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Initial analyses showed that asteroid Ryugu's composition is close to CI (Ivuna-like) carbonaceous chondrites (CCs) - the chemically most primitive meteorites, characterized by near-solar abundances for most elements. However, some isotopic signatures (for example, Ti, Cr) overlap with other CC groups, so the details of the link between Ryugu and the CI chondrites are not yet fully clear. Here we show that Ryugu and CI chondrites have the same zinc and copper isotopic composition. As the various chondrite groups have very distinct Zn and Cu isotopic signatures, our results point at a common genetic heritage between Ryugu and CI chondrites, ruling out any affinity with other CC groups. Since Ryugu's pristine samples match the solar elemental composition for many elements, their Zn and Cu isotopic compositions likely represent the best estimates of the solar composition. Earth's mass-independent Zn isotopic composition is intermediate between Ryugu/CC and non-carbonaceous chondrites (NCs), suggesting a contribution of Ryugu-like material to Earth's budgets of Zn and other moderately volatile elements.

First cross-calibration of all existing Zr isotopic standards and two certified reference materials to a new commercially available standard NRC ZIRC-1, and the first report of the Zr isotopic composition of Allende chondrite.

We explore the heating and differentiation of rocky planets that grow by rapid pebble accretion. Our terrestrial planets grow outside of the ice line and initially accrete 28\% water ice by mass. The accretion of water stops after the protoplanet reaches a mass of $0.01\,M_{\rm E}$ where the gas envelope becomes hot enough to sublimate the ice and transport the vapour back to the protoplanetary disc by recycling flows. The energy released by the decay of $^{26}$Al melts the accreted ice to form clay (phyllosilicates), oxidized iron (FeO), and a water surface layer with ten times the mass of Earth's modern oceans. The ocean--atmosphere system undergoes a run-away greenhouse effect after the effective accretion temperature crosses a threshold of around 300 K. The run-away greenhouse process vaporizes the water layer, thereby trapping the accretion heat and heating the surface to more than 6,000 K. This causes the upper part of the mantle to melt and form a global magma ocean. Metal melt separates from silicate melt and sediments towards the bottom of the magma ocean; the gravitational energy released by the sedimentation leads to positive feedback where the beginning differentiation of the planet causes the whole mantle to melt and differentiate. All rocky planets thus naturally experience a magma ocean stage. We demonstrate that Earth's small excess of $^{182}$W (the decay product of $^{182}$Hf) relative to the chondrites is consistent with such rapid core formation within 5 Myr followed by equilibration of the W reservoir in Earth's mantle with $^{182}$W-poor material from the core of a planetary-mass impactor, provided that the equilibration degree is at least 25%-50%, depending on the initial Hf/W ratio. The planetary collision must have occurred at least 35 Myr after the main accretion phase of the terrestrial planets., Version accepted for Astronomy & Astrophysics

Various chemical elements including nickel (Ni) exhibit mass-independent isotope heterogeneity on a bulk meteorite level, which is generally accepted to reflect the heterogeneous distribution of presolar carrier(s) from different nucleosynthetic sources. Thus, understanding the nature of the carriers can help decipher the origin of the observed nucleosynthetic variability, which remains elusive. In this study, we present the first high precision measurements of mass-independent and mass-dependent Ni isotope compositions for step-leaches of the CI chondrite Ivuna and Efremovka CAIs supplemented by bulk chondrite measurements. Step-leaches record highly anomalous Ni isotope signatures that can be attributed to at least four diverse nucleosynthetic sources. The most anomalous leachates show either large deficits (up to 0.1 %) in the neutron-poor 58Ni and 60Ni nuclides (L11, thought to contain mainly s-process derived Ni) or minor enrichments and deficits (∼100 ppm) in 60Ni or 64Ni (L6, L8, L9 and L10, all thought to derive mainly from supernovae). Pristine CAIs record Ni isotope compositions typified by enrichments in 58Ni of up to 400 ppm. Our new data for bulk chondrites agree with earlier work and emphasize the appropriateness of using the 62Ni/61Ni ratio for internal normalization. Based on the compositional relations between the step-leaches data, CAIs, and bulk meteorites, we show that 60Ni variability is consistent with being of nucleosynthetic origin as opposed to reflecting variable Fe/Ni ratios in the presence of live 60Fe. Finally, we infer that the observed Ni nucleosynthetic disk variability is predominantly driven by a combination of processes separating different nucleosynthetic carriers in the disk from each other, including thermal processing and size-based sorting.

Correction to: Nature Astronomy https://doi.org/10.1038/s41550-022-01846-1. Published online 12 December 2022.

The terrestrial planets endured a phase of bombardment following their accretion, but the nature of this late accreted material is debated, preventing a full understanding of the origin of inner solar system volatiles. We report the discovery of nucleosynthetic chromium isotope variability (μ54Cr) in Martian meteorites that represent mantle-derived magmas intruded in the Martian crust. The μ54Cr variability, ranging from -33.1 ± 5.4 to +6.8 ± 1.5 parts per million, correlates with magma chemistry such that samples having assimilated crustal material define a positive μ54Cr endmember. This compositional endmember represents the primordial crust modified by impacting outer solar system bodies of carbonaceous composition. Late delivery of this volatile-rich material to Mars provided an exotic water inventory corresponding to a global water layer >300 meters deep, in addition to the primordial water reservoir from mantle outgassing. This carbonaceous material may also have delivered a source of biologically relevant molecules to early Mars., Science Advances, 8 (46), ISSN:2375-2548

Carbonaceous meteorites are thought to be fragments of C-type (carbonaceous) asteroids. Samples of the C-type asteroid (162173) Ryugu were retrieved by the Hayabusa2 spacecraft. We measured the mineralogy and bulk chemical and isotopic compositions of Ryugu samples. The samples are mainly composed of materials similar to those of carbonaceous chondrite meteorites, particularly the CI (Ivuna-type) group. The samples consist predominantly of minerals formed in aqueous fluid on a parent planetesimal. The primary minerals were altered by fluids at a temperature of 37° ± 10°C, about 5.2 − 0.7 + 0.8 million (statistical) or 5.2 − 2.1 + 1.6 million (systematic) years after the formation of the first solids in the Solar System. After aqueous alteration, the Ryugu samples were likely never heated above ~100°C. The samples have a chemical composition that more closely resembles that of the Sun’s photosphere than other natural samples do.

Volatile molecules containing hydrogen, carbon, and nitrogen are key components of planetary atmospheres. In the pebble accretion model for rocky planet formation, these volatile species are accreted during the main planetary formation phase. For this study, we modelled the partitioning of volatiles within a growing planet and the outgassing to the surface. The core stores more than 90\% of the hydrogen and carbon budgets of Earth for realistic values of the partition coefficients of H and C between metal and silicate melts. The magma oceans of Earth and Venus are sufficiently deep to undergo oxidation of ferrous Fe$^{2+}$ to ferric Fe$^{3+}$. This increased oxidation state leads to the outgassing of primarily CO$_2$ and H$_2$O from the magma ocean of Earth. In contrast, the oxidation state of Mars' mantle remains low and the main outgassed hydrogen carrier is H$_2$. This hydrogen easily escapes the atmosphere due to the irradiation from the young Sun in XUV wavelengths, dragging with it the majority of the CO, CO$_2$, H$_2$O, and N$_2$ contents of the atmosphere. A small amount of surface water is maintained on Mars, in agreement with proposed ancient ocean shorelines, for moderately low values of the mantle oxidation. Nitrogen partitions relatively evenly between the core and the atmosphere due to its extremely low solubility in magma; the burial of large reservoirs of nitrogen in the core is thus not possible. The overall low N contents of Earth disagree with the high abundance of N in all chondrite classes and favours a volatile delivery by pebble snow. Our model of rapid rocky planet formation by pebble accretion displays broad consistency with the volatile contents of the Sun's terrestrial planets. The diversity of the terrestrial planets can therefore be used as benchmark cases to calibrate models of extrasolar rocky planets and their atmospheres., Comment: Version accepted for Astronomy & Astrophysics

WOS:000600550100030; International audience; Chromium (Cr) isotopes play an important role in cosmochemistry and planetary science because they are powerful tools for dating (Mn-53-Cr-53 short-lived chronometry), tracing (Cr-54 nucleosynthetic anomalies) the origins of the materials, and studying the processes involved in volatile element fractionation and planetary differentiation (Cr stable isotopic fractionation). To use Cr isotopes for these purposes, it is essential to precisely know the compositions of the various chondritic reservoirs. However, the Cr isotope composition of Rumuruti (R) chondrites remains unknown. Here, we report high-precision mass-independent (average 2SE uncertainty of similar to 0.02 and similar to 0.06 for epsilon Cr-53 and epsilon Cr-54, respectively; epsilon indicates 10,000 deviation) and mass-dependent (uncertainty of average 0.03 parts per thousand for delta Cr-53; .delta indicates 1000 deviation) Cr isotope data for 12 bulk R chondrites of petrologic types 3-6 (including R chondrite breccias), and one R chondrite-like clast (MS-CH) in the Almahata Sitta polymict ureilite. All the R chondrites show homogeneous bulk epsilon Cr-54 values, -0.06 +/- 0.08 (2SD), similar only to those of the Earth-Moon system and enstatite chondrites. This first epsilon Cr-54 dataset for R chondrites provides significant addition to the epsilon Cr-54-A, Delta O-17 diagram, and positions them as a potential endmember for planetary precursors. The R chondrites possess a higher Mn-55/Cr-52 of 0.68 +/- 0.04 relative to most of carbonaceous chondrites and higher epsilon Cr-53 values 0.23 +/- 0.05 (2SD) relative to most of chondrite groups. This likely results from the lower chondrule abundance in R chondrites compared to that of ordinary and enstatite chondrites. The stable Cr isotope composition of R chondrites is homogeneous with a delta Cr-53 = -0.12 +/- 0.03%e (2SD). Combined with previous data of other groups of chondrites, we show that the stable Cr isotopic composition of all the chondrites is homogeneous with delta Cr-53 of -0.12 +/- 0.04%e (2SD, N = 42) and is independent of the petrologic type and redox conditions. The lack of mass-dependent fractionation between all groups of chondrites suggests that the average chondrite delta Cr-53 value is also representative for the initial composition of all differentiated planets in the Solar System. Finally, the MS-CH clast in Almahata Sitta has a Cr isotopic composition (epsilon Cr-53 = 0.18 +/- 0.04, epsilon Cr-54 = 0.16 +/- 0.07, and delta Cr-53 = -0.11 +/- 0.05%e) that is consistent (within error) with it being an R chondrite-like clast. (C) 2020 Elsevier Ltd. All rights reserved.

Prominent among the models for protocells is the spherical biosurfactant shell, freely suspended in aqueous media. This model explains initial, but not subsequent events in the development process towards structured protocells. Taking into consideration the involvement of naturally occurring surfaces, which were abundant on the early Earth, feasible and productive pathways for the development of primitive cells are reported. Surfaces intrinsically possess energy, easily utilized by the interfacing amphiphiles, such as lipids, to attain self-organization and spontaneous transformations. This work shows that the physical interaction of phospholipid pools with 20 Hadean Earth analogue materials as well as a Martian meteorite composed of fused regolith representing the ancient crust of Mars consistently lead to the shape transformation and autonomous formation of surfactant compartment assemblies. Dense, colony-like protocell populations grow from these lipid deposits, predominantly at the grain boundaries or cleavages of the investigated natural surfaces, and remain there for several days. The model protocells in this study are able to autonomously develop, transform and pseudo-divide, and encapsulate RNA as well as DNA. Moreover, they can accommodate non-enzymatic, DNA strand displacement reactions. These findings suggest a feasible route towards the transformation from non-living to living entities, and provide fresh support for the 'Lipid World' hypothesis.

Significance We discovered a zircon record in a Martian meteorite that spans 4.2 Gyr, nearly the entire geologic history of Mars. Ancient zircons define a bimodal distribution with groupings at 4474 ± 10 Ma and 4442 ± 17 Ma, reflecting intense bombardment episodes triggered by the migration of the gas giant planets. A group of younger detrital zircons record ages from 1548.0 ± 8.8 Ma to 299.5 ± 0.6 Ma. The only plausible sources for these grains are the Elysium and Tharsis volcanic provinces that are the expressions of deep-seated mantle plumes. The chondritic-like Hf-isotope compositions of these zircons require the existence of a primitive and convecting mantle reservoir. Thus, these grains provide a tangible record of the deep Martian interior., Combining U–Pb ages with Lu–Hf data in zircon provides insights into the magmatic history of rocky planets. The Northwest Africa (NWA) 7034/7533 meteorites are samples of the southern highlands of Mars containing zircon with ages as old as 4476.3 ± 0.9 Ma, interpreted to reflect reworking of the primordial Martian crust by impacts. We extracted a statistically significant zircon population (n = 57) from NWA 7533 that defines a temporal record spanning 4.2 Gyr. Ancient zircons record ages from 4485.5 ± 2.2 Ma to 4331.0 ± 1.4 Ma, defining a bimodal distribution with groupings at 4474 ± 10 Ma and 4442 ± 17 Ma. We interpret these to represent intense bombardment episodes at the planet’s surface, possibly triggered by the early migration of gas giant planets. The unradiogenic initial Hf-isotope composition of these zircons establishes that Mars’s igneous activity prior to ∼4.3 Ga was limited to impact-related reworking of a chemically enriched, primordial crust. A group of younger detrital zircons record ages from 1548.0 ± 8.8 Ma to 299.5 ± 0.6 Ma. The only plausible sources for these grains are the temporally associated Elysium and Tharsis volcanic provinces that are the expressions of deep-seated mantle plumes. The chondritic-like Hf-isotope compositions of these zircons require the existence of a primitive and convecting mantle reservoir, indicating that Mars has been in a stagnant-lid tectonic regime for most of its history. Our results imply that zircon is ubiquitous on the Martian surface, providing a faithful record of the planet’s magmatic history.

We present a series of papers dedicated to modelling the accretion and differentiation of rocky planets that form by pebble accretion within the lifetime of the protoplanetary disc. In this first paper, we focus on how the accreted ice determines the distribution of iron between the mantle (oxidized FeO and FeO$_{1.5}$) and the core (metallic Fe and FeS). We find that an initial primitive composition of ice-rich material leads, upon heating by the decay of $^{26}$Al, to extensive water flow and the formation of clay minerals inside planetesimals. Metallic iron dissolves in liquid water and precipitates as oxidized magnetite Fe$_3$O$_4$. Further heating by $^{26}$Al destabilizes the clay at a temperature of around 900 K. The released supercritical water ejects the entire water content from the planetesimal. Upon reaching the silicate melting temperature of 1,700 K, planetesimals further differentiate into a core (made mainly of iron sulfide FeS) and a mantle with a high fraction of oxidized iron. We propose that the asteroid Vesta's significant FeO fraction in the mantle is a testimony of its original ice content. We consider Vesta to be a surviving member of the population of protoplanets from which Mars, Earth, and Venus grew by pebble accretion. We show that the increase in the core mass fraction and decrease in FeO contents with increasing planetary mass (in the sequence Vesta -- Mars -- Earth) is naturally explained by the growth of terrestrial planets outside of the water ice line through accretion of pebbles containing iron that was dominantly in metallic form with an intrinsically low oxidation degree., Comment: Version accepted for Astronomy & Astrophysics

International audience; Chondrites are rocky fragments of asteroids that formed at different times and heliocentric distances in the early solar system. Most chondrite groups contain water-bearing minerals, attesting that both water-ice and dust were accreted on their parent asteroids. Nonetheless, the hydrogen isotopic composition (D/H) of water in the different chondrite groups remains poorly constrained, due to the intimate mixture of hydrated minerals and organic compounds, the other main H-bearing phase in chondrites. Building on our recent works using in situ secondary ion mass spectrometry analyses, we determined the H isotopic composition of water in a large set of chondritic samples (CI, CM, CO, CR, CY, and C-ungrouped carbonaceous chondrites) and report that water in each group shows a distinct and unique D/H signature. Based on a comparison with literature data on bulk chondrites and their water and organics, our data do not support a preponderant role of parent-body processes in controlling the D/H variations among chondrites. Instead, we propose that the water and organic D/H signatures were mostly shaped by interactions between the protoplanetary disk and the molecular cloud that episodically fed the disk over several million years. Because the 2 preservation of D-rich interstellar water and/or organics in chondritic materials is only possible below their respective sublimation temperatures (160 and 350-450 K), the H isotopic signatures of chondritic materials depend on both the timing and location at which their parent body formed.

We describe the AMBITION project, a mission to return the first-ever cryogenically-stored sample of a cometary nucleus, that has been proposed for the ESA Science Programme Voyage 2050. Comets are the leftover building blocks of giant planet cores and other planetary bodies, and fingerprints of Solar System’s formation processes. We summarise some of the most important questions still open in cometary science and Solar System formation after the successful Rosetta mission. We show that many of these scientific questions require sample analysis using techniques that are only possible in laboratories on Earth. We summarize measurements, instrumentation and mission scenarios that can address these questions. We emphasize the need for returning a sample collected at depth or, still more challenging, at cryogenic temperatures while preserving the stratigraphy of the comet nucleus surface layers. We provide requirements for the next generation of landers, for cryogenic sample acquisition and storage during the return to Earth. Rendezvous missions to the main belt comets and Centaurs, expanding our knowledge by exploring new classes of comets, are also discussed. The AMBITION project is discussed in the international context of comet and asteroid space exploration.

Significance We have discovered 2 major oceanic anoxic events (OAEs) in the early Cambrian at the time when animals markedly diversified. We present a multiproxy constraint on the global biogeochemical cycles to show that these events, in contrast to most younger OAEs, could have been driven by declining atmospheric O2 levels, plausibly set off by the appearance of bioturbating animals. Pulses of animal appearances may have occurred at different times on different continents, but the last pulse occurred after the OAEs and at a time when we predict higher marine productivity and O2 levels in the surface oceans suggesting energy supply into the marine food chain was maximal., The proliferation of large, motile animals 540 to 520 Ma has been linked to both rising and declining O2 levels on Earth. To explore this conundrum, we reconstruct the global extent of seafloor oxygenation at approximately submillion-year resolution based on uranium isotope compositions of 187 marine carbonates samples from China, Siberia, and Morocco, and simulate O2 levels in the atmosphere and surface oceans using a mass balance model constrained by carbon, sulfur, and strontium isotopes in the same sedimentary successions. Our results point to a dynamically viable and highly variable state of atmosphere–ocean oxygenation with 2 massive expansions of seafloor anoxia in the aftermath of a prolonged interval of declining atmospheric pO2 levels. Although animals began diversifying beforehand, there were relatively few new appearances during these dramatic fluctuations in seafloor oxygenation. When O2 levels again rose, it occurred in concert with predicted high rates of photosynthetic production, both of which may have fueled more energy to predators and their armored prey in the evolving marine ecosystem.

The primitive cells that emerged at the origin of life are commonly viewed as spherical biosurfactant shells, freely suspended in aqueous media1–3. This model explains initial, but not subsequent events in the development process towards structured protocells. Taking into consideration the involvement of naturally occurring surfaces, which were abundant on the early Earth4, we report feasible and productive pathways for the development of primitive cells. Surfaces intrinsically possess energy, easily utilized by the interfacing amphiphiles, such as lipids, to attain self-organization and spontaneous transformations5–7. We show that the physical interaction of phospholipid pools with 20 Hadean Earth analogue materials as well as a Martian meteorite composed of fused regolith representing the ancient crust of Mars, consistently lead to the shape transformation and autonomous formation of surfactant compartment assemblies. Dense, colony-like protocell populations grow from these lipid deposits, predominantly at the grain boundaries or cleavages of the investigated natural surfaces, and remain there for several days. The model protocells in our study are able to autonomously develop, transform and pseudo-divide, and encapsulate RNA as well as DNA. We also demonstrate that they can accommodate non-enzymatic, DNA strand displacement reactions. Our findings suggest a feasible route towards the transformation from nonliving to living entities, and provide fresh support for the ‘Lipid World’ hypothesis8.

Understanding the origin of chondritic components and their accretion pathways is critical to unravel the magnitude of mass transport in the protoplanetary disk, the accretionary history of the terrestrial planet region and, by extension, its prebiotic inventory. Here, we trace the heritage of pristine components from the relatively unaltered CV chondrite Leoville through their mass-independent Cr and mass-dependent Zn isotope compositions. Investigating these chondritic fractions in such detail reveals an onion-shell structure of chondrules, which is characterized by 54Cr- and 66Zn-poor cores surrounded by increasingly 54Cr- and 66Zn-rich igneous rims and an outer coating of fine-grained dust. This is interpreted as a progressive addition of 54Cr- and 66Zn-rich, CI-like material to the accretion region of these carbonaceous chondrites. Our findings show that the observed Cr isotopic range in chondrules from more altered CV chondrites is the result of chemical equilibration between chondrules and matrix during secondary alteration. The 54Cr-poor nature of the cores of Leoville chondrules implies formation in the inner Solar System and subsequent massive outward chondrule transport past the Jupiter barrier. At the same time, CI-like dust is transferred inwards. We propose that the accreting Earth acquired CI-like dust through this mechanism within the lifetime of the disk. This radial mixing of chondrules and matrix shows the limited capacity of Jupiter to act as an efficient barrier and maintain the proposed non-carbonaceous and carbonaceous chondrite dichotomy over time. Finally, also considering current astrophysical models, we explore both inner and outer Solar System origins for the CV chondrite parent body., accepted after peer-review

Pebbles of millimeter sizes are abundant in protoplanetary discs around young stars. Chondrules inside primitive meteorites - formed by melting of dust aggregate pebbles or in impacts between planetesimals - have similar sizes. The role of pebble accretion for terrestrial planet formation is nevertheless unclear. Here we present a model where inwards-drifting pebbles feed the growth of terrestrial planets. The masses and orbits of Venus, Earth, Theia (which later collided with the Earth to form the Moon) and Mars are all consistent with pebble accretion onto protoplanets that formed around Mars' orbit and migrated to their final positions while growing. The isotopic compositions of Earth and Mars are matched qualitatively by accretion of two generations of pebbles, carrying distinct isotopic signatures. Finally, we show that the water and carbon budget of Earth can be delivered by pebbles from the early generation before the gas envelope became hot enough to vaporise volatiles., Comment: Science Advances, in press

We use high-precision neodymium isotope data for sequentially acid-leached components of the primitive carbonaceous chondrite Tagish Lake to identify a non-classical 150Nd-rich presolar carrier phase that has not been identified as of yet in meteorites. The distinct isotopic signature of this carrier can be attributed to the intermediate neutron capture process (i-process) occurring in asymptotic giant branch (AGB), super-AGB, or post-AGB stars or, alternatively, the slow capture process (s-process) occurring in rotating massive stars. The 150Nd-rich carrier appears to be heterogeneously distributed in the solar protoplanetary disk resulting in systematic isotope variations between carbonaceous and non-carbonaceous solar system materials. Carbonaceous chondrites that accreted in the outer disk are depleted in this carrier relative to non-carbonaceous materials that accreted in the terrestrial planet-forming region. Calcium-aluminum-rich inclusions that represent the earliest formed disk solids record the largest depletion of this carrier. This distribution pattern is contrary to that seen for the carriers of other neutron-rich isotope anomalies (48Ca, 54Cr, 95,97Mo, etc.) that have defined carbonaceous/non-carbonaceous isotope dichotomy so far. Irrespective of the exact astrophysical origin of these carriers, divergent distribution of presolar dust as a function of physicochemical processing in the solar protoplanetary disk best explains the solar system isotope dichotomy as opposed to changes in the composition of the infall.

Dating meteoritic materials by the Pb–Pb isochron method depends on constructing linear arrays typically defined by mixtures of initial and radiogenic Pb after the removal of terrestrial contaminant Pb. The method also depends on minimizing the amount of laboratory Pb blank added to the sample during processing and analyses. With the aim to analyze smaller sample sizes and decrease processing times, we have devised a new method for the construction of isochrons using the stepwise dissolution of meteoritic materials that better defines reduced amounts of Pb blank, reduces the risk of random anomalous Pb contamination, and increases sample throughput. Samples are processed in a PFA Teflon™ pipette tip fitted with a frit inside a heated, sealed chamber that can be manually over-pressured to expel reagents directly into a PFA Teflon™ vial below. With four independent chambers, three samples can be processed simultaneously with a fourth position to assess the Pb contribution of the combined blank and spike for each step. The matched blank-spike Pb for each step provides a specific blank estimate for each step that ensures a more accurate correction for non-sample Pb and, therefore, reduces the uncertainty on each analysis. We assess the performance of this new method by reporting the results of dating a fragment of a chondrule from the well-characterized CBa chondrite Gujba and compare these results with previously published data for this meteorite. The improvements reduce the minimum sample sizes that can be successfully dated by the Pb–Pb method, an important development for size-limited materials such as small chondrules and samples returned from space missions.

We report on the discovery of 33 oxygen-anomalous grains from the CH3/CBb3 chondrite Isheyevo and the CR2 chondrite Northwest Africa (NWA) 801. Oxygen isotopic compositions indicate the origin of the majority grains in stellar outflows of low-mass (∼1.2 to ∼2.2 M ⊙), solar-metallicity red giant or asymptotic giant branch stars, while highly 17O-enriched grains probably have nova origins. Isotopic compositions of the eight 18O-rich grains, including an extremely 18O-rich grain (∼16 times solar 18O/16O ratio), are reproduced by zone mixing of SNe II ejecta. Close-to-normal silicon, magnesium, and calcium isotopic compositions of grains are consistent with the isotope exchange in the interstellar medium or the meteorite parent body, while two grains with Si isotopic anomalies and one grain with Mg isotopic anomalies reflect the Galactic chemical evolution. An Isheyevo clast showed several hot spots with moderate to high 15N enrichments, including a hot spot with an extreme 15N excess of (7225 ± 316)‰. However, no correlation between 15N enrichment and presolar oxygen-rich grain abundance is found. Grains with elliptical shapes probably indicate primary condensation feature. Two complex grains possibly display decoupling of the isotopic and elemental compositions in the grain formation environments. The low silicate-to-oxide abundance ratio for the fine-grained chondrule rims in NWA 801 likely reflects the preferential destruction of silicates due to terrestrial weathering. In NWA 801, the presolar O-rich grain abundance in fine-grained chondrule rims is higher than in the interchondrule matrix, similar to the trend observed for some aqueously altered chondrites of petrologic type 2.

Impact-induced oxidation of Mars’ crust by water >4.4 Ga ago likely supplied enough atmospheric H2 to attain a warm climate., Despite the abundant geomorphological evidence for surface liquid water on Mars during the Noachian epoch (>3.7 billion years ago), attaining a warm climate to sustain liquid water on Mars at the period of the faint young Sun is a long-standing question. Here, we show that melts of ancient mafic clasts from a martian regolith meteorite, NWA 7533, experienced substantial Fe-Ti oxide fractionation. This implies early, impact-induced, oxidation events that increased by five to six orders of magnitude the oxygen fugacity of impact melts from remelting of the crust. Oxygen isotopic compositions of sequentially crystallized phases from the clasts show that progressive oxidation was due to interaction with an 17O-rich water reservoir. Such an early oxidation of the crust by impacts in the presence of water may have supplied greenhouse gas H2 that caused an increase in surface temperature in a CO2-thick atmosphere.

Constraining the duration of magmatic activity on the Moon is essential to understand how the lunar mantle evolved chemically through time. Determining age and initial isotopic compositions of mafic lunar meteorites is a critical step in defining the periods of magmatic activity that occurred during the history of the Moon and to constrain the chemical characteristics of mantle components involved in the sources of the magmas. We have used the in situ Pb-Pb SIMS technique to investigate eight lunar gabbros and basalts, including six meteorites from the Northwest Africa (NWA) 773 clan (NWA 2727, NWA 2700, NWA 3333, NWA 2977, NWA 773, and NWA 3170), NWA 4734, and Dhofar 287A. These samples have been selected as there is no clear agreement on their age and they are all from the dominant low titanium chemical group. We have obtained ages of 2981 +/- 12 Ma for NWA 4734 and 3208 +/- 22 Ma for Dhofar 287. For the NWA 773 clan, four samples (the fine-grained basalt NWA 2727 and the three gabbros NWA 773, NWA 2977, NWA 3170) out of six yielded isochron-calculated ages that are identical within uncertainties and yielding an average age of 3086 +/- 5 Ma. The age obtained for the fine-grained basalt NWA 2700 is not precise enough for comparison with the other samples. The gabbroic sample NWA 3333 yielded an age of 3038 +/- 20 Ma suggesting that two distinct magmatic events may be recorded in the meteorites of the NWA 773 clan. The present study aims to identify and assess all potential issues that are associated with different ways to date lunar rocks using U-Pb-based methods. To achieve this, we have compared the new ages with the previously published data set. The entire age data set from lunar mafic meteorites was also screened to identify data showing analytical issues and evidence of resetting and terrestrial contamination. The data set combining the ages of mafic lunar meteorites and Apollo rocks suggests pulses of magmatic activity with two distinct phases between 3950 and 3575 Ma and between 3375 and 3075 Ma with the two phases separated by a gap of approximately 200 Ma. The evolution of the Pb initial ratios of the low-Ti mare basalts between approximately 3400 and 3100 Ma suggests that these rocks were progressively contaminated by a KREEP-like component.

Constraining the duration of magmatic activity on the Moon is essential to understand how the lunar mantle evolved chemically through time. Determining age and initial isotopic compositions of mafic lunar meteorites is a critical step in defining the periods of magmatic activity that occurred during the history of the Moon and to constrain the chemical characteristics of mantle components involved in the sources of the magmas.We have used the in-situ Pb–Pb SIMS technique to investigate lunar gabbros and basalts, including meteorites from the Northwest Africa (NWA) 773 clan (NWA 2727, NWA 3333, NWA 2977, NWA 773 and NWA 3170), LAP 02224, NWA 4734 and Dhofar 287A. These samples have been selected as they all belong to the dominant chemical group of low-titanium mare basalts and there is no clear agreement on their age. We have obtained ages of 2978 ± 13 Ma for LAP02224, 2981 ± 12 Ma for NWA 4734 and 3208 ± 22 Ma for Dhofar 287. For the NWA 773 clan, four samples (NWA 2727, NWA 773, NWA 2977, NWA 3170) yielded isochron-calculated ages that are identical within uncertainties with an average age of 3086.1 ± 4.8 Ma. The gabbroic sample NWA 3333 yielded an age of 3038 ± 20 Ma suggesting that two distinct magmatic events are recorded in the meteorites of the NWA 773 clan.The entire age dataset from lunar mafic meteorites was screened to identify data that are problematic from an analytical viewpoint and/or show evidence of resetting and terrestrial contamination. This refined dataset combines the ages of mafic lunar meteorites and Apollo samples and suggests pulses in magmatic activity, with two main phases between 3350 and 3100 Ma and between 3900 and 3550 Ma followed by a minor phase at ~3000 Ma.The evolution of the Pb initial ratios of the low-Ti mare basalts between 3400 Ma and 3100 Ma suggests that these rocks were progressively contaminated by a KREEP-like component. Nevertheless, the ~3000 Ma mafic rocks (NWA4734 and LAP02224) show significant differences in terms of initial 204Pb/206Pb ratios that illustrates that the lunar mantle is probably more heterogeneous than has previously been assumed.

Introduction Primitive extraterrestrial materials like carbonaceous chondrite matrices and interplanetary dust particles contain tiny dust grains that were formed in the winds of red giant branch, or asymptotic giant branch stars (AGB) and in the ejecta of novae and supernovae (SNe) explosions before the formation of our solar system. Following their formation, these tiny stardust grains of submicron size traversed through the interstellar medium before being incorporated into the cloud of gas and dust that collapsed and created our solar system. Presolar grains survived the high energy processes that created our solar system and, in their isotopic compositions, preserved the fingerprints that are the nucleosynthetic signatures of the parent stellar sources of the grains.1 Correlating isotopic data of individual presolar silicates with microstructural and chemical analyses obtained by (S)TEM, provides a unique opportunity to provide better insights into physiochemical conditions of grain formation in stellar environments, grain alteration in the interstellar and parent body processes and also helps constraining various astrophysical grain condensation models. In this work, isotopic, structural and chemical analysis of nine presolar silicate grains from the CH3/CBb3 chondrite Isheyevo and CR2 chondrite NWA801 are reported. The grains studied here are found within the lithic clasts in Isheyevo and fine grained chondrule rims in NWA801 that have experienced lower amount of parent body alteration and hence the chemical compositions of presolar grains studied here are minimally altered. Experimental Presolar oxygen anomalous grain search using oxygen isotope imaging was done in-situ using NanoSIMS50 ion microprobe and five grains from AGB and four grains from SNe, were selected for (S)TEM investigations. The TEM lamellas were prepared using a TESCAN LYRA3 FIB-SEM at Curtin University. Structural and chemical analysis of presolar grains were performed by combining high-resolution scanning TEM imaging, spatially-resolved electron energy-loss spectroscopy (EELS) and spatially-resolved energy-dispersive X-ray spectroscopy (EDS) by using a FEI Titan Cubed Themis 60-300 microscope at the University of Cádiz which was operated at 200 kV. EDS quantification was corrected by using a standard reference sample of known composition and density and by taking into account the thickness of the probed area as determined by using low-loss EELS. EELS spectrum images for fine structures (mostly, O-K, Si-L2,3 and Fe-L2,3 edges) analyses were acquired with the monochromator excited allowing an energy resolution of about 0.4 eV. After denoising using principal components analysis and removal of the multiple scattering, we were able to map the heterogeneities related to the Fe oxidation states and to the oxygen local chemical environment. For the chemical mapping of the Fe3+/ ∑Fe ratios, we have used a home-made Python routine based on the determination of the modified white-lines ratio.2 It allowed us to compare the degree of aqueous alteration of the grain with the surrounding rim and matrix grains. Results TEM and STEM data have revealed a strong heterogeneity and a broad range of structural and chemical compositions of the grains that enabled us to compare the stellar grain condensation environments (e.g. AGB stars and SNe), and suggest widely varying formation conditions for the presolar silicates identified in this study. Only one of the grains originally condensed as an amorphous grain has shown preferential sputtering of Mg, indicating that Mg-rich amorphous grains are not preferentially destroyed. Several grains are found with signatures that represent interstellar, nebular and parent body alteration. An oldhamite-like grain (Figure 1) within a presolar enstatite grain is probably the first observation of an oldhamite grain as a seed grain for the condensation of an enstatite grain in stellar atmospheres. This grain corresponds to a local increase in Mg and a local decrease in Fe with respect to the surrounding matrix. The surface of the grain surface of up to ~40 nm is composed of higher amounts of Ca and S. Below the surface of the grain and on the left side, diffusion streaks rich in Ca can be observed up to the lower boundary of the grain (on about 250 nm). The diffusion of Ca could be related to thermal processes and/or aqueous alterations undergone by the grain. Figure 2 shows typical EELS chemical maps acquired on the same grain. A very thin Fe-rich rim is also seen around the enstatite grain with a Fe3+/ΣFe ratio of about 0.6-0.7. The presence of several spherical nodules of Fe and Ni sulfide can also be highlighted in the matrix around the grain in the EDS and EELS chemical maps (red arrows in Figures 8 and 9). They have a diameter of about 30-45 nm and are similar to GEMS-like materials. Interestingly, they present a core/shell structure All these results, which will be discussed in detail, point out the importance of coordinated isotopic, microstructural and chemical studies of presolar silicates to investigate the processes that may have played a role in shaping our solar system. Zinner, E., (2014) Treatise on Geochemistry, Vol. 1 2nd ed. ed AM Davis Van Aken, P. A., B. Liebscher, and V. J. Styrsa. "Quantitative determination of iron oxidation states in minerals using Fe L 2, 3-edge electron energy-loss near-edge structure spectroscopy." Physics and Chemistry of Minerals 25.5 (1998): 323-327 Figure 1. a) STEM-HAADF micrograph of the grain Isheyevo_9. The red dashed lines line highlights the boundary of the grain. b) Superposition of HAADF micrograph and Ca chemical maps derived from EDS analysis. Chemical maps derived from EDS analyses corresponding to c) Fe, d) Ni, e) Mg and f) S elements. The red arrows highlight the presence of GEMS-like materials. Figure 2. Chemical maps derived from the EELS analysis for the grain Isheyevo_9 and corresponding to a) Fe, b) O, c) the O-K pre-peak, d) F and e) the Fe+3/ΣFe ratio. The black scale bar represents 0.1 µm. The red arrows highlight the presence of GEMS-like materials.