Sediment subduction in Hadean revealed by machine learning.

Due to the scarcity of rock samples, the Hadean Era predating 4 billion years ago (Ga) poses challenges in understanding geological processes like subaerial weathering and plate tectonics that are critical for the evolution of life. The Jack Hills zircon from Western Australia, the primary Hadean samples available, offer valuable insights into magma sources and tectonic genesis through trace element signatures. However, a consensus on these signatures has not been reached. To address this, we developed a machine learning classifier capable of deciphering the geochemical fingerprints of zircon. This allowed us to identify the oldest detrital zircon originating from sedimentary-derived "S-type" granites. Our results indicate the presence of S-type granites as early as 4.24 Ga, persisting throughout the Hadean into the Archean. Examining global detrital zircon across Earth's history reveals consistent supercontinent-like cycles from the present back to the Hadean. These findings suggest that a significant amount of Hadean continental crust was exposed, weathered into sediments, and incorporated into the magma sources of Jack Hills zircon. Only the early operation of both subaerial weathering and plate subduction can account for the prevalence of S-type granites we observe. Additionally, the periodic evolution of S-type granite proportions implies that subduction-driven tectonic cycles were active during the Hadean, at least around 4.2 Ga. The evidence thus points toward an early Earth resembling the modern Earth in terms of active tectonics and habitable surface conditions. This suggests the potential for life to originate in environments like warm ponds rather than extreme hydrothermal settings.

Heterogeneous Hadean crust with ambient mantle affinity recorded in detrital zircons of the Green Sandstone Bed, South Africa.

The nature of Earth's earliest crust and the processes by which it formed remain major issues in Precambrian geology. Due to the absence of a rock record older than ∼4.02 Ga, the only direct record of the Hadean is from rare detrital zircon and that largely from a single area: the Jack Hills and Mount Narryer region of Western Australia. Here, we report on the geochemistry of Hadean detrital zircons as old as 4.15 Ga from the newly discovered Green Sandstone Bed in the Barberton greenstone belt, South Africa. We demonstrate that the U-Nb-Sc-Yb systematics of the majority of these Hadean zircons show a mantle affinity as seen in zircon from modern plume-type mantle environments and do not resemble zircon from modern continental or oceanic arcs. The zircon trace element compositions furthermore suggest magma compositions ranging from higher temperature, primitive to lower temperature, and more evolved tonalite-trondhjemite-granodiorite (TTG)-like magmas that experienced some reworking of hydrated crust. We propose that the Hadean parental magmas of the Green Sandstone Bed zircons formed from remelting of mafic, mantle-derived crust that experienced some hydrous input during melting but not from the processes seen in modern arc magmatism.

An Early Oligocene age for the oldest known monkeys and rodents of South America.

The Santa Rosa fossil locality in eastern Perú produced the first Paleogene vertebrate fauna from the Amazon Basin, including the oldest known monkeys from South America. This diverse paleofauna was originally assigned an Eocene age based largely on the stage of evolution of the site's caviomorph rodents and marsupials. Here, we present detrital zircon dates that indicate that the maximum composite age of Santa Rosa is 29.6 ± 0.08 Ma (Lower Oligocene), although several zircons from Santa Rosa date to the Upper Oligocene. The first appearance datum for Caviomorpha in South America is purported to be the CTA-27 site in the Contamana region of Perú, which is hypothesized to be ∼41 Ma (Middle Eocene) in age. However, the presence of the same caviomorph species and/or genera at both CTA-27 and at Santa Rosa is now difficult to reconcile with a >11-My age difference. To further test the Middle Eocene age estimate for CTA-27, we ran multiple Bayesian tip-dating analyses of Caviomorpha, treating the ages of all Paleogene species from Perú as unknown. These analyses produced mean age estimates for Santa Rosa that closely approximate the maximum 29.6 ± 0.08 Ma composite date provided by detrital zircons, but predict that CTA-27 is much younger than currently thought (∼30 Ma). We conclude that the ∼41 Ma age proposed for CTA-27 is incorrect, and that there are currently no compelling Eocene records of either rodents or primates in the known fossil record of South America.

Growth and thermal maturation of the Toba magma reservoir.

The Toba volcanic system in Indonesia has produced two of the largest eruptions (>2,000 km3 dense-rock equivalent [DRE] each) on Earth since the Quaternary. U-Pb crystallization ages of zircon span a period of ∼600 ky before each eruptive event, and in the run-up to each eruption, the mean and variance of the zircons' U content decrease. To quantify the process of accumulation of eruptible magma underneath the Toba caldera, we integrated these observations with thermal and geochemical modeling. We show that caldera-forming eruptions at Toba are the result of progressive thermal maturation of the upper crustal magma reservoir, which grows and chemically homogenizes, by sustained magma influx at average volumetric rates between 0.008 and 0.01 km3/y over the past 2.2 My. Protracted thermal pulses related to magma-recharge events prime the system for eruption without necessarily requiring an increased magma-recharge rate before the two supereruptions. If the rate of magma input was maintained since the last supereruption of Toba at 75 ka, eruptible magma is currently accumulating at a minimum rate of ∼4.2 km3 per millennium, and the current estimate of the total volume of potentially eruptible magma available today is a minimum of ∼315 km3 Our approach to evaluate magma flux and the rate of eruptible magma accumulation is applicable to other volcanic systems capable of producing supereruptions and thereby could help in assessing the potential of active volcanic systems to feed supereruptions.

Identifying crustal contributions in the Patagonian Chon Aike Silicic Large Igneous Province.

The volcanic rocks of the Chon Aike Silicic Large Igneous Province (CASP) are recognized as magmas dominantly produced by crustal anatexis. Investigating the zircon of the CASP provides an opportunity to gain further insight into geochemical and isotopic differences of the potential magmatic sources (i.e., crust versus mantle), to identify crustal reservoirs that contributed to the felsic magmas during anatexis, and to quantify the contributions of the respective sources. We present a combined zircon oxygen and hafnium isotope and trace element dataset for 16 volcanic units of the two youngest volcanic phases in Patagonia, dated here with LA-ICP-MS U-Pb geochronology at ca. 148-153 Ma (El Quemado Complex, EQC) and ca. 159 Ma (western Chon Aike Formation, WCA). The EQC zircon have 18O-enriched values (δ18O from 7 to 9.5‰) with correspondingly negative initial εHf values (- 2.0 to - 8.0). The WCA zircon have δ18O values between 6 and 7‰ and εHf values ranging between - 4.0 and + 1.5. Binary δ18O-εHf mixing models require an average of 70 and 60% melt derived from partial melting of isotopically distinct metasedimentary basements for the EQC and WCA, respectively. Zircon trace element compositions are consistent with anatexis of sedimentary protoliths derived from LIL-depleted upper continental crustal sources. The overlap between a high heat flux environment (i.e., widespread extension and lithospheric thinning) during supercontinental breakup and a fertile metasedimentary crust was key in producing voluminous felsic volcanism via anatexis following the injection and emplacement of basaltic magmas into the lower crust. Supplementary Information: The online version contains supplementary material available at 10.1007/s00410-023-02065-1.

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.

Diachronous development of Great Unconformities before Neoproterozoic Snowball Earth.

The Great Unconformity marks a major gap in the continental geological record, separating Precambrian basement from Phanerozoic sedimentary rocks. However, the timing, magnitude, spatial heterogeneity, and causes of the erosional event(s) and/or depositional hiatus that lead to its development are unknown. We present field relationships from the 1.07-Ga Pikes Peak batholith in Colorado that constrain the position of Cryogenian and Cambrian paleosurfaces below the Great Unconformity. Tavakaiv sandstone injectites with an age of ≥676 ± 26 Ma cut Pikes Peak granite. Injection of quartzose sediment in bulbous bodies indicates near-surface conditions during emplacement. Fractured, weathered wall rock around Tavakaiv bodies and intensely altered basement fragments within unweathered injectites imply still earlier regolith development. These observations provide evidence that the granite was exhumed and resided at the surface prior to sand injection, likely before the 717-Ma Sturtian glaciation for the climate appropriate for regolith formation over an extensive region of the paleolandscape. The 510-Ma Sawatch sandstone directly overlies Tavakaiv-injected Pikes granite and drapes over core stones in Pikes regolith, consistent with limited erosion between 717 and 510 Ma. Zircon (U-Th)/He dates for basement below the Great Unconformity are 975 to 46 Ma and are consistent with exhumation by 717 Ma. Our results provide evidence that most erosion below the Great Unconformity in Colorado occurred before the first Neoproterozoic Snowball Earth and therefore cannot be a product of glacial erosion. We propose that multiple Great Unconformities developed diachronously and represent regional tectonic features rather than a synchronous global phenomenon.

Significant Zr isotope variations in single zircon grains recording magma evolution history.

Zircons widely occur in magmatic rocks and often display internal zonation finely recording the magmatic history. Here, we presented in situ high-precision (2SD <0.15‰ for δ94Zr) and high-spatial-resolution (20 µm) stable Zr isotope compositions of magmatic zircons in a suite of calc-alkaline plutonic rocks from the juvenile part of the Gangdese arc, southern Tibet. These zircon grains are internally zoned with Zr isotopically light cores and increasingly heavier rims. Our data suggest the preferential incorporation of lighter Zr isotopes in zircon from the melt, which would drive the residual melt to heavier values. The Rayleigh distillation model can well explain the observed internal zoning in single zircon grains, and the best-fit models gave average zircon-melt fractionation factors for each sample ranging from 0.99955 to 0.99988. The average fractionation factors are positively correlated with the median Ti-in-zircon temperatures, indicating a strong temperature dependence of Zr isotopic fractionation. The results demonstrate that in situ Zr isotope analyses would be another powerful contribution to the geochemical toolbox related to zircon. The findings of this study solve the fundamental issue on how zircon fractionates Zr isotopes in calc-alkaline magmas, the major type of magmas that led to forming continental crust over time. The results also show the great potential of stable Zr isotopes in tracing magmatic thermal and chemical evolution and thus possibly continental crustal differentiation.

Secondary magnetite in ancient zircon precludes analysis of a Hadean geodynamo.

Zircon crystals from the Jack Hills, Western Australia, are one of the few surviving mineralogical records of Earth's first 500 million years and have been proposed to contain a paleomagnetic record of the Hadean geodynamo. A prerequisite for the preservation of Hadean magnetization is the presence of primary magnetic inclusions within pristine igneous zircon. To date no images of the magnetic recorders within ancient zircon have been presented. Here we use high-resolution transmission electron microscopy to demonstrate that all observed inclusions are secondary features formed via two distinct mechanisms. Magnetite is produced via a pipe-diffusion mechanism whereby iron diffuses into radiation-damaged zircon along the cores of dislocations and is precipitated inside nanopores and also during low-temperature recrystallization of radiation-damaged zircon in the presence of an aqueous fluid. Although these magnetites can be recognized as secondary using transmission electron microscopy, they otherwise occur in regions that are indistinguishable from pristine igneous zircon and carry remanent magnetization that postdates the crystallization age by at least several hundred million years. Without microscopic evidence ruling out secondary magnetite, the paleomagnetic case for a Hadean-Eoarchean geodynamo cannot yet been made.

Neoproterozoic glacial origin of the Great Unconformity.

The Great Unconformity, a profound gap in Earth's stratigraphic record often evident below the base of the Cambrian system, has remained among the most enigmatic field observations in Earth science for over a century. While long associated directly or indirectly with the occurrence of the earliest complex animal fossils, a conclusive explanation for the formation and global extent of the Great Unconformity has remained elusive. Here we show that the Great Unconformity is associated with a set of large global oxygen and hafnium isotope excursions in magmatic zircon that suggest a late Neoproterozoic crustal erosion and sediment subduction event of unprecedented scale. These excursions, the Great Unconformity, preservational irregularities in the terrestrial bolide impact record, and the first-order pattern of Phanerozoic sedimentation can together be explained by spatially heterogeneous Neoproterozoic glacial erosion totaling a global average of 3-5 vertical kilometers, along with the subsequent thermal and isostatic consequences of this erosion for global continental freeboard.

Origin and significance of Si and O isotope heterogeneities in Phanerozoic, Archean, and Hadean zircon.

Hydrosphere interactions and alteration of the terrestrial crust likely played a critical role in shaping Earth's surface, and in promoting prebiotic reactions leading to life, before 4.03 Ga (the Hadean Eon). The identity of aqueously altered material strongly depends on lithospheric cycling of abundant and water-soluble elements such as Si and O. However, direct constraints that define the character of Hadean sedimentary material are absent because samples from this earliest eon are limited to detrital zircons (ZrSiO4). Here we show that concurrent measurements of Si and O isotope ratios in Phanerozoic and detrital pre-3.0 Ga zircon constrain the composition of aqueously altered precursors incorporated into their source melts. Phanerozoic zircon from (S)edimentary-type rocks contain heterogeneous δ18O and δ30Si values consistent with assimilation of metapelitic material, distinct from the isotopic character of zircon from (I)gneous- and (A)norogenic-type rocks. The δ18O values of detrital Archean zircons are heterogeneous, although yield Si isotope compositions like mantle-derived zircon. Hadean crystals yield elevated δ18O values (vs. mantle zircon) and δ30Si values span almost the entire range observed for Phanerozoic samples. Coupled Si and O isotope data represent a constraint on Hadean weathering and sedimentary input into felsic melts including remelting of amphibolites possibly of basaltic origin, and fractional addition of chemical sediments, such as cherts and/or banded iron formations (BIFs) into source melts. That such sedimentary deposits were extensive enough to change the chemical signature of intracrustal melts suggests they may have been a suitable niche for (pre)biotic chemistry as early as 4.1 Ga.

Application of Ti-in-zircon thermometry to granite studies: problems and possible solutions.

The application of the Ti-in-zircon thermometer to granitic rock requires consideration of a TiO 2 and a SiO 2 during zircon crystallization. Thermodynamic software programs such as rhyolite-MELTS or Perple_X permit the estimation of a TiO 2 and a SiO 2 values from whole-rock geochemical data as a function of pressure and temperature. Model calculations carried out on a set of 14 different granite types at 2 kbar, 5 kbar, and H2O = 3 wt% show a SiO 2 during zircon crystallization close to 1 (0.75-1) and a TiO 2 generally far below unity (0.1-0.6). This would suggest that Ti-in-zircon temperatures for granites must be significantly upward corrected relative to the original TiO2- and SiO2-saturated calibration of the thermometer. Both the rhyolite-MELTS and Perple_X calculations indicate that a TiO 2 is typically around 0.5 in ilmenite-bearing granites. Thus, for ilmenite-series granites (that is, almost all S-type and many I-type granites), it could be a reasonable first order approximation to apply a constant temperature correction of + 70 °C to the Ti-in-zircon thermometer. Granites lacking the paragenesis zircon-ilmenite, that is, some A-type granites and a few special I-type granites may have even lower a TiO 2 (0.1-0.5) and some of them may require a huge upward correction of Ti-in-zircon temperatures on the order of 100-200 °C. Using a set of Ti-in-zircon measurements from a Variscan granite of the Bohemian Massif, we introduce a novel T-dependent a TiO 2 and a SiO 2 correction of Ti-in-zircon calculated temperatures which is based on a TiO 2 -, a SiO 2 -T functions modelled with rhyolite-MELTS. This method takes into account that early and late zircons in granitic systems may crystallize at different a SiO 2 and a TiO 2 . Furthermore, we highlight the usefulness of comparing the corrected results of Ti-in-zircon thermometry with bulk-rock-Zr-based zircon solubility thermometry and ideal zircon crystallization temperature distributions for granites, and we present a graphical method that enables this comparison. In addition, this paper addresses the problem that Ti-in-zircon measurements are commonly collected with only moderate spatial analytical resolution, which leads to an averaging effect and to difficulties in recording accurate crystallization temperatures. Therefore, we propose that Ti-in-zircon thermometry for granites should generally rely on the more representative median-T (T med) value of a series of zircon analyses. Peak magma temperatures will be, in general, 35-50 °C above T med, as can be modelled using zircon crystallization temperature distributions.

Warm storage for arc magmas.

Felsic magmatic systems represent the vast majority of volcanic activity that poses a threat to human life. The tempo and magnitude of these eruptions depends on the physical conditions under which magmas are retained within the crust. Recently the case has been made that volcanic reservoirs are rarely molten and only capable of eruption for durations as brief as 1,000 years following magma recharge. If the "cold storage" model is generally applicable, then geophysical detection of melt beneath volcanoes is likely a sign of imminent eruption. However, some arc volcanic centers have been active for tens of thousands of years and show evidence for the continual presence of melt. To address this seeming paradox, zircon geochronology and geochemistry from both the frozen lava and the cogenetic enclaves they host from the Soufrière Volcanic Center (SVC), a long-lived volcanic complex in the Lesser Antilles arc, were integrated to track the preeruptive thermal and chemical history of the magma reservoir. Our results show that the SVC reservoir was likely eruptible for periods of several tens of thousands of years or more with punctuated eruptions during these periods. These conclusions are consistent with results from other arc volcanic reservoirs and suggest that arc magmas are generally stored warm. Thus, the presence of intracrustal melt alone is insufficient as an indicator of imminent eruption, but instead represents the normal state of magma storage underneath dormant volcanoes.

Early earth geodynamics: cross examining the geological testimony.

Many studies link the presence of continents on Earth to the operation of plate tectonics. Radiogenic isotope data have, however, long consigned the bulk of crust generation and preservation to the murky realm of the Precambrian Earth, where the prevailing geodynamic systems are highly uncertain due to the sparse and complex nature of the geological record of these early eons. The purpose of this paper is to examine the nature of this geological record, considering the biases and artefacts that may undermine its fidelity, and to assess what are the most robust lines of evidence from which meaningful geodynamic inferences can be drawn. This is pursued with reference to Hadean detrital zircons, Archean gneiss complexes and Archean granite-greenstone terranes, and by considering isotopic proxies of crust-mantle interaction. The evidence reinforces long held views that the formation of some of the oldest continental nuclei involved a distinctive mode of planetary geodynamics that rests uneasily within definitions of modern style plate tectonics. A detailed interrogation of the oldest rocks, integrating multi-scale information from the best preserved whole-rock and mineral archives, and emphasizing careful selection at the sampling and analytical stages, will lead to the most robust input data for petrological and thermodynamic models of early Earth processes.This article is part of a discussion meeting issue 'Earth dynamics and the development of plate tectonics'.

Metasomatism and the crystallization of zircon megacrysts in Archaean peridotites from the Lewisian complex, NW Scotland.

Zircon megacrysts are locally abundant in 1-40 cm-thick orthopyroxenite veins within peridotite host rocks in the Archaean Lewisian gneiss complex from NW Scotland. The veins formed by metasomatic interaction between the ultramafic host and Si-rich melts are derived from partial melting of the adjacent granulite-facies orthogneisses. The interaction produced abundant orthopyroxene and, within the thicker veins, phlogopite, pargasite and feldspathic bearing assemblages. Two generations of zircon are present with up to 1 cm megacrystic zircon and a later smaller equant population located around the megacryst margins. Patterns of zoning, rare earth element abundance and oxygen isotopic compositions indicate that the megacrysts crystallized from crustal melts, whereas the equant zircon represents new neocryst growth and partial replacement of the megacryst zircon within the ultramafic host. Both zircon types have U-Pb ages of ca. 2464 Ma, broadly contemporaneous with granulite-facies events in the adjacent gneisses. Zircon megacrysts locally form > 10% of the assemblage and may be associated to zones of localized nucleation or physically concentrated during movement of the siliceous melts. Their unusual size is linked to the suppression of zircon nucleation and increased Zr solubility in the Si-undersaturated melts. The metasomatism between crustal melts and peridotite may represent an analog for processes in the mantle wedge above subducting slabs. As such, the crystallization of abundant zircon in ultramafic host rocks has implications for geochemistry of melts generated in the mantle and the widely reported depletion of high field strength elements in arc magmas.

Source and fractionation controls on subduction-related plutons and dike swarms in southern Patagonia (Torres del Paine area) and the low Nb/Ta of upper crustal igneous rocks.

The subduction system in southern Patagonia provides direct evidence for the variability of the position of an active continental arc with respect to the subducting plate through time, but the consequences on the arc magmatic record are less well studied. Here we present a geochemical and geochronological study on small plutons and dykes from the upper crust of the southern Patagonian Andes at ~ 51°S, which formed as a result of the subduction of the Nazca and Antarctic plates beneath the South American continent. In situ U-Pb geochronology on zircons and bulk rock geochemical data of plutonic and dyke rocks are used to constrain the magmatic evolution of the retro-arc over the last 30 Ma. We demonstrate that these combined U-Pb and geochemical data for magmatic rocks track the temporal and spatial migration of the active arc, and associated retro-arc magmatism. Our dataset indicates that the rear-arc area is characterized by small volumes of alkaline basaltic magmas at 29-30 Ma that are characterized by low La/Nb and Th/Nb ratios with negligible arc signatures. Subsequent progressive eastward migration of the active arc culminated with the emplacement of calc-alkaline plutons and dikes ~ 17-16 Ma with elevated La/Nb and Th/Nb ratios and typical subduction signatures constraining the easternmost position of the southern Patagonian batholith at that time. Geochemical data on the post-16 Ma igneous rocks including the Torres del Paine laccolith indicate an evolution to transitional K-rich calc-alkaline magmatism at 12.5 ± 0.2 Ma. We show that trace element ratios such as Nb/Ta and Dy/Yb systematically decrease with increasing SiO2, for both the 17-16 Ma calc-alkaline and the 12-13 Ma K-rich transitional magmatism. In contrast, Th/Nb and La/Nb monitor the changes in the source composition of these magmas. We suggest that the transition from the common calc-alkaline to K-rich transitional magmatism involves a change in the source component, while the trace element ratios, such as Nb/Ta and Dy/Yb, of derivative higher silica content liquids are controlled by similar fractionating mineral assemblages. Analysis of a global compilation of Nb/Ta ratios of arc magmatic rocks and simple geochemical models indicate that amphibole and variable amounts of biotite exert a major control on the low Dy/Yb and Nb/Ta of derivative granitic liquids. Lastly, we suggest that the low Nb/Ta ratio of silica-rich magmas is a natural consequence of biotite fractionation and that alternative models such as amphibolite melting in subduction zones and diffusive fractionation are not required to explain the Nb/Ta ratio of the upper continental crust.

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.

Metallic lead nanospheres discovered in ancient zircons.

Zircon (ZrSiO4) is the most commonly used geochronometer, preserving age and geochemical information through a wide range of geological processes. However, zircon U-Pb geochronology can be affected by redistribution of radiogenic Pb, which is incompatible in the crystal structure. This phenomenon is particularly common in zircon that has experienced ultra-high temperature metamorphism, where ion imaging has revealed submicrometer domains that are sufficiently heterogeneously distributed to severely perturb ages, in some cases yielding apparent Hadean (>4 Ga) ages from younger zircons. Documenting the composition and mineralogy of these Pb-enriched domains is essential for understanding the processes of Pb redistribution in zircon and its effects on geochronology. Using high-resolution scanning transmission electron microscopy, we show that Pb-rich domains previously identified in zircons from East Antarctic granulites are 5-30 nm nanospheres of metallic Pb. They are randomly distributed with respect to zircon crystallinity, and their association with a Ti- and Al-rich silica melt suggests that they represent melt inclusions generated during ultra-high temperature metamorphism. Metallic Pb is exceedingly rare in nature and previously has not been reported in association with high-grade metamorphism. Formation of these metallic nanospheres within annealed zircon effectively halts the loss of radiogenic Pb from zircon. Both the redistribution and phase separation of radiogenic Pb in this manner can compromise the precision and accuracy of U-Pb ages obtained by high spatial resolution methods.

Potentially biogenic carbon preserved in a 4.1 billion-year-old zircon.

Evidence of life on Earth is manifestly preserved in the rock record. However, the microfossil record only extends to ∼ 3.5 billion years (Ga), the chemofossil record arguably to ∼ 3.8 Ga, and the rock record to 4.0 Ga. Detrital zircons from Jack Hills, Western Australia range in age up to nearly 4.4 Ga. From a population of over 10,000 Jack Hills zircons, we identified one >3.8-Ga zircon that contains primary graphite inclusions. Here, we report carbon isotopic measurements on these inclusions in a concordant, 4.10 ± 0.01-Ga zircon. We interpret these inclusions as primary due to their enclosure in a crack-free host as shown by transmission X-ray microscopy and their crystal habit. Their δ(13)CPDB of -24 ± 5‰ is consistent with a biogenic origin and may be evidence that a terrestrial biosphere had emerged by 4.1 Ga, or ∼ 300 My earlier than has been previously proposed.

Meteorite zircon constraints on the bulk Lu-Hf isotope composition and early differentiation of the Earth.

Knowledge of planetary differentiation is crucial for understanding the chemical and thermal evolution of terrestrial planets. The (176)Lu-(176)Hf radioactive decay system has been widely used to constrain the timescales and mechanisms of silicate differentiation on Earth, but the data interpretation requires accurate estimation of Hf isotope evolution of the bulk Earth. Because both Lu and Hf are refractory lithophile elements, the isotope evolution can be potentially extrapolated from the present-day (176)Hf/(177)Hf and (176)Lu/(177)Hf in undifferentiated chondrite meteorites. However, these ratios in chondrites are highly variable due to the metamorphic redistribution of Lu and Hf, making it difficult to ascertain the correct reference values for the bulk Earth. In addition, it has been proposed that chondrites contain excess (176)Hf due to the accelerated decay of (176)Lu resulting from photoexcitation to a short-lived isomer. If so, the paradigm of a chondritic Earth would be invalid for the Lu-Hf system. Herein we report the first, to our knowledge, high-precision Lu-Hf isotope analysis of meteorite crystalline zircon, a mineral that is resistant to metamorphism and has low Lu/Hf. We use the meteorite zircon data to define the Solar System initial (176)Hf/(177)Hf (0.279781 ± 0.000018) and further to identify pristine chondrites that contain no excess (176)Hf and accurately represent the Lu-Hf system of the bulk Earth ((176)Hf/(177)Hf = 0.282793 ± 0.000011; (176)Lu/(177)Hf = 0.0338 ± 0.0001). Our results provide firm evidence that the most primitive Hf in terrestrial zircon reflects the development of a chemically enriched silicate reservoir on Earth as far back as 4.5 billion years ago.