Description: Earth exhibits a dichotomy in elevation and chemical composition between the continents and ocean floor. Reconstructing when this dichotomy arose is important for understanding when plate tectonics started and how the supply of nutrients to the oceans changed through time. We measured the titanium isotopic composition of shales to constrain the chemical composition of the continental crust exposed to weathering and found that shales of all ages have a uniform isotopic composition. This can only be explained if the emerged crust was predominantly felsic (silica-rich) since 3.5 billion years ago, requiring an early initiation of plate tectonics. We also observed a change in the abundance of biologically important nutrients phosphorus and nickel across the Archean-Proterozoic boundary, which might have helped trigger the rise in atmospheric oxygen.

Description: Generation of large-volume rhyolites in the shallow crust is an important, yet enigmatic, process in the Snake River Plain and worldwide. Here, we present data for voluminous rhyolites from the 6·6–4·5 Ma Heise volcanic field in eastern Idaho. Heise is arguably the best site to evaluate shallow rhyolite genesis in the Snake River Plain; it is the youngest complete record of caldera cluster volcanism along the Yellowstone hotspot track and it culminated with the eruption of the most voluminous low- 18 O rhyolite known on Earth: the 1800 km 3 Kilgore Tuff ( 18 O = 3·4). Such low- 18 O values fingerprint meteoric waters, and thus the shallow crust. New oxygen isotope data for phenocrysts, obtained by laser fluorination, correspond to a low- 18 O magma value of 3·4 ± 0·1 (2 standard error) for Kilgore Tuff samples erupted 〉100 km apart; however, ion microprobe data for single zircon crystals show significant diversity, with 18 O values that range from –1·3 to 6·1. U–Pb zircon ages, mineral chemistry, whole-rock major and trace element geochemistry, Sr and Nd isotope data, and magmatic (liquidus) temperatures are similar and/or overlapping for all studied samples of the Kilgore Tuff. Normal- 18 O Heise tuff units that preceded the Kilgore Tuff define a temporal compositional trend in trace element concentrations, trace element ratios, and Sr and Nd isotope ratios that is consistent with fractional crystallization from a common reservoir, whereas low- 18 O Kilgore cycle units have compositions that define a sharp reversal in the temporal trend back towards the composition of the first normal- 18 O Heise tuff (6·62 Ma Blacktail Creek Tuff). The data support derivation of the voluminous low- 18 O Kilgore Tuff from remelting of hydrothermally altered ( 18 O depleted) intracaldera and subvolcanic portions of the Blacktail Creek Tuff. Single pockets of melt with variable low- 18 O values were assembled and homogenized on a caldera-wide scale prior to the climactic Kilgore Tuff eruption, and the best record of this process is provided by the 18 O diversity in Kilgore Tuff zircons. Temporal trends of oxygen isotopic depletion and recovery in rhyolite eruptions of the Heise volcanic field are clearly linked to caldera collapse events, and remarkably consistent with trends in the Yellowstone Plateau volcanic field. At Heise and Yellowstone, magmatic 18 O values can be predicted on the basis of cumulative eruptive volumes, with a decrease in 18 O by ~1 for every ~1000 km 3 of erupted rhyolite. The Kilgore Tuff of the Heise volcanic field has the same timing, magnitude of 18 O depletion, and cumulative eruptive volume as the youngest phase of voluminous rhyolitic eruptions in the Yellowstone Plateau volcanic field, indicating that the Kilgore Tuff may serve as a useful analog for these and perhaps other large-volume low- 18 O rhyolites on Earth.

Description: Recent discoveries of isotopically diverse minerals, i.e., zircons, quartz, and feldspars, in large-volume ignimbrites and smaller lavas from the Snake River Plain (SRP; Idaho, USA), Iceland, Kamchatka Peninsula, and other environments suggest that this phenomenon characterizes many silicic units studied by in situ methods. This observation leads to the need for new models of silicic magma petrogenesis that involve double or triple recycling of zircon-saturated rocks. Initial partial melts are produced in small quantities in which zircons and other minerals undergo solution reprecipitation and inherit isotopic signatures of the immediate environment of the host magma batch. Next, isotopically diverse polythermal magma batches with inherited crystals merge together into larger volume magma bodies, where they mix and then erupt. Concave-up and polymodal crystal size distributions of zircons and quartz observed in large-volume ignimbrites may be explained by two or three episodes of solution and reprecipitation. Hafnium isotope diversity in zircons demonstrates variable mixing of crustal melts and mantle-derived silicic differentiates. The low 18 O values of magmas with 18 O-diverse zircons indicate that magma generation happens by remelting of variably hydrothermally altered, and thus diverse in 18 O, protoliths from which the host magma batch, minute or voluminous, inherited low- 18 O values. This also indicates that the processes that generate zircon diversity happen at shallow depths of a few kilometers, where meteoric water can circulate at large water/rock ratios to imprint low 18 O values on the protolith. We further review newly emerging isotopic evidence of diverse zircons and their appearance at the end of the magmatic evolution of many long-lived large-volume silicic centers in the SRP and elsewhere, evidence indicating that the genesis of rhyolites by recycling their sometimes hydrothermally altered subsolidus predecessors may be a common evolutionary trend for many rhyolites worldwide, especially in hotspot and rift environments with high magma and heat fluxes. Next, we use thermomechanical finite element modeling of rhyolite genesis and to explain (1) the formation of magma batches in stress fields by dike capture or deflection as a function of underpressurization and overpressurization, respectively; (2) the merging of neighboring magma batches together via four related mechanisms: melting through the screen rock and melt zone expansion, brittle failure of a separating screen of rocks, buoyant merging of magmas, and explosive merging by an overpressurized interstitial fluid phase (heated meteoric water); and (3) mixing time scales and their efficacies on extended horizontal scales, as expressed by marker method particle tracking. The envisioned advective thermomechanical mechanisms of magma segregation in the upper crust may characterize periods of increased basaltic output from the mantle, leading to increased silicic melt production, but may also serve as analogues for magma chambers made of dispersed magma batches. Although not the focus of this work, dispersed magma batches may be stable in the long term, but their coalescence creates ephemeral, short-lived eruptable magma bodies that erupt nearly completely.

Description: The geological record contains evidence of volcanic eruptions that were as much as two orders of magnitude larger than the most voluminous eruption experienced by modern civilizations, the A.D. 1815 Tambora (Indonesia) eruption. Perhaps nowhere on Earth are deposits of such supereruptions more prominent than in the Snake River Plain–Yellowstone Plateau (SRP-YP) volcanic province (northwest United States). While magmatic activity at Yellowstone is still ongoing, the Heise volcanic field in eastern Idaho represents the youngest complete caldera cycle in the SRP-YP, and thus is particularly instructive for current and future volcanic activity at Yellowstone. The Heise caldera cycle culminated 4.5 Ma ago in the eruption of the ~1800 km 3 Kilgore Tuff. Accessory zircons in the Kilgore Tuff display significant intercrystalline and intracrystalline oxygen isotopic heterogeneity, and the vast majority are 18 O depleted. This suggests that zircons crystallized from isotopically distinct magma batches that were generated by remelting of subcaldera silicic rocks previously altered by low- 18 O meteoric-hydrothermal fluids. Prior to eruption these magma batches were assembled and homogenized into a single voluminous reservoir. U-Pb geochronology of isotopically diverse zircons using chemical abrasion–isotope dilution–thermal ionization mass spectrometry yielded indistinguishable crystallization ages with a weighted mean 206 Pb/ 238 U date of 4.4876 ± 0.0023 Ma (MSWD = 1.5; n = 24). These zircon crystallization ages are also indistinguishable from the sanidine 40 Ar/ 39 Ar dates, and thus zircons crystallized close to eruption. This requires that shallow crustal melting, assembly of isolated batches into a supervolcanic magma reservoir, homogenization, and eruption occurred extremely rapidly, within the resolution of our geochronology (10 3 –10 4 yr). The crystal-scale image of the reservoir configuration, with several isolated magma batches, is very similar to the reservoir configurations inferred from seismic data at active supervolcanoes. The connection of magma batches vertically distributed over several kilometers in the upper crust would cause a substantial increase of buoyancy overpressure, providing an eruption trigger mechanism that is the direct consequence of the reservoir assembly process.

Description: Late Cenozoic faulting and large-magnitude extension in the Great Basin of the western USA has created locally deep windows into the upper crust, permitting direct study of volcanic and plutonic rocks within individual calderas. The Caetano caldera in north–central Nevada, formed during the mid-Tertiary ignimbrite flare-up, offers one of the best exposed and most complete records of caldera magmatism. Integrating whole-rock geochemistry, mineral chemistry, isotope geochemistry and geochronology with field studies and geologic mapping, we define the petrologic evolution of the magmatic system that sourced the 〉1100 km 3 Caetano Tuff. The intra-caldera Caetano Tuff is up to ~5 km thick, composed of crystal-rich (30–45 vol. %), high-silica rhyolite, overlain by a smaller volume of comparably crystal-rich, low-silica rhyolite. It defies classification as either a monotonous intermediate or crystal-poor zoned rhyolite, as commonly ascribed to ignimbrite eruptions. Crystallization modeling based on the observed mineralogy and major and trace element geochemistry demonstrates that the compositional zonation can be explained by liquid–cumulate evolution in the Caetano Tuff magma chamber, with the more evolved lower Caetano Tuff consisting of extracted liquids that continued to crystallize and mix in the upper part of the chamber following segregation from a cumulate-rich, and more heterogeneous, source mush. The latter is represented in the caldera stratigraphy by the less evolved upper Caetano Tuff. Whole-rock major, trace and rare earth element geochemistry, modal mineralogy and mineral chemistry, O, Sr, Nd and Pb isotope geochemistry, sanidine Ar–Ar geochronology, and zircon U–Pb geochronology and trace element geochemistry provide robust evidence that the voluminous caldera intrusions (Carico Lake pluton and Redrock Canyon porphyry) are genetically equivalent to the least evolved Caetano Tuff and formed from magma that remained in the lower chamber after ignimbrite eruption and caldera collapse. Thus, the Caetano Tuff contradicts models for the mutually exclusive origins of voluminous volcanic and plutonic magmas in the upper crust. Crystal-scale O isotope data indicate that the Caetano Tuff is one of the most 18 O-enriched rhyolites in the Great Basin ( 18 O magma = 10·2 ± 0·2), supporting anatexis of local metasedimentary basement crust. Metapelite xenoliths in the Carico Lake pluton and ubiquitous xenocrystic zircons in the Caetano Tuff provide constraints for the anatexis process; these data point to shallow (〈15 km) dehydration melting of a protolith similar to the Proterozoic McCoy Creek Group siliciclastic sediments in eastern Nevada, projected beneath Caetano in fault-stacked shelf sediments that were thickened during Mesozoic crustal shortening. Mean zircon U–Pb ages for different stratigraphic levels of the intra-caldera Caetano Tuff are 34·2–34·5 Ma, 0·2–0·5 Myr older than the caldera sanidine 40 Ar/ 39 Ar age of 34·00 ± 0·03 Ma, documenting protracted duration of assembly and homogenization of isotopically diverse upper crustal melts, followed by crystallization and zonation to generate the Caetano Tuff magma chamber. Sanidine rims in the least evolved Caetano Tuff and in the Carico Lake pluton and Redrock Canyon porphyry have sharply zoned Ba domains that point to crystal growth during magmatic recharge events. The recharge magma is inferred to have been compositionally similar to the Caetano Tuff magma, with increased Ba resulting from remelting of Ba-rich sanidine cumulates. Mush reactivation to generate the Caetano Tuff eruption was sufficiently rapid to preserve compositional gradients in the intracaldera ignimbrite, calling into question models that predict homogeneity as a prerequisite for remobilizing crystal-rich ignimbrite magmas.

Description: The 1.85 Ga Belomorian Belt, Karelia, Russia, hosts ultralow 18 O and D (as low as –27.3 and –235 standard mean ocean water [SMOW], respectively), high-Al gneisses and amphibolites that we attribute to the Paleoproterozoic "Slushball Earth" glaciation. They now occur in at least 11 localities spanning 450 km. To constrain distribution of 18 O-depleted rocks, we performed detailed field mapping in Khitostrov, where 18 O values are the lowest. Using 430 new and previously published laser fluorination isotope analyses, we show that the elongated, concentrically zoned area of 18 O depletion is greater than 6 x 2 km in areal extent, ~10 times larger than previously thought. Relationships between 17 O versus 18 O strictly adhere to the equilibrium terrestrial mass-dependent fractionation with a slope of 0.527. We also report the results of ion microprobe U-Pb geochronology of zircons coupled with co-registered oxygen isotope spot analyses for mafic intrusions and host gneisses in six localities. The 2.9–2.7 Ga gneiss zircon cores are normal in 18 O (5–7). They show truncated oscillatory cathodoluminescence (CL) patterns and rounded shape indicative of original igneous crystallization with subsequent detrital overprinting. A younger 2.6–2.55 Ga metamorphic zircon domain with normal 18 O, low Th/U, dark cathodoluminescence, and also with rounded crystal morphology is commonly preserved. Cores are surrounded by ubiquitous rims highly depleted in 18 O (re-)crystallized with Svecofennian (1.85–1.89 Ga) ages. Rims are interpreted as metamorphic due to bright and uniform CL and Th/U 〈0.05. Mafic intrusions preserve few igneous zircon crystals between ca. 2.23 and 2.4 Ga in age, but neoblastic zircon in these intrusions originated mostly during 1.85 Ga Svecofennian metamorphism. The 18 O-age relationship for metamorphic rims in zircon and corundum grains suggests that 18 O values of fluids were subtly increasing with time during metamorphism. Large metamorphic corundum grains have ~3 intracrystalline 18 O isotope zonation from –24 to –21, which likely developed during interaction with metamorphic fluids. The Zr-in-rutile geothermometer temperatures are in the range of 760 to 720 °C, in accordance with mineral assemblages and amphibolite metamorphic grade. High and irregular rare-earth element (REE) abundance in cores and rims of many zircons correlates with high phosphorus content and is explained by nanometer-scale xenotime and monazite inclusions, likely in metamict zones during 1.85 Ga Svecofennian metamorphism. A survey of oxygen isotopes in ultrahigh-pressure diamond and coesite-bearing metamorphic terrains around the world reveals normal to high- 18 O values, suggesting that the low 18 O in metamorphic rocks of Dabie Shan, Kokchetav, and in Karelia, are genetically unrelated to metamorphism. We discuss alternative ways to achieve extreme 18 O depletion by kinetic, Rayleigh, and thermal diffusion processes, and by metamorphism. We prefer an interpretation where the low- 18 O and high-Al signature of the rocks predates metamorphism, and is caused by shallow hydrothermal alteration and partial dissolution of the protolith surrounding shallow mafic intrusions by glacial meltwaters during pan-global Paleoproterozoic "Slushball Earth" glaciations between ca. 2.4 and ca. 2.23 Ga.

Description: The eruption and storage temperatures of rhyolitic magmas are critical factors for understanding the mechanisms of their eruption and petrogenesis. Temperatures are particularly important when comparing the magmatic histories of hot-dry rhyolites from the Yellowstone-Snake River Plain (YSRP) and Iceland to cold-wet rhyolites such as the Bishop Tuff. Here we employ mineral pair oxygen isotope fractionations for estimating rhyolite temperatures independent of pressure and other compositional factors. We report high precision oxygen isotope analyses of quartz, pyroxene, magnetite, and zircon that we use to estimate crystallization and storage temperatures. Temperatures for YSRP and Icelandic rhyolites are highest for quartz-magnetite and quartz-clinopyroxene (~950 °C), with lower quartz-zircon (850 °C) temperatures that are similar to estimates of zircon saturation. The magnitude and pattern of these temperatures is consistent with crystallization from near-liquidus rhyolites. In contrast, oxygen isotope temperatures calculated for the Bishop and other "cold-wet" type tuffs define low ~760 °C temperatures for all three mineral pairs consistent with prolonged mineral residence at near-solidus conditions. Preservation of a down-temperature crystallization sequence of hot magnetite and clinopyroxene with colder zircon in hot-dry YSRP and Icelandic rhyolites suggest 〈1000 yr magma residence, where magnetite does not have sufficient time to diffusively equilibrate oxygen in a lower temperature melt. This is consistent with recently determined high precision U-Pb crystallization ages zircons from the same units indicating magma generation shortly before eruption.

Description: Improved geochronological methods and in situ isotopic (O, Hf) and trace element studies of zircon require a new physical model that explains its behaviour during crustal melting. We present results of numerical modeling of zircon dissolution in melts of variable composition, water content, temperature, and thermal history. The model is implemented in spherical coordinates with two moving boundaries (for the crystal and the surrounding melt cell outer edge) using simplified mineral phase relationships, and accounting for melt proportion histories as a function of melting and crystallization of major minerals. We explore in detail the dissolution of variably sized zircons and zircon growth inside rock cells of different size, held at different temperatures and undersaturations, and provide an equation for zircon survivability. Similar modeling is performed for other accessory minerals: apatite and monazite. We observe the critical role of rock cell size surrounding zircons in their survivability. Diffusive fill away from a dissolving 100 μm zircon into a large 〉3 mm cell takes 10 2 –10 4 years at 750–950°C, but zircon cores may survive infinitely in smaller than 1 mm cells. Heating followed by cooling for a similar amount of time leads to dissolution followed by nucleation and growth, but new zircon growth remains smaller than the original within the cell. The final zircon size is also investigated as a function of microzircons crystallizing on a front of major minerals, leading to shrinking cell sizes and bulldozing of Zr onto the growing zircon surface. We explore in detail the survivability and regrowth of zircon inside and outside dikes and sills of different sizes and temperatures, and in different rock compositions, on timescales of their conductive cooling and heating, respectively. For zircon-rich rocks, only the largest 〉200 m igneous bodies are capable of complete dissolution–reprecipitation of typically sized zircons at significant distances from the intrusion. Smaller intrusions result in partial dissolution and rim overgrowth. Zircons captured near the contact of conductively cooling sills undergo more overgrowth than dissolution. In contrast, heat wave propagation from the sill will completely dissolve and reprecipitate zircons in Zr-poorer rocks many diameters of the sill away and often 10 3 –10 4 years after the sill intrusion. A single thermal spike and melting episode is capable of generating the observed complexity of isotopically diverse and geochronologically zoned zircons. A MATLAB program is presented for users to apply in their specific situations.