The impactor flux record to Earth has largely been erased by active tectonics, weathering, and continual reworking of the crust. Instead, a record of highly siderophile elements (HSE: Re, Os, Ir, Ru, Rh, Pt, Pd, and Au) in lunar impactites has been used as aproxy for the type of impactor material added to the Earth-Moon system. Quantifying impactor mass and flux with the HSE can potentially be complicated by numerous secondary processes, however, including silicate-metal segregation and multiple impact heritage. In contrast, because oxygen has an invariant geochemical affinity, triple oxygen isotope compositions have the potential to offer a robust long-term record of impactor fluxes in complex mixtures such as regolith. Here, we use high-precision triple oxygen isotopes to deconvolve the influences of meteorite addition and silicate vaporization and identify a ubiquitous impactor contaminant comprised of partially evaporated CM or ureilite-like material representing at least 1 wt% of the lunar regolith. Water delivered to Earth by meteorite material over 4 billion years therefore is only a fraction of an ocean's worth of water but is a significant contributor to the ice reservoir of the lunar cold traps.

Abstract The Neogene expansion of C 4 grasslands transformed terrestrial ecosystems with marked influence on mammalian evolution, including hominins. However, the asynchronous C 4 expansion on different continents makes it difficult to identify the environmental drivers, especially for higher latitudes. Here we show that rainfall seasonality governed extratropical Plio-Pleistocene C 4 distributions in East Asia. Rainfall oxygen isotope ratios and clumped isotope soil temperatures exhibit coupled variations on the Chinese Loess Plateau (CLP) from 7 to 2.5 million years ago, indicating more spring rain during warmer times when the subtropical westerly jet was further poleward, and more concentrated summer rain under cooler climates. We attribute these changes to meridional shifts of a summer rain band on orbital and longer timescales. The most C 4 -rich ecosystems, as identified by organic carbon δ 13 C records, tracked this summer rain band, eventually eclipsing the southern CLP margin during the late Pleistocene cooling. Our model refines the East Asian paleomonsoon concept and explains the equatorward migration of extratropical C 4 ecosystems, highlighting the tight coupling between regional rainfall seasonality and vegetation.

Pebble accretion is an efficient mechanism for early terrestrial protoplanet growth and differentiation. Metal-silicate partitioning of moderately siderophile elements offers constraints on the role of pebble accretion in Earth's formation and the segregation of its core. Here, we determine pebble accretion properties of the proto-Earth that are consistent with metal-silicate partitioning measurements and siderophile abundances in the mantle and core. We combine a pebble accretion model that includes mass balances for siderophile abundances in the mantle and core of a growing terrestrial protoplanet with experimentally-determined partition functions for seven moderately siderophile elements: Ni, Co, V, Cr, Mo, Mn, and W. Mantle and core abundances of these elements during pebble accretion are calculated, as well as changes to their abundances following the addition of large and giant impactors built with pebbles. Model results are compared to the estimated abundances of these elements in Earth's primitive mantle and core. We find that metal-silicate partitioning of these elements is especially sensitive to the total mass of accreted pebbles. Best fits to primitive mantle and core siderophile abundances are found in cases where the proto-Earth accreted with pebbles to approximately 0.6 times its present mass under slightly reducing conditions, then added the remaining mass via one or more impactors with the same composition. We also find that pebbles consisting of chondritic components (chondrules, metal grains, AOAs, and CAIs) generally yield better partitioning results compared to pebbles made from chondrites.

The Dinaric Alps formed as a result of the collision between the Adria microplate with Eurasia during ongoing closure of the Tethys Ocean. However, there remain a number of questions regarding the mechanisms that created and sustained the high topography (maximum modern elevation of ~2500 m) of this region. We take advantage of a series of lacustrine basins—known as the Dinaride Lake System (DLS)—that formed in the Early and Middle Miocene to constrain paleo-elevations of the Dinaric Alps using stable isotope paleoaltimetry. We collected authigenic lacustrine carbonate samples from six basins in Croatia and Bosnia and Herzegovina that span the range from sea-level to high-elevation (~1200 m) and measured these samples for δ18O. In addition, we also collected stream samples that span the range to constrain the modern change in δ18O across the Dinaric Alps. Stable-isotope paleoaltimetry is based on the concept that, as moist air parcels are forced upwards by orography, 18O is preferentially removed by the resulting precipitation, resulting in lower δ18O at higher-elevations and in the lee of ranges. Today, meteoric water δ18O is high (~ -6‰) at the coast and is ~5‰ lower at the crest of the range (~ -11‰). However, Middle Miocene lacustrine carbonate δ18O is high (~ -3‰) at the crest of the range and lower (~ -6‰) at the coast. Because lacustrine carbonate δ18O is frequently impacted by evaporation, we analyzed a subset of our samples for Δ17O, which is sensitive to the degree of evaporation. These carbonates have Δ17O values ranging from -68 to -150 per meg. Using our Δ17O data and a model of lake evaporation, we reconstruct the unevaporated meteoric water δ18O. Our preliminary results show a similar trend as in the modern, with higher δ18O values at the coast and lower δ18O at the crest of the range. Reconstructed unevaporated meteoric water δ18O at the crest is lower by 2-5‰ than modern water δ18O at the crest of the Dinaric Alps. That unevaporated meteoric water δ18O might have been lower than today at the crest of the range suggest that the Dinaric Alps were higher in the Middle Miocene that today, assuming that coastal meteoric water δ18O was similar to today. Thus, ongoing extension within the Dinaric Alps due to slab rollback may be responsible for lowering of topography.

Pebble accretion provides new insights into Earth's building blocks and early protoplanetary disk conditions. Here, we show that mixtures of chondritic components: metal grains, chondrules, calcium-aluminum-rich inclusions (CAIs), and amoeboid olivine aggregates (AOAs) match Earth's major element composition (Fe, Ni, Si, Mg, Ca, Al, O) within uncertainties, whereas no combination of chondrites and iron meteorites does. Our best fits also match the epsilon 54Cr and epsilon 50Ti values of Earth precisely, whereas the best fits for chondrites, or components with a high proportion of E chondrules, fails to match Earth. In contrast to some previous studies, our best-fitting component mixture is predominantly carbonaceous, rather than enstatite chondrules. It also includes 15 wt% of early-formed refractory inclusions (CAIs + AOAs), which is similar to that found in some C chondrites (CO, CV, CK), but notably higher than NC chondrites. High abundances of refractory materials is lacking in NC chondrites, because they formed after the majority of refractory grains were either drawn into the Sun or incorporated into terrestrial protoplanets via pebble accretion. We show that combinations of Stokes numbers of chondritic components build 0.35-0.7 Earth masses in 2 My in the Hill regime accretion, for a typical pebble column density of 1.2 kg/m2 at 1 au. However, a larger or smaller column density leads to super-Earth or moon-mass bodies, respectively. Our calculations also demonstrate that a few My of pebble accretion with these components yields a total protoplanet mass inside 1 au exceeding the combined masses of Earth, Moon, Venus, and Mercury. Accordingly, we conclude that pebble accretion is a viable mechanism to build Earth and its major element composition from primitive chondritic components within the solar nebula lifetime.

Fossiliferous carbonate concretions are commonly found in sediments deposited in the Late Cretaceous Western Interior Seaway. Although concretions are diagenetic features, well-preserved fossils from within them have been instrumental in reconstructing the temperature and S18O value of Western Interior Seaway seawater, which is essential for accurate reconstruction of Late Cretaceous climate. Here, we constrain formation conditions of Late Campanian and early Maastrichtian carbonate concretions by combining triple oxygen isotope measurements with carbonate clumped isotope paleothermometry on different carbonate phases within the concretions. We measured both fossil skeletal aragonite and sparry calcite infill from cracks and within macrofossil voids to evaluate differences between "primary" and "altered" geochemical signals. Based on the two temperature-sensitive isotope systems of the primary fossil shell aragonite, the temperature of the Western Interior Seaway was between 20 degrees C and 40 degrees C and was likely thermally stratified during the Campanian. The reconstructed S 18 O seawater values of similar to - 1 parts per thousand for Campanian Western Interior Seaway waters are similar to those expected for the open ocean during greenhouse climates, while the Maastrichtian Western Interior Seaway may have been more restricted, with a S 18 O seawater value of similar to 2 parts per thousand, which reflects more evaporative conditions. We reconstructed the diagenetic history of the sparry infill and altered fossils using a fluid-rock mixing model. Alteration temperature, alteration fluid S18O value, and the initial formation temperature were calculated by applying the fluid-rock mixing model to a particle swarm optimization algorithm. We found a different range of initial formation temperatures between the Campanian (25-38 degrees C) and Maastrichtian (9-28 degrees C). We also found that alteration in the presence of light meteoric fluids (S18O approximate to - 10 parts per thousand) is required to explain both the sparry infill and the altered fossil isotopic values. Based on our results, both lithification and alteration of the carbonates occurred soon after burial, and light meteoric fluids support prior findings that high-topographic relief existed on the western margin of the Western Interior Seaway during the Late Cretaceous. As one of the first studies to apply these techniques in concert and across multiple mineralogical phases within samples, our results provide important constraints on paleoenvironmental conditions in an enigmatic ocean system and will improve interpretations of the overall health of ecosystems leading into the end-Cretaceous mass extinction.

Triple oxygen isotope values of xylem water were measured along the length of smooth horsetail stems (Equisetum laevigatum). Extreme isotope enrichment is observed moving from base to stem tip. δ18O values range from -8.3‰ at the base to 82.6‰ at the tip. Δ'17O values range from 0 to -1,797 per meg. The δ18O and Δ'17O values are the most extreme measured for any terrestrial material and expand the known range of Δ'17O values by fivefold for mass-dependent fractionation on Earth. The extreme isotope enrichments are explained using a hybrid evaporation/chain-of-lakes model, allowing us to refine the leaf respiration coefficient to θk = 0.511 ± 0.001. This new value is required to explain the low Δ'17O values previously measured in desert plants and animals and is critical when using fossil samples for paleoclimate reconstruction. Coexisting phytoliths and stem water were also measured. The 1000ln18αsilica-water value at the plant base (35.89‰) appears to be in isotopic equilibrium, with far smaller fractionations of 10.3‰ near the tip. The smaller fractionations at higher levels are explained by continual silica deposition as the plant elongates and the δ18O values of each segment become higher. The overall integrated phytolith value is a combination of early and late silica growth. The Δ'17Osilica - Δ'17Owater values are not in equilibrium, explained by a kinetic isotope effect, with a λ value of 0.5205 vs. 0.5244 for equilibrium. Phytolith isotope values may lead to erroneous interpretations for paleoclimate reconstruction.

Numerous missions to the Moon have identified and documented volatile deposits associated with permanently shadowed regions. A series of science goals for the Artemis Program is to explore these volatile deposits and return samples to Earth. Volatiles in these reservoirs may consist of a variety of species whose stable isotope characteristics could elucidate both their sources and the processes instrumental in their formation. For example, the δD of potential contributors to the deposits can be used to identify a uniquely light solar wind component. Because of the exceptionally low temperatures of these volatile deposits, examining and interpreting their stable isotope systems to fulfill Artemis science goals through sampling, preserving, curating, and analyzing these samples are far more difficult than for other sample return missions. Collecting and preserving the samples at cryogenic temperatures dramatically increases science yield but is technologically demanding and poses increased risk during transport.

Morbidelli, Kleine Nimmo (2024) (MKN) recently published a critical analysis on whether the terrestrial planets in the Solar System formed by rapid pebble accretion or by the classical route of multiple giant impacts between planetary embryos after the dissipation of the protoplanetary disc. They arrive at the conclusion that the terrestrial planets did not form by pebble accretion. Although we welcome debate on this topic, we want to emphasize here several points that we disagree on. We will not address in detail every claim made in MKN, but rather stick to four main points. Our conclusion is that pebble accretion remains a viable mechanism to drive significant growth of protoplanets in the protoplanetary disc, with as much as 70 pebble accretion. This rapid growth phase must nevertheless have been followed by an extended period of collisional growth after the end of the protoplanetary disc phase, likely culminating with the moon-forming giant impact. We emphasize here an important recent result from Sharp Olson (2023), namely that significant growth by pebble accretion can be reconciled with the Hf-W decay system even for a canonical moon-forming giant impact with a Mars-mass protoplanet - a near-equal mass impactor, as proposed in Johansen et al. (2023), is not necessary. Given that terrestrial planet formation naturally involves both pebble accretion and a combination of small and large impactors, this challenges the very notion of making an either/or distinction between the classical collision model and the pebble accretion model.

AbstractTriple oxygen isotopes of Cenozoic intrusive rocks emplaced along the Ross Sea coastline in Antarctica, reveal that meteoric-hydrothermal waters imprinted their stable isotope composition on mineral phases, leaving a clear record of oxygen and hydrogen isotope variations during the establishment of the polar cap. Calculated O- and H-isotope compositions of meteoric waters vary from −9 ± 2‰ and −92 ± 5‰ at 40 ± 0.6 Ma, to −30 and −234 ± 5‰ at 34 ± 1.9 Ma, and intersect the modern Global Meteoric Water Line. These isotopic variations likely depict the combined variations in temperature, humidity, and moisture source regions, resulting from rearrangement of oceanic currents and atmospheric cooling during the onset of continental ice cap. Here, we report a paleo-climatic proxy based on triple oxygen geochemistry of crystalline rocks that reveals changes in the hydrological cycle. We discuss the magnitude of temperature changes at high latitudes during the Eocene-Oligocene climatic transition.