Analysis of Cation Composition in Dolomites on the Intact Particles Sampled from Asteroid Ryugu.

Characterization of the elemental distribution of samples with rough surfaces has been strongly desired for the analysis of various natural and artificial materials. Particularly for pristine and rare analytes with micrometer sizes embedded on specimen surfaces, non-invasive and matrix effect-free analysis is required without surface polishing treatment. To satisfy these requirements, we proposed a new method employing the sequential combination of two imaging modalities, i.e., microenergy-dispersive X-ray fluorescence (micro-XRF) and Raman micro-spectroscopy. The applicability of the developed method is tested by the quantitative analysis of cation composition in micrometer-sized carbonate grains on the surfaces of intact particles sampled directly from the asteroid Ryugu. The first step of micro-XRF imaging enabled a quick search for the sparsely scattered and micrometer-sized carbonates by the codistributions of Ca2+ and Mn2+ on the Mg2+- and Fe2+-rich phyllosilicate matrix. The following step of Raman micro-spectroscopy probed the carbonate grains and analyzed their cation composition (Ca2+, Mg2+, and Fe2+ + Mn2+) in a matrix effect-free manner via the systematic Raman shifts of the lattice modes. The carbonates were basically assigned to ferroan dolomite bearing a considerable amount of Fe2+ + Mn2+ at around 10 atom %. These results are in good accordance with the assignments reported by scanning electron microscopy-energy-dispersive X-ray spectroscopy, where the thin-sectioned and surface-polished Ryugu particles were applicable. The proposed method requires neither sectioning nor surface polishing; hence, it can be applied to the remote sensing apparatus on spacecrafts and planetary rovers. Furthermore, the non-invasive and matrix effect-free characterization will provide a reliable analytical tool for quantitative analysis of the elemental distribution on the samples with surface roughness and chemical heterogeneity at a micrometer scale, such as art paintings, traditional crafts with decorated shapes, as well as sands and rocks with complex morphologies in nature.

Water circulation in Ryugu asteroid affected the distribution of nucleosynthetic isotope anomalies in returned sample.

Studies of material returned from Cb asteroid Ryugu have revealed considerable mineralogical and chemical heterogeneity, stemming primarily from brecciation and aqueous alteration. Isotopic anomalies could have also been affected by delivery of exogenous clasts and aqueous mobilization of soluble elements. Here, we show that isotopic anomalies for mildly soluble Cr are highly variable in Ryugu and CI chondrites, whereas those of Ti are relatively uniform. This variation in Cr isotope ratios is most likely due to physicochemical fractionation between 54Cr-rich presolar nanoparticles and Cr-bearing secondary minerals at the millimeter-scale in the bulk samples, likely due to extensive aqueous alteration in their parent bodies that occurred [Formula: see text] after Solar System birth. In contrast, Ti isotopes were marginally affected by this process. Our results show that isotopic heterogeneities in asteroids are not all nebular or accretionary in nature but can also reflect element redistribution by water.

Earth's evolving geodynamic regime recorded by titanium isotopes.

Earth's mantle has a two-layered structure, with the upper and lower mantle domains separated by a seismic discontinuity at about 660 km (refs. 1,2). The extent of mass transfer between these mantle domains throughout Earth's history is, however, poorly understood. Continental crust extraction results in Ti-stable isotopic fractionation, producing isotopically light melting residues3-7. Mantle recycling of these components can impart Ti isotope variability that is trackable in deep time. We report ultrahigh-precision 49Ti/47Ti ratios for chondrites, ancient terrestrial mantle-derived lavas ranging from 3.8 to 2.0 billion years ago (Ga) and modern ocean island basalts (OIBs). Our new Ti bulk silicate Earth (BSE) estimate based on chondrites is 0.052 ± 0.006‰ heavier than the modern upper mantle sampled by normal mid-ocean ridge basalts (N-MORBs). The 49Ti/47Ti ratio of Earth's upper mantle was chondritic before 3.5 Ga and evolved to a N-MORB-like composition between approximately 3.5 and 2.7 Ga, establishing that more continental crust was extracted during this epoch. The +0.052 ± 0.006‰ offset between BSE and N-MORBs requires that <30% of Earth's mantle equilibrated with recycled crustal material, implying limited mass exchange between the upper and lower mantle and, therefore, preservation of a primordial lower-mantle reservoir for most of Earth's geologic history. Modern OIBs record variable 49Ti/47Ti ratios ranging from chondritic to N-MORBs compositions, indicating continuing disruption of Earth's primordial mantle. Thus, modern-style plate tectonics with high mass transfer between the upper and lower mantle only represents a recent feature of Earth's history.

Abundant presolar grains and primordial organics preserved in carbon-rich exogenous clasts in asteroid Ryugu.

Preliminary analyses of asteroid Ryugu samples show kinship to aqueously altered CI (Ivuna-type) chondrites, suggesting similar origins. We report identification of C-rich, particularly primitive clasts in Ryugu samples that contain preserved presolar silicate grains and exceptional abundances of presolar SiC and isotopically anomalous organic matter. The high presolar silicate abundance (104 ppm) indicates that the clast escaped extensive alteration. The 5 to 10 times higher abundances of presolar SiC (~235 ppm), N-rich organic matter, organics with N isotopic anomalies (1.2%), and organics with C isotopic anomalies (0.2%) in the primitive clasts compared to bulk Ryugu suggest that the clasts formed in a unique part of the protoplanetary disk enriched in presolar materials. These clasts likely represent previously unsampled outer solar system material that accreted onto Ryugu after aqueous alteration ceased, consistent with Ryugu's rubble pile origin.

Silicon isotope constraints on terrestrial planet accretion.

Understanding the nature and origin of the precursor material to terrestrial planets is key to deciphering the mechanisms and timescales of planet formation1. Nucleosynthetic variability among rocky Solar System bodies can trace the composition of planetary building blocks2-5. Here we report the nucleosynthetic composition of silicon (µ30Si), the most abundant refractory planet-building element, in primitive and differentiated meteorites to identify terrestrial planet precursors. Inner Solar System differentiated bodies, including Mars, record µ30Si deficits of -11.0 ± 3.2 parts per million to -5.8 ± 3.0 parts per million whereas non-carbonaceous and carbonaceous chondrites show µ30Si excesses from 7.4 ± 4.3 parts per million to 32.8 ± 2.0 parts per million relative to Earth. This establishes that chondritic bodies are not planetary building blocks. Rather, material akin to early-formed differentiated asteroids must represent a major planetary constituent. The µ30Si values of asteroidal bodies correlate with their accretion ages, reflecting progressive admixing of a µ30Si-rich outer Solar System material to an initially µ30Si-poor inner disk. Mars' formation before chondrite parent bodies is necessary to avoid incorporation of µ30Si-rich material. In contrast, Earth's µ30Si composition necessitates admixing of 26 ± 9 per cent of µ30Si-rich outer Solar System material to its precursors. The µ30Si compositions of Mars and proto-Earth are consistent with their rapid formation by collisional growth and pebble accretion less than three million years after Solar System formation. Finally, Earth's nucleosynthetic composition for s-process sensitive (molybdenum and zirconium) and siderophile (nickel) tracers are consistent with pebble accretion when volatility-driven processes during accretion and the Moon-forming impact are carefully evaluated.

Samples returned from the asteroid Ryugu are similar to Ivuna-type carbonaceous meteorites.

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 [Formula: see text] million (statistical) or [Formula: see text] 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.

Potassium isotope heterogeneity in the early Solar System controlled by extensive evaporation and partial recondensation.

Volatiles are vital ingredients for a habitable planet. Angrite meteorites sample the most volatile-depleted planetesimal in the Solar System, particularly for the alkali elements. They are prime targets for investigating the formation of volatile-poor rocky planets, yet their exceptionally low volatile content presents a major analytical challenge. Here, we leverage improved sensitivity and precision of K isotopic analysis to constrain the mechanism of extreme K depletion (>99.8%) in angrites. In contrast with the isotopically heavy Moon and Vesta, we find that angrites are strikingly depleted in the heavier K isotopes, which is best explained by partial recondensation of vaporized K following extensive evaporation on the angrite parent body (APB) during magma-ocean stage. Therefore, the APB may provide a rare example of isotope fractionation controlled by condensation, rather than evaporation, at a planetary scale. Furthermore, nebula-wide K isotopic variations primarily reflect volatility-driven fractionations instead of presolar nucleosynthetic heterogeneity proposed previously.

Oxygen isotopes of anhydrous primary minerals show kinship between asteroid Ryugu and comet 81P/Wild2.

The extraterrestrial materials returned from asteroid (162173) Ryugu consist predominantly of low-temperature aqueously formed secondary minerals and are chemically and mineralogically similar to CI (Ivuna-type) carbonaceous chondrites. Here, we show that high-temperature anhydrous primary minerals in Ryugu and CI chondrites exhibit a bimodal distribution of oxygen isotopic compositions: 16O-rich (associated with refractory inclusions) and 16O-poor (associated with chondrules). Both the 16O-rich and 16O-poor minerals probably formed in the inner solar protoplanetary disk and were subsequently transported outward. The abundance ratios of the 16O-rich to 16O-poor minerals in Ryugu and CI chondrites are higher than in other carbonaceous chondrite groups but are similar to that of comet 81P/Wild2, suggesting that Ryugu and CI chondrites accreted in the outer Solar System closer to the accretion region of comets.

Late delivery of exotic chromium to the crust of Mars by water-rich carbonaceous asteroids.

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.

Ryugu's nucleosynthetic heritage from the outskirts of the Solar System.

Little is known about the origin of the spectral diversity of asteroids and what it says about conditions in the protoplanetary disk. Here, we show that samples returned from Cb-type asteroid Ryugu have Fe isotopic anomalies indistinguishable from Ivuna-type (CI) chondrites, which are distinct from all other carbonaceous chondrites. Iron isotopes, therefore, demonstrate that Ryugu and CI chondrites formed in a reservoir that was different from the source regions of other carbonaceous asteroids. Growth and migration of the giant planets destabilized nearby planetesimals and ejected some inward to be implanted into the Main Belt. In this framework, most carbonaceous chondrites may have originated from regions around the birthplaces of Jupiter and Saturn, while the distinct isotopic composition of CI chondrites and Ryugu may reflect their formation further away in the disk, owing their presence in the inner Solar System to excitation by Uranus and Neptune.

Natural separation of two primordial planetary reservoirs in an expanding solar protoplanetary disk.

Meteorites display an isotopic composition dichotomy between noncarbonaceous (NC) and carbonaceous (CC) groups, indicating that planetesimal formation in the solar protoplanetary disk occurred in two distinct reservoirs. The prevailing view is that a rapidly formed Jupiter acted as a barrier between these reservoirs. We show a fundamental inconsistency in this model: If Jupiter is an efficient blocker of drifting pebbles, then the interior NC reservoir is depleted by radial drift within a few hundred thousand years. If Jupiter lets material pass it, then the two reservoirs will be mixed. Instead, we demonstrate that the arrival of the CC pebbles in the inner disk is delayed for several million years by the viscous expansion of the protoplanetary disk. Our results support the hypothesis that Jupiter formed in the outer disk (>10 astronomical units) and allowed a considerable amount of CC material to pass it and become accreted by the terrestrial planets.

Chromium isotopic insights into the origin of chondrite parent bodies and the early terrestrial volatile depletion.

Chondrites are meteorites from undifferentiated parent bodies that provide fundamental information about early Solar System evolution and planet formation. The element Cr is highly suitable for deciphering both the timing of formation and the origin of planetary building blocks because it records both radiogenic contributions from 53Mn-53Cr decay and variable nucleosynthetic contributions from the stable 54Cr nuclide. Here, we report high-precision measurements of the massindependent Cr isotope compositions (ε53Cr and ε54Cr) of chondrites (including all carbonaceous chondrites groups) and terrestrial samples using for the first time a multi-collection inductively-coupled-plasma mass-spectrometer to better understand the formation histories and genetic relationships between chondrite parent bodies. With our comprehensive dataset, the order of decreasing ε54Cr (per ten thousand deviation of the 54Cr/52Cr ratio relative to a terrestrial standard) values amongst the carbonaceous chondrites is updated to CI = CH ≥ CB ≥ CR ≥ CM ≈ CV ≈ CO ≥ CK > EC > OC. Chondrites from CO, CV, CR, CM and CB groups show intra-group ε54Cr heterogeneities that may result from sample heterogeneity and/or heterogeneous accretion of their parent bodies. Resolvable ε54Cr (with 2SE uncertainty) differences between CV and CK chondrites rule out an origin from a common parent body or reservoir as has previously been suggested. The CM and CO chondrites share common ε54Cr characteristics, which suggests their parent bodies may have accreted their components in similar proportions. The CB and CH chondrites have low-Mn/Cr ratios and similar ε53Cr values to the CI chondrites, invalidating them as anchors for a bulk 53Mn-53Cr isochron for carbonaceous chondrites. Bulk Earth has a ε53Cr value that is lower than the average of chondrites, including enstatite chondrites. This depletion may constrain the timing of volatile loss from the Earth or its precursors to be within the first million years of Solar System formation and is incompatible with Earth's accretion via any of the known chondrite groups as main contributors, including enstatite chondrites.

Impact glasses from Belize represent tektites from the Pleistocene Pantasma impact crater in Nicaragua.

Tektites are terrestrial impact-generated glasses that are ejected long distance (up to 11,000 km), share unique characteristics and have a poorly understood formation process. Only four tektite strewn-fields are known, and three of them are sourced from known impact craters. Here we show that the recently discovered Pantasma impact crater (14 km diameter) in Nicaragua is the source of an impact glass strewn-field documented in Belize 530 km away. Their cogenesis is documented by coincidental ages, at 804 ± 9 ka, as well as consistent elemental compositions and isotopic ratios. The Belize impact glass share many characteristics with known tektites but also present several peculiar features. We propose that these glasses represent a previously unrecognized tektite strewn-field. These discoveries shed new light on the tektite formation process, which may be more common than previously claimed, as most known Pleistocene >10 km diameter cratering events have generated tektites.

A pebble accretion model for the formation of the terrestrial planets in the Solar System.

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 inward-drifting pebbles feed the growth of terrestrial planets. The masses and orbits of Venus, Earth, Theia (which later collided with 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. Last, 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 vaporize volatiles.

The internal structure and geodynamics of Mars inferred from a 4.2-Gyr zircon record.

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.

Early oxidation of the martian crust triggered by impacts.

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.

Oxygen isotopic heterogeneity in the early Solar System inherited from the protosolar molecular cloud.

The Sun is 16O-enriched (Δ17O = -28.4 ± 3.6‰) relative to the terrestrial planets, asteroids, and chondrules (-7‰ < Δ17O < 3‰). Ca,Al-rich inclusions (CAIs), the oldest Solar System solids, approach the Sun's Δ17O. Ultraviolet CO self-shielding resulting in formation of 16O-rich CO and 17,18O-enriched water is the currently favored mechanism invoked to explain the observed range of Δ17O. However, the location of CO self-shielding (molecular cloud or protoplanetary disk) remains unknown. Here we show that CAIs with predominantly low (26Al/27Al)0, <5 × 10-6, exhibit a large inter-CAI range of Δ17O, from -40‰ to -5‰. In contrast, CAIs with the canonical (26Al/27Al)0 of ~5 × 10-5 from unmetamorphosed carbonaceous chondrites have a limited range of Δ17O, -24 ± 2‰. Because CAIs with low (26Al/27Al)0 are thought to have predated the canonical CAIs and formed within first 10,000-20,000 years of the Solar System evolution, these observations suggest oxygen isotopic heterogeneity in the early solar system was inherited from the protosolar molecular cloud.

The role of Bells in the continuous accretion between the CM and CR chondrite reservoirs.

CM meteorites are dominant members of carbonaceous chondrites (CCs), which evidently accreted in a region separated from the terrestrial planets. These chondrites are key in determining the accretion regions of solar system materials, since in Mg and Cr isotope space, they intersect between what are identified as inner and outer solar system reservoirs. In this model, the outer reservoir is represented by metal-rich carbonaceous chondrites (MRCCs), including CR chondrites. An important question remains whether the barrier between MRCCs and CCs was a temporal or spatial one. CM chondrites and chondrules are used here to identify the nature of the barrier as well as the timescale of chondrite parent body accretion. We find based on high precision Mg and Cr isotope data of seven CM chondrites and 12 chondrules, that accretion in the CM chondrite reservoir was continuous lasting <3 Myr and showing late accretion of MRCC-like material reflected by the anomalous CM chondrite Bells. We further argue that although MRCCs likely accreted later than CM chondrites, CR chondrules must have initially formed from a reservoir spatially separated from CM chondrules. Finally, we hypothesize on the nature of the spatial barrier separating these reservoirs.

Iron isotope evidence for very rapid accretion and differentiation of the proto-Earth.

Nucleosynthetic isotope variability among solar system objects provides insights into the accretion history of terrestrial planets. We report on the nucleosynthetic Fe isotope composition (µ54Fe) of various meteorites and show that the only material matching the terrestrial composition is CI (Ivuna-type) carbonaceous chondrites, which represent the bulk solar system composition. All other meteorites, including carbonaceous, ordinary, and enstatite chondrites, record excesses in µ54Fe. This observation is inconsistent with protracted growth of Earth by stochastic collisional accretion, which predicts a µ54Fe value reflecting a mixture of the various meteorite parent bodies. Instead, our results suggest a rapid accretion and differentiation of Earth during the ~5-million year disk lifetime, when the volatile-rich CI-like material is accreted to the proto-Sun via the inner disk.

Atmosphere-ocean oxygen and productivity dynamics during early animal radiations.

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.