The origin of volatile elements in the Earth-Moon system.

The origin of volatile species such as water in the Earth-Moon system is a subject of intense debate but is obfuscated by the potential for volatile loss during the Giant Impact that resulted in the formation of these bodies. One way to address these topics and place constraints on the temporal evolution of volatile components in planetary bodies is by using the observed decay of 87Rb to 87Sr because Rb is a moderately volatile element, whereas Sr is much more refractory. Here, we show that lunar highland rocks that crystallized ∼4.35 billion years ago exhibit very limited ingrowth of 87Sr, indicating that prior to the Moon-forming impact, the impactor commonly referred to as "Theia" and the proto-Earth both must have already been strongly depleted in volatile elements relative to primitive meteorites. These results imply that 1) the volatile element depletion of the Moon did not arise from the Giant Impact, 2) volatile element distributions on the Moon and Earth were principally inherited from their precursors, 3) both Theia and the proto-Earth probably formed in the inner solar system, and 4) the Giant Impact occurred relatively late in solar system history.

Fossil records of early solar irradiation and cosmolocation of the CAI factory: A reappraisal.

Calcium-aluminum­rich inclusions (CAIs) in meteorites carry crucial information about the environmental conditions of the nascent Solar System prior to planet formation. Based on models of 50V­10Be co-production by in-situ irradiation, CAIs are considered to have formed within ~0.1 AU from the proto-Sun. Here, we present vanadium (V) and strontium (Sr) isotopic co-variations in fine- and coarse-grained CAIs and demonstrate that kinetic isotope effects during partial condensation and evaporation best explain V isotope anomalies previously attributed to solar particle irradiation. We also report initial excesses of 10Be and argue that CV CAIs possess essentially a homogeneous level of 10Be, inherited during their formation. Based on numerical modeling of 50V­10Be co-production by irradiation, we show that CAI formation during protoplanetary disk build-up likely occurred at greater heliocentric distances than previously considered, up to planet-forming regions (~1AU), where solar particle fluxes were sufficiently low to avoid substantial in-situ irradiation of CAIs.

Samarium isotope compositions of uranium ore concentrates: A novel nuclear forensic signature.

Uranium ore is mined and milled to produce uranium ore concentrate (UOC), a regulated product of the nuclear fuel cycle. Diversion of UOC from the fuel cycle into possible weapons production is a key concern in global nonproliferation efforts. As such, the ability to trace the origin of seized nuclear materials is imperative to law enforcement efforts. Although isotopic signatures of UOCs have proven fruitful to pinpoint sample provenance, new isotopic signatures are needed because most existing isotopic signatures are not indicative of the original ore body from which the U is derived. In this work, we developed a new method to separate samarium (Sm) from a U-rich sample matrix and report the first Sm isotope compositions of 32 UOCs derived from a variety of worldwide uranium mines. Relative to terrestrial standards, approximately half the UOCs have resolved and anticorrelated 149Sm-150Sm isotope compositions, consistent with the capture of thermal neutrons by 149Sm in the ore body. The UOCs with anomalous Sm isotope compositions tend to derive from older (~>1.5Ga) and higher-grade ore bodies, although other factors, such as the presence of neutron moderators like water, also play a role. Nonetheless, the Sm isotope compositions of UOCs directly reflects the neutron fluence over the history of the original ore body and can be used to discern different geologic conditions associated with that ore body. As such, this work demonstrates the potential use of Sm isotopes as a novel nuclear forensics signature for origin assessment of UOCs.

Astronomical context of Solar System formation from molybdenum isotopes in meteorite inclusions.

Calcium-aluminum-rich inclusions (CAIs) in meteorites are the first solids to have formed in the Solar System, defining the epoch of its birth on an absolute time scale. This provides a link between astronomical observations of star formation and cosmochemical studies of Solar System formation. We show that the distinct molybdenum isotopic compositions of CAIs cover almost the entire compositional range of material that formed in the protoplanetary disk. We propose that CAIs formed while the Sun was in transition from the protostellar to pre-main sequence (T Tauri) phase of star formation, placing Solar System formation within an astronomical context. Our results imply that the bulk of the material that formed the Sun and Solar System accreted within the CAI-forming epoch, which lasted less than 200,000 years.

Combined mass-dependent and nucleosynthetic isotope variations in refractory inclusions and their mineral separates to determine their original Fe isotope compositions.

Calcium-aluminum-rich inclusions (CAIs) are the oldest dated materials that provide crucial information about the isotopic reservoirs present in the early Solar System. For a variety of elements, CAIs have isotope compositions that are uniform yet distinct from later formed solid material. However, despite being the most abundant metal in the Solar System, the isotopic composition of Fe in CAIs is not well constrained. In an attempt to determine the Fe isotopic compositions of CAIs, we combine extensive work from a previously studied CAI sample set with new isotopic work characterizing mass-dependent and mass-independent (nucleosynthetic) signatures in Mg, Ca, and Fe. This investigation includes work on three mineral separates of the Allende CAI Egg 2. For all isotope systems investigated, we find that in general, fine-grained CAIs exhibit light mass-dependent isotopic signatures relative to terrestrial standards, whereas igneous CAIs have heavier isotopic compositions relative to the fine-grained CAIs. Importantly, the mass-dependent Fe isotope signatures of bulk CAIs show a range of both light (fine-grained CAIs) and heavy (igneous CAIs) isotopic signatures relative to bulk chondrites, suggesting that Fe isotope signatures in CAIs largely derive from mass fractionation events such as condensation and evaporation occurring in the nebula. Such signatures show that a significant portion of the secondary alteration experienced by CAIs, particularly prevalent in fine-grained inclusions, occurred in the nebula prior to accretion into their respective parent bodies. Regarding nucleosynthetic Fe isotope signatures, we do not observe any variation outside of analytical uncertainty in bulk CAIs compared to terrestrial standards. In contrast, all three Egg 2 mineral separates display resolved mass-independent excesses in 56Fe compared to terrestrial standards. Furthermore, we find that the combined mass-dependent and nucleosynthetic Fe isotopic compositions of the Egg 2 mineral separates are well correlated, likely indicating that Fe indigenous to the CAI is mixed with less anomalous Fe, presumably from the solar nebula. Thus, these reported nucleosynthetic anomalies may point in the direction of the original Fe isotope composition of the CAI-forming region, but they likely only provide a minimum isotopic difference between the original mass-independent Fe isotopic composition of CAIs and that of later formed solids.

Titanium isotope signatures of calcium-aluminum-rich inclusions from CV and CK chondrites: Implications for early Solar System reservoirs and mixing.

Calcium-aluminum-rich inclusions (CAIs) are the first solids to form in the early Solar System, and they exhibit nucleosynthetic anomalies in many isotope systems. The overwhelming majority of isotopic data for CAIs has been limited to inclusions from the CV chondrite Allende and a select few other CV, CO, CM, and ordinary chondrites. It is therefore important to ascertain whether previously reported values for CAIs are representative of the broader CAI-forming region and to make a more rigorous assessment of the extent and implications of isotopic heterogeneity in the early Solar System. Here, we report the mass-independent Ti isotopic compositions of a suite of 23 CAIs of diverse petrologic and geochemical types, including 11 from Allende and 12 from seven other CV3 and CK3 chondrites; the data for CAIs from CK chondrites represent the first reported measurements of Ti isotope compositions of refractory inclusions from this meteorite class. The resolved variation in the mass-independent Ti isotopic compositions of these CAIs indicates that the CAI-forming region of the early Solar System preserved isotopic variability at their time of formation. Nevertheless, the range of Ti isotope compositions reported here for CAIs from CV and CK chondrites falls within the range observed in previously analyzed CAIs from CV, CO, CM, and ordinary chondrites. This implies that CAIs from CV, CK, CO, CM, and ordinary chondrites originated from a common nebular source reservoir characterized by mass-independent isotopic variability in Ti (and other select elements). We further interpret these data to indicate that the Ti isotope anomalies in CAIs represent the isotopic signatures of supernova components in presolar grains that were incorporated into the Solar System in an initially poorly mixed reservoir that was progressively homogenized over time. We conclude that the differing degrees of isotopic variability observed for different elements in normal CAIs are the result of distinct carrier phases and that these CAIs were likely formed towards the final stages of homogenization of the large-scale isotopic heterogeneity that initially existed in the solar nebula.

Evidence for supernova injection into the solar nebula and the decoupling of r-process nucleosynthesis.

The isotopic composition of our Solar System reflects the blending of materials derived from numerous past nucleosynthetic events, each characterized by a distinct isotopic signature. We show that the isotopic compositions of elements spanning a large mass range in the earliest formed solids in our Solar System, calcium-aluminum-rich inclusions (CAIs), are uniform, and yet distinct from the average Solar System composition. Relative to younger objects in the Solar System, CAIs contain positive r-process anomalies in isotopes A < 140 and negative r-process anomalies in isotopes A > 140. This fundamental difference in the isotopic character of CAIs around mass 140 necessitates (i) the existence of multiple sources for r-process nucleosynthesis and (ii) the injection of supernova material into a reservoir untapped by CAIs. A scenario of late supernova injection into the protoplanetary disk is consistent with formation of our Solar System in an active star-forming region of the galaxy.

Uranium isotope compositions of the basaltic angrite meteorites and the chronological implications for the early Solar System.

Events occurring within the first 10 million years of the Solar System's approximately 4.5 billion-year history, such as formation of the first solids, accretion, and differentiation of protoplanetary bodies, have determined the evolutionary course of our Solar System and the planetary bodies within it. The application of high-resolution chronometers based on short-lived radionuclides is critical to our understanding of the temporal sequence of these critical events. However, to map the relative ages from such chronometers onto the absolute time scale, they must be "anchored" to absolute ages of appropriate meteoritic materials using the high-precision lead-lead (Pb-Pb) chronometer. Previously reported Pb-Pb dates of the basaltic angrite meteorites, some of which have been used extensively as time anchors, assumed a constant (238)U/(235)U ratio (= 137.88). In this work, we report measurements of (238)U/(235)U ratios in several angrites that are distinct from the previously assumed value, resulting in corrections to the Pb-Pb ages of ≥ 1 million years. There is no resolvable variation in the (238)U/(235)U ratio among the angrite bulk samples or mineral separates, suggesting homogeneity in the U isotopic composition of the angrite parent body. Based on these measurements, we recalculated the Pb-Pb age for the commonly used anchor, the D'Orbigny angrite, to be 4563.37 ± 0.25 Ma. An adjustment to the Pb-Pb age of a time anchor (such as D'Orbigny) requires a corresponding correction to the "model ages" of all materials dated using that anchor and a short-lived chronometer. This, in turn, has consequences for accurately defining the absolute timeline of early Solar System events.

Rapid expansion of oceanic anoxia immediately before the end-Permian mass extinction.

Periods of oceanic anoxia have had a major influence on the evolutionary history of Earth and are often contemporaneous with mass extinction events. Changes in global (as opposed to local) redox conditions can be potentially evaluated using U system proxies. The intensity and timing of oceanic redox changes associated with the end-Permian extinction horizon (EH) were assessed from variations in (238)U/(235)U (δ(238)U) and Th/U ratios in a carbonate section at Dawen in southern China. The EH is characterized by shifts toward lower δ(238)U values (from -0.37‰ to -0.65‰), indicative of an expansion of oceanic anoxia, and higher Th/U ratios (from 0.06 to 0.42), indicative of drawdown of U concentrations in seawater. Using a mass balance model, we estimate that this isotopic shift represents a sixfold increase in the flux of U to anoxic facies, implying a corresponding increase in the extent of oceanic anoxia. The intensification of oceanic anoxia coincided with, or slightly preceded, the EH and persisted for an interval of at least 40,000 to 50,000 y following the EH. These findings challenge previous hypotheses of an extended period of whole-ocean anoxia prior to the end-Permian extinction.

Uranium isotope fractionation during adsorption to Mn-oxyhydroxides.

Previous work has shown uranium (U) isotope fractionation between natural ferromanganese crusts and seawater. Understanding the mechanism that causes (238)U/(235)U fractionation during adsorption to ferromanganese oxides is a critical step in the utilization of (238)U/(235)U as a tracer of U adsorption reactions in groundwater as well as a potential marine paleoredox proxy. We conducted U adsorption experiments using synthetic K-birnessite and U-bearing solutions. These experiments revealed a fractionation matching that observed between seawater and natural ferromanganese sediments: adsorbed U is isotopically lighter by ∼0.2‰ (δ(238/235)U) than dissolved U. As the redox state of U does not change during adsorption, a difference in the coordination environment between dissolved and adsorbed U is likely responsible for this effect. To test this hypothesis, we analyzed U adsorbed to K-birnessite in our experimental study using extended X-ray absorption fine structure (EXAFS) spectroscopy, to obtain information about U coordination in the adsorbed complex. Comparison of our EXAFS spectra with those for aqueous U species reveals subtle, but important, differences in the U-O coordination shell between dissolved and adsorbed U. We hypothesize that these differences are responsible for the fractionation observed in our experiments as well as for some U isotope variations in nature.