side that consists of a sequence of spinel followed by anorthite and an outer layer of augite. The abundance of the fine-grained regions containing iron oxides and iron sulfides, secondary phases such as rutile, and oriented anorthite grains is evidence for recrystallization associated with a high degree of thermal metamorphism. The EPMA analyses on both coarse- and fine-grained spinel show that the fine spinel grains are more enriched in Cr (1-2 wt. %) than their coarse counterparts (0.1-0.5 wt. %). The data suggest thermal metamorphism drove chemical exchange of the previously refractory inclusion, introducing chromium and iron as well as sulfur, which is moderately volatile. Conclusions: The three CAIs analyzed record distinct secondary nebular and parent body processes. Saguaro melted in the nebula as seen by the twinned melilite and spinel palisades. Hoopoe experienced intense shock which deformed its melilite and recrystallized perovskite, augite, and spinel in fine-grained regions. Cottonwood shows evidence of recrystallization and chemical changes consistent with thermal metamorphism occurring after accretion into the parent-body.