Methodologies for 176Lu-176Hf Analysis of Zircon Grains from the Moon and Beyond.

Zircons are found in extraterrestrial rocks from the Moon, Mars, and some differentiated meteorite parent-bodies. These zircons are rare, often of small size, and have been affected by neutron capture induced by cosmic ray exposure. The application of the 176Lu-176Hf decay system to zircons from planetary bodies such as the Moon can help establish the chronology of large-scale differentiation processes such as the crystallization of the lunar magma ocean. Here, we present methods to measure the isotopic composition of Hf of extraterrestrial zircons dated using ID-TIMS U-Pb after chemical abrasion. We introduce a 2-stage elution scheme to separate Hf from Zr while preserving the unused Zr fraction for future isotopic analysis. The effect of neutron capture is also re-examined using the latest thermal neutron capture cross sections and epithermal resonance integrals. Our tests show that the precision of Hf isotopic analyses is close to what is theoretically attainable. We have tested this method to a limited set of zircon grains from lunar rocks returned by the Apollo missions (lunar soil 14163, fragmental polymict breccia 72275, and clast-rich breccia 14321). The model ages align with previously reported values, but further work is needed to assess the chronology of lunar magma ocean crystallization as only a handful of small zircons (5 zircons from 3 samples) were analyzed, and the precision of the analyses can be improved by measuring more and larger lunar zircon grains.

Long-term repeatability and interlaboratory reproducibility of high-precision ID-TIMS U-Pb geochronology.

Age determination of minerals using the U-Pb technique is widely used to quantify time in Earth's history. A number of geochronology laboratories produce the highest precision U-Pb dates employing the EARTHTIME 202Pb-205Pb-233U-235U tracer solution for isotope dilution, and the EARTHTIME ET100 and ET2000 solutions for system calibration and laboratory intercalibration. Here, we report ET100 and ET2000 solution data from the geochronology laboratory of University of Geneva obtained between 2008 and 2021 and compare the most recent data with results from the geochronology laboratories of Princeton University and ETH Zürich. This compilation demonstrates that (i) the choice of the thermal ionization mass spectrometer model has no influence on precision and accuracy of the data; (ii) the often observed excess scatter of apparent ET100 solution 206Pb/238U dates can be mitigated by more careful tracer-sample equilibration; and (iii) natural zircon reference materials are not suitable for evaluating intra-laboratory repeatability and inter-laboratory reproducibility, since they combine several phenomena of natural system complexities (especially domains of different age within the same zircon grain, and residual loss of radiogenic lead in domains of high decay damage after chemical abrasion pre-treatment). We provide our best estimates of apparent dates for the ET100 solution (206Pb/238U date, 100.173 ± 0.003 Ma), for ET2000 solution (207Pb/206Pb date, 1999.935 ± 0.063 Ma), as well as for natural reference zircon Temora-2 (206Pb/238U date, 417.353 ± 0.052 Ma). These data will allow U-Pb laboratories to evaluate their analytical performance and to independently calibrate non-EARTHTIME tracer solutions in use.

Transient rhyolite melt extraction to produce a shallow granitic pluton.

Rhyolitic melt that fuels explosive eruptions often originates in the upper crust via extraction from crystal-rich sources, implying an evolutionary link between volcanism and residual plutonism. However, the time scales over which these systems evolve are mainly understood through erupted deposits, limiting confirmation of this connection. Exhumed plutons that preserve a record of high-silica melt segregation provide a critical subvolcanic perspective on rhyolite generation, permitting comparison between time scales of long-term assembly and transient melt extraction events. Here, U-Pb zircon petrochronology and 40Ar/39Ar thermochronology constrain silicic melt segregation and residual cumulate formation in a ~7 to 6 Ma, shallow (3 to 7 km depth) Andean pluton. Thermo-petrological simulations linked to a zircon saturation model map spatiotemporal melt flux distributions. Our findings suggest that ~50 km3 of rhyolitic melt was extracted in ~130 ka, transient pluton assembly that indicates the thermal viability of advanced magma differentiation in the upper crust.

Geologic evidence for an icehouse Earth before the Sturtian global glaciation.

Snowball Earth episodes, times when the planet was covered in ice, represent the most extreme climate events in Earth's history. Yet, the mechanisms that drive their initiation remain poorly constrained. Current climate models require a cool Earth to enter a Snowball state. However, existing geologic evidence suggests that Earth had a stable, warm, and ice-free climate before the Neoproterozoic Sturtian global glaciation [ca. 717 million years (Ma) ago]. Here, we present eruption ages for three felsic volcanic units interbedded with glaciolacustrine sedimentary rocks from southwest Virginia, USA, that demonstrate that glacially influenced sedimentation occurred at tropical latitudes ca. 751 Ma ago. Our findings are the first geologic evidence of a cool climate teetering on the edge of global glaciation several million years before the Sturtian Snowball Earth.

U-Pb constraints on pulsed eruption of the Deccan Traps across the end-Cretaceous mass extinction.

Temporal correlation between some continental flood basalt eruptions and mass extinctions has been proposed to indicate causality, with eruptive volatile release driving environmental degradation and extinction. We tested this model for the Deccan Traps flood basalt province, which, along with the Chicxulub bolide impact, is implicated in the Cretaceous-Paleogene (K-Pg) extinction approximately 66 million years ago. We estimated Deccan eruption rates with uranium-lead (U-Pb) zircon geochronology and resolved four high-volume eruptive periods. According to this model, maximum eruption rates occurred before and after the K-Pg extinction, with one such pulse initiating tens of thousands of years prior to both the bolide impact and extinction. These findings support extinction models that incorporate both catastrophic events as drivers of environmental deterioration associated with the K-Pg extinction and its aftermath.

Rapid eruption of the Columbia River flood basalt and correlation with the mid-Miocene climate optimum.

Flood basalts, the largest volcanic events in Earth history, are thought to drive global environmental change because they can emit large volumes of CO2 and SO2 over short geologic time scales. Eruption of the Columbia River Basalt Group (CRBG) has been linked to elevated atmospheric CO2 and global warming during the mid-Miocene climate optimum (MMCO) ~16 million years (Ma) ago. However, a causative relationship between volcanism and warming remains speculative, as the timing and tempo of CRBG eruptions is not well known. We use U-Pb geochronology on zircon-bearing volcanic ash beds intercalated within the basalt stratigraphy to build a high-resolution CRBG eruption record. Our data set shows that more than 95% of the CRBG erupted between 16.7 and 15.9 Ma, twice as fast as previous estimates. By suggesting a recalibration of the geomagnetic polarity time scale, these data indicate that the onset of flood volcanism is nearly contemporaneous with that of the MMCO.

GZ7 and GZ8 - Two Zircon Reference Materials for SIMS U-Pb Geochronology.

Here, we document a detailed characterisation of two zircon gemstones, GZ7 and GZ8. Both stones had the same mass at 19.2 carats (3.84 g) each; both came from placer deposits in the Ratnapura district, Sri Lanka. The U-Pb data are in both cases concordant within the uncertainties of decay constants and yield weighted mean 206Pb/238U ages (95% confidence uncertainty) of 530.26 Ma ± 0.05 Ma (GZ7) and 543.92 Ma ± 0.06 Ma (GZ8). Neither GZ7 nor GZ8 have been subjected to any gem enhancement by heating. Structure-related parameters correspond well with the calculated alpha doses of 1.48 × 1018 g-1 (GZ7) and 2.53 × 1018 g-1 (GZ8), respectively, and the (U-Th)/He ages of 438 Ma ± 3 Ma (2s) for GZ7 and 426 Ma ± 9 Ma (2s) for GZ8 are typical of unheated zircon from Sri Lanka. The mean U mass fractions are 680 µg g-1 (GZ7) and 1305 µg g-1 (GZ8). The two zircon samples are proposed as reference materials for SIMS (secondary ion mass spectrometry) U-Pb geochronology. In addition, GZ7 (Ti mass fractions 25.08 µg g-1 ± 0.18 µg g-1; 95% confidence uncertainty) may prove useful as reference material for Ti-in-zircon temperature estimates.

Early formation of the Moon 4.51 billion years ago.

Establishing the age of the Moon is critical to understanding solar system evolution and the formation of rocky planets, including Earth. However, despite its importance, the age of the Moon has never been accurately determined. We present uranium-lead dating of Apollo 14 zircon fragments that yield highly precise, concordant ages, demonstrating that they are robust against postcrystallization isotopic disturbances. Hafnium isotopic analyses of the same fragments show extremely low initial 176Hf/177Hf ratios corrected for cosmic ray exposure that are near the solar system initial value. Our data indicate differentiation of the lunar crust by 4.51 billion years, indicating the formation of the Moon within the first ~60 million years after the birth of the solar system.

Thermal erosion of cratonic lithosphere as a potential trigger for mass-extinction.

The temporal coincidence between large igneous provinces (LIPs) and mass extinctions has led many to pose a causal relationship between the two. However, there is still no consensus on a mechanistic model that explains how magmatism leads to the turnover of terrestrial and marine plants, invertebrates and vertebrates. Here we present a synthesis of ammonite biostratigraphy, isotopic data and high precision U-Pb zircon dates from the Triassic-Jurassic (T-J) and Pliensbachian-Toarcian (Pl-To) boundaries demonstrating that these biotic crises are both associated with rapid change from an initial cool period to greenhouse conditions. We explain these transitions as a result of changing gas species emitted during the progressive thermal erosion of cratonic lithosphere by plume activity or internal heating of the lithosphere. Our petrological model for LIP magmatism argues that initial gas emission was dominated by sulfur liberated from sulfide-bearing cratonic lithosphere before CO2 became the dominant gas. This model offers an explanation of why LIPs erupted through oceanic lithosphere are not associated with climatic and biotic crises comparable to LIPs emitted through cratonic lithosphere.

Volcanic-plutonic parity and the differentiation of the continental crust.

The continental crust is central to the biological and geological history of Earth. However, crustal heterogeneity has prevented a thorough geochemical comparison of its primary igneous building blocks-volcanic and plutonic rocks-and the processes by which they differentiate to felsic compositions. Our analysis of a comprehensive global data set of volcanic and plutonic whole-rock geochemistry shows that differentiation trends from primitive basaltic to felsic compositions for volcanic versus plutonic samples are generally indistinguishable in subduction-zone settings, but are divergent in continental rifts. Offsets in major- and trace-element differentiation patterns in rift settings suggest higher water content in plutonic magmas and reduced eruptibility of hydrous silicate magmas relative to dry rift volcanics. In both tectonic settings, our results indicate that fractional crystallization, rather than crustal melting, is predominantly responsible for the production of intermediate and felsic magmas, emphasizing the role of mafic cumulates as a residue of crustal differentiation.

Earth history. U-Pb geochronology of the Deccan Traps and relation to the end-Cretaceous mass extinction.

The Chicxulub asteroid impact (Mexico) and the eruption of the massive Deccan volcanic province (India) are two proposed causes of the end-Cretaceous mass extinction, which includes the demise of nonavian dinosaurs. Despite widespread acceptance of the impact hypothesis, the lack of a high-resolution eruption timeline for the Deccan basalts has prevented full assessment of their relationship to the mass extinction. Here we apply uranium-lead (U-Pb) zircon geochronology to Deccan rocks and show that the main phase of eruptions initiated ~250,000 years before the Cretaceous-Paleogene boundary and that >1.1 million cubic kilometers of basalt erupted in ~750,000 years. Our results are consistent with the hypothesis that the Deccan Traps contributed to the latest Cretaceous environmental change and biologic turnover that culminated in the marine and terrestrial mass extinctions.

Statistical geochemistry reveals disruption in secular lithospheric evolution about 2.5 Gyr ago.

The Earth has cooled over the past 4.5 billion years (Gyr) as a result of surface heat loss and declining radiogenic heat production. Igneous geochemistry has been used to understand how changing heat flux influenced Archaean geodynamics, but records of systematic geochemical evolution are complicated by heterogeneity of the rock record and uncertainties regarding selection and preservation bias. Here we apply statistical sampling techniques to a geochemical database of about 70,000 samples from the continental igneous rock record to produce a comprehensive record of secular geochemical evolution throughout Earth history. Consistent with secular mantle cooling, compatible and incompatible elements in basalts record gradually decreasing mantle melt fraction through time. Superimposed on this gradual evolution is a pervasive geochemical discontinuity occurring about 2.5 Gyr ago, involving substantial decreases in mantle melt fraction in basalts, and in indicators of deep crustal melting and fractionation, such as Na/K, Eu/Eu* (europium anomaly) and La/Yb ratios in felsic rocks. Along with an increase in preserved crustal thickness across the Archaean/Proterozoic boundary, these data are consistent with a model in which high-degree Archaean mantle melting produced a thick, mafic lower crust and consequent deep crustal delamination and melting--leading to abundant tonalite-trondhjemite-granodiorite magmatism and a thin preserved Archaean crust. The coincidence of the observed changes in geochemistry and crustal thickness with stepwise atmospheric oxidation at the end of the Archaean eon provides a significant temporal link between deep Earth geochemical processes and the rise of atmospheric oxygen on the Earth.