Hot spring oases in the periglacial desert as the Last Glacial Maximum refugia for temperate trees in Central Europe.

Northern glacial refugia are a hotly debated concept. The idea that many temperate organisms survived the Last Glacial Maximum (LGM; ~26.5 to 19 thousand years) in several sites across central and northern Europe stems from phylogeographic analyses, yet direct fossil evidence has thus far been missing. Here, we present the first unequivocal proof that thermophilous trees such as oak (Quercus), linden (Tilia), and common ash (Fraxinus excelsior) survived the LGM in Central Europe. The persistence of the refugium was promoted by a steady influx of hydrothermal waters that locally maintained a humid and warm microclimate. We reconstructed the geological and palaeohydrological factors responsible for the emergence of hot springs during the LGM and argue that refugia of this type, allowing the long-term survival and rapid post-LGM dispersal of temperate elements, were not exceptional in the European periglacial zone.

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.

Igneous meteorites suggest Aluminium-26 heterogeneity in the early Solar Nebula.

The short-lived radionuclide aluminium-26 (26Al) isotope is a major heat source for early planetary melting. The aluminium-26 - magnesium-26 (26Al-26Mg) decay system also serves as a high-resolution relative chronometer. In both cases, however, it is critical to establish whether 26Al was homogeneously or heterogeneously distributed throughout the solar nebula. Here we report a precise lead-207 - lead-206 (207Pb-206Pb) isotopic age of 4565.56 ± 0.12 million years (Ma) for the andesitic achondrite Erg Chech 002. Our analysis, in conjunction with published 26Al-26Mg data, reveals that the initial 26Al/27Al in the source material of this achondrite was notably higher than in various other well-preserved and precisely dated achondrites. Here we demonstrate that the current data clearly indicate spatial heterogeneity of 26Al by a factor of 3-4 in the precursor molecular cloud or the protoplanetary disk of the Solar System, likely associated with the late infall of stellar materials with freshly synthesized radionuclides.

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.

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.

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.

Scientific Value of Including an Atmospheric Sample as Part of Mars Sample Return (MSR).

The Perseverance rover is meant to collect samples of the martian surface for eventual return to Earth. The headspace gas present over the solid samples within the sample tubes will be of significant scientific interest for what it reveals about the interactions of the solid samples with the trapped atmosphere and for what it will reveal about the martian atmosphere itself. However, establishing the composition of the martian atmosphere will require other dedicated samples. The headspace gas as the sole atmospheric sample is problematic for many reasons. The quantity of gas present within the sample tube volume is insufficient for many investigations, and there will be exchange between solid samples, headspace gas, and tube walls. Importantly, the sample tube materials and preparation were not designed for optimal Mars atmospheric gas collection and storage as they were not sent to Mars in a degassed evacuated state and have been exposed to both Earth's and Mars' atmospheres. Additionally, there is a risk of unconstrained seal leakage in transit back to Earth, which would allow fractionation of the sample (leak-out) and contamination (leak-in). The science return can be improved significantly (and, in some cases, dramatically) by adding one or more of several strategies listed here in increasing order of effectiveness and difficulty of implementation: (1) Having Perseverance collect a gas sample in an empty sample tube, (2) Collecting gas in a newly-designed, valved, sample-tube-sized vessel that is flown on either the Sample Fetch Rover (SFR) or the Sample Retrieval Lander (SRL), (3) Adding a larger (50-100 cc) dedicated gas sampling volume to the Orbiting Sample container (OS), (4) Adding a larger (50-100 cc) dedicated gas sampling volume to the OS that can be filled with compressed martian atmosphere.

Olivine-rich achondrites from Vesta and the missing mantle problem.

Mantles of rocky planets are dominantly composed of olivine and its high-pressure polymorphs, according to seismic data of Earth's interior, the mineralogy of natural samples, and modelling results. The missing mantle problem represents the paucity of olivine-rich material among meteorite samples and remote observation of asteroids, given how common differentiated planetesimals were in the early Solar System. Here we report the discovery of new olivine-rich meteorites that have asteroidal origins and are related to V-type asteroids or vestoids. Northwest Africa 12217, 12319, and 12562 are dunites and lherzolite cumulates that have siderophile element abundances consistent with origins on highly differentiated asteroidal bodies that experienced core formation, and with trace element and oxygen and chromium isotopic compositions associated with the howardite-eucrite-diogenite meteorites. These meteorites represent a step towards the end of the shortage of olivine-rich material, allowing for full examination of differentiation processes acting on planetesimals in the earliest epoch of the Solar System.

A CO2 greenhouse efficiently warmed the early Earth and decreased seawater 18O/16O before the onset of plate tectonics.

The low 18O/16O stable isotope ratios (δ18O) of ancient chemical sediments imply ∼70 °C Archean oceans if the oxygen isotopic composition of seawater (sw) was similar to modern values. Models suggesting lower δ18Osw of Archean seawater due to intense continental weathering and/or low degrees of hydrothermal alteration are inconsistent with the triple oxygen isotope composition (Δ'17O) of Precambrian cherts. We show that high CO2 sequestration fluxes into the oceanic crust, associated with extensive silicification, lowered the δ18Osw of seawater on the early Earth without affecting the Δ'17O. Hence, the controversial long-term trend of increasing δ18O in chemical sediments over Earth's history partly reflects increasing δ18Osw due to decreasing atmospheric pCO2 We suggest that δ18Osw increased from about -5‰ at 3.2 Ga to a new steady-state value close to -2‰ at 2.6 Ga, coinciding with a profound drop in pCO2 that has been suggested for this time interval. Using the moderately low δ18Osw values, a warm but not hot climate can be inferred from the δ18O of the most pristine chemical sediments. Our results are most consistent with a model in which the "faint young Sun" was efficiently counterbalanced by a high-pCO2 greenhouse atmosphere before 3 Ga.

Ingredients for microbial life preserved in 3.5 billion-year-old fluid inclusions.

It is widely hypothesised that primeval life utilised small organic molecules as sources of carbon and energy. However, the presence of such primordial ingredients in early Earth habitats has not yet been demonstrated. Here we report the existence of indigenous organic molecules and gases in primary fluid inclusions in c. 3.5-billion-year-old barites (Dresser Formation, Pilbara Craton, Western Australia). The compounds identified (e.g., H2S, COS, CS2, CH4, acetic acid, organic (poly-)sulfanes, thiols) may have formed important substrates for purported ancestral sulfur and methanogenic metabolisms. They also include stable building blocks of methyl thioacetate (methanethiol, acetic acid) - a putative key agent in primordial energy metabolism and thus the emergence of life. Delivered by hydrothermal fluids, some of these compounds may have fuelled microbial communities associated with the barite deposits. Our findings demonstrate that early Archaean hydrothermal fluids contained essential primordial ingredients that provided fertile substrates for earliest life on our planet.

Past aquatic environments in the Levant inferred from stable isotope compositions of carbonate and phosphate in fish teeth.

Here we explore the carbon and oxygen isotope compositions of the co-existing carbonate and phosphate fractions of fish tooth enameloid as a tool to reconstruct past aquatic fish environments and harvesting grounds. The enameloid oxygen isotope compositions of the phosphate fraction (δ18OPO4) vary by as much as ~4‰ for migratory marine fish such as gilthead seabream (Sparus aurata), predominantly reflecting the different saline habitats it occupies during its life cycle. The offset in enameloid Δ18OCO3-PO4 values of modern marine Sparidae and freshwater Cyprinidae from the Southeast Mediterranean region vary between 8.1 and 11.0‰, similar to values reported for modern sharks. The mean δ13C of modern adult S. aurata and Cyprinus carpio teeth of 0.1±0.4‰ and -6.1±0.7‰, respectively, mainly reflect the difference in δ13C of dissolved inorganic carbon (DIC) of the ambient water and dietary carbon sources. The enameloid Δ18OCO3-PO4 and δ13C values of ancient S. aurata (Holocene) and fossil Luciobarbus sp. (Cyprinidae; mid Pleistocene) teeth agree well with those of modern specimens, implying little diagenetic alteration of these tooth samples. Paired δ18OPO4-δ13C data from ancient S. aurata teeth indicate that hypersaline water bodies formed in the Levant region during the Late Holocene from typical Mediterranean coastal water with high evaporation rates and limited carbon input from terrestrial sources. Sparid tooth stable isotopes further suggest that coastal lagoons in the Eastern Mediterranean had already formed by the Early Holocene and were influenced by terrestrial carbon sources. Overall, combined enameloid oxygen and carbon isotope analysis of fish teeth is a powerful tool to infer the hydrologic evolution of aquatic environments and assess past fishing grounds of human populations in antiquity.

Determination of the triple oxygen and carbon isotopic composition of CO2 from atomic ion fragments formed in the ion source of the 253 Ultra high-resolution isotope ratio mass spectrometer.

RATIONALE: Determination of δ17 O values directly from CO2 with traditional gas source isotope ratio mass spectrometry is not possible due to isobaric interference of 13 C16 O16 O on 12 C17 O16 O. The methods developed so far use either chemical conversion or isotope equilibration to determine the δ17 O value of CO2 . In addition, δ13 C measurements require correction for the interference from 12 C17 O16 O on 13 C16 O16 O since it is not possible to resolve the two isotopologues. METHODS: We present a technique to determine the δ17 O, δ18 O and δ13 C values of CO2 from the fragment ions that are formed upon electron ionization in the ion source of the Thermo Scientific 253 Ultra high-resolution isotope ratio mass spectrometer (hereafter 253 Ultra). The new technique is compared with the CO2 -O2 exchange method and the 17 O-correction algorithm for δ17 O and δ13 C values, respectively. RESULTS: The scale contractions for δ13 C and δ18 O values are slightly larger for fragment ion measurements than for molecular ion measurements. The δ17 O and Δ17 O values of CO2 can be measured on the 17 O+ fragment with an internal error that is a factor 1-2 above the counting statistics limit. The ultimate precision depends on the signal intensity and on the total time that the 17 O+ beam is monitored; a precision of 14 ppm (parts per million) (standard error of the mean) was achieved in 20 hours at the University of Göttingen. The Δ17 O measurements with the O-fragment method agree with the CO2 -O2 exchange method over a range of Δ17 O values of -0.3 to +0.7‰. CONCLUSIONS: Isotope measurements on atom fragment ions of CO2 can be used as an alternative method to determine the carbon and oxygen isotopic composition of CO2 without chemical processing or corrections for mass interferences.

Zhamanshin astrobleme provides evidence for carbonaceous chondrite and post-impact exchange between ejecta and Earth's atmosphere.

Chemical fingerprints of impacts are usually compromised by extreme conditions in the impact plume, and the contribution of projectile matter to impactites does not often exceed a fraction of per cent. Here we use chromium and oxygen isotopes to identify the impactor and impact-plume processes for Zhamanshin astrobleme, Kazakhstan. ε54Cr values up to 1.54 in irghizites, part of the fallback ejecta, represent the 54Cr-rich extremity of the Solar System range and suggest a CI-like chondrite impactor. Δ17O values as low as -0.22‰ in irghizites, however, are incompatible with a CI-like impactor. We suggest that the observed 17O depletion in irghizites relative to the terrestrial range is caused by partial isotope exchange with atmospheric oxygen (Δ17O = -0.47‰) following material ejection. In contrast, combined Δ17O-ε54Cr data for central European tektites (distal ejecta) fall into the terrestrial range and neither impactor fingerprint nor oxygen isotope exchange with the atmosphere are indicated.Identifying the original impactor from craters remains challenging. Here, the authors use chromium and oxygen isotopes to indicate that the Zhamanshin astrobleme impactor was a carbonaceous chrondrite by demonstrating that depleted 17O values are due to exchange with atmospheric oxygen.

Tracing the oxygen isotope composition of the upper Earth's atmosphere using cosmic spherules.

Molten I-type cosmic spherules formed by heating, oxidation and melting of extraterrestrial Fe,Ni metal alloys. The entire oxygen in these spherules sources from the atmosphere. Therefore, I-type cosmic spherules are suitable tracers for the isotopic composition of the upper atmosphere at altitudes between 80 and 115 km. Here we present data on I-type cosmic spherules collected in Antarctica. Their composition is compared with the composition of tropospheric O2. Our data suggest that the Earth's atmospheric O2 is isotopically homogenous up to the thermosphere. This makes fossil I-type micrometeorites ideal proxies for ancient atmospheric CO2 levels.

Temperature and atmospheric CO2 concentration estimates through the PETM using triple oxygen isotope analysis of mammalian bioapatite.

The Paleocene-Eocene Thermal Maximum (PETM) is a remarkable climatic and environmental event that occurred 56 Ma ago and has importance for understanding possible future climate change. The Paleocene-Eocene transition is marked by a rapid temperature rise contemporaneous with a large negative carbon isotope excursion (CIE). Both the temperature and the isotopic excursion are well-documented by terrestrial and marine proxies. The CIE was the result of a massive release of carbon into the atmosphere. However, the carbon source and quantities of CO2 and CH4 greenhouse gases that contributed to global warming are poorly constrained and highly debated. Here we combine an established oxygen isotope paleothermometer with a newly developed triple oxygen isotope paleo-CO2 barometer. We attempt to quantify the source of greenhouse gases released during the Paleocene-Eocene transition by analyzing bioapatite of terrestrial mammals. Our results are consistent with previous estimates of PETM temperature change and suggest that not only CO2 but also massive release of seabed methane was the driver for CIE and PETM.

Revealing the climate of snowball Earth from Δ17O systematics of hydrothermal rocks.

The oxygen isotopic composition of hydrothermally altered rocks partly originates from the interacting fluid. We use the triple oxygen isotope composition ((17)O/(16)O, (18)O/(16)O) of Proterozoic rocks to reconstruct the (18)O/(16)O ratio of ancient meteoric waters. Some of these waters have originated from snowball Earth glaciers and thus give insight into the climate and hydrology of these critical intervals in Earth history. For a Paleoproterozoic [∼2.3-2.4 gigayears ago (Ga)] snowball Earth, δ(18)O = -43 ± 3‰ is estimated for pristine meteoric waters that precipitated at low paleo-latitudes (≤35°N). Today, such low (18)O/(16)O values are only observed in central Antarctica, where long distillation trajectories in combination with low condensation temperatures promote extreme (18)O depletion. For a Neoproterozoic (∼0.6-0.7 Ga) snowball Earth, higher meltwater δ(18)O estimates of -21 ± 3‰ imply less extreme climate conditions at similar paleo-latitudes (≤35°N). Both estimates are single snapshots of ancient water samples and may not represent peak snowball Earth conditions. We demonstrate how (17)O/(16)O measurements provide information beyond traditional (18)O/(16)O measurements, even though all fractionation processes are purely mass dependent.

Trachyandesitic volcanism in the early Solar System.

Volcanism is a substantial process during crustal growth on planetary bodies and well documented to have occurred in the early Solar System from the recognition of numerous basaltic meteorites. Considering the ureilite parent body (UPB), the compositions of magmas that formed a potential UPB crust and were complementary to the ultramafic ureilite mantle rocks are poorly constrained. Among the Almahata Sitta meteorites, a unique trachyandesite lava (with an oxygen isotope composition identical to that of common ureilites) documents the presence of volatile- and SiO2-rich magmas on the UPB. The magma was extracted at low degrees of disequilibrium partial melting of the UPB mantle. This trachyandesite extends the range of known ancient volcanic, crust-forming rocks and documents that volcanic rocks, similar in composition to trachyandesites on Earth, also formed on small planetary bodies ∼ 4.56 billion years ago. It also extends the volcanic activity on the UPB by ∼ 1 million years (Ma) and thus constrains the time of disruption of the body to later than 6.5 Ma after the formation of Ca-Al-rich inclusions.

Identification of the giant impactor Theia in lunar rocks.

The Moon was probably formed by a catastrophic collision of the proto-Earth with a planetesimal named Theia. Most numerical models of this collision imply a higher portion of Theia in the Moon than in Earth. Because of the isotope heterogeneity among solar system bodies, the isotopic composition of Earth and the Moon should thus be distinct. So far, however, all attempts to identify the isotopic component of Theia in lunar rocks have failed. Our triple oxygen isotope data reveal a 12 ± 3 parts per million difference in Δ(17)O between Earth and the Moon, which supports the giant impact hypothesis of Moon formation. We also show that enstatite chondrites and Earth have different Δ(17)O values, and we speculate on an enstatite chondrite-like composition of Theia. The observed small compositional difference could alternatively be explained by a carbonaceous chondrite-dominated late veneer.