Early Earth zircons formed in residual granitic melts produced by tonalite differentiation

The oldest geological materials on Earth are Hadean (>4 Ga) detrital zircon grains. Their chemistry and apparently low Ti-in-zircon temperatures (≤700 °C) are considered to be inconsistent with crystallization in a magma of the tonalite-trondhjemite-granodiorite (TTG) suite, although these are the dominant Archean (4.0–2.5 Ga) silicic rocks. Using a new data set of trace element contents in zircons from Paleoarchean Barberton TTGs (South Africa) and thermodynamic modeling, we show that these zircons have crystallized at near-solidus conditions from a compositionally uniform granitic melt. This melt is residual from the crystallization of a less evolved (tonalitic) parent and thereby shows major and trace element compositions different from bulk TTG rocks. A global compilation reveals that most Hadean detrital and Archean TTG-hosted grains share a peculiar zircon trace element signature that is distinct from the chemical trends defined by Phanerozoic zircons. Our model shows that the low Ti contents of early Earth zircons reflect crystallization at higher temperatures (720–800 °C) than initially inferred due to lower modeled TiO2 activity in the melt relative to previous estimates. We therefore propose that near-solidus zircon crystallization from a chemically evolved melt in a TTG-like magmatic environment was the dominant zircon-forming process on the early Earth.

Timescales and thermal evolution of large silicic magma reservoirs during an ignimbrite flare-up: perspectives from zircon

Four voluminous ignimbrites (150–500 km3) erupted in rapid succession at 27 Ma in the central San Juan caldera cluster, Colorado. To reconstruct the timescales and thermal evolution of these magma reservoirs, we used zircon ID-TIMS U–Pb geochronology, zircon LA-ICP-MS geochemistry, thermal modeling, and zircon age and crystallization modeling. Zircon geochronology reveals dispersed zircon age spectra in all ignimbrites, with decreasing age dispersion through time that we term a ‘chimney sweeping’ event. Zircon whole-grain age modeling suggests that 2σ zircon age spans represent approximately one-quarter of total zircon crystallization timescales due to the averaging effect of whole-grain, individual zircon ages, resulting in zircon crystallization timescales of 0.8–2.7 m.y. Thermal and zircon crystallization modeling combined with Ti-in-zircon temperatures indicates that magma reservoirs were built over millions of years at relatively low magmatic vertical accretion rates (VARs) of 2–5 × 10–3 m y−1 (2–5 × 10–6 km3 y−1 km−2), and we suggest that such low VARs were characteristic of the assembly of the greater San Juan magmatic body. Though we cannot unequivocally discern between dispersed zircon age spectra caused by inheritance (xenocrystic or antecrystic) versus prolonged crystallization from the same magma reservoir (autocrystic), our findings suggest that long-term magma input at relatively low VARs produced thermally mature upper crustal magma reservoirs resulting in protracted zircon crystallization timescales. Compiling all U–Pb ID-TIMS zircon ages of large ignimbrites, we interpret the longer timescales of subduction-related ignimbrites as a result of longer term, lower flux magmatism, and the shorter timescales of Snake River Plain ignimbrites as a result of shorter term, higher flux magmatism.

THE PALEOARCHEAN (3.3 Ga) AND MESOARCHEAN (3.0 Ga) TTGs OF THE WESTERN AZOV AREA, THE UKRAINIAN SHIELD

A large anticline structure that includes the West Azov and Remivka blocks occurs in the western part of the Azov Domain of the Ukrainian Shield. These blocks are composed of rocks of the Mesoarchean (3.2-3.0 Ga) granite-greenstone association and relics of an older basement. The anticline is divided into two parts by the Bilotserkivka structure of sub-latitudinal strike; the northern part includes the Huliaipole and Remivka blocks, and the southern part is comprised of the Saltycha anticline. The Archean plagiogranitoids of the West Azov underwent intense dislocation metamorphism during the Paleoproterozoic. In many areas they were transformed into plagioclase gneisses that were attributed to the Paleoarchean “Kainkulak thickness” of the Azov Series. Detailed geological-structural and geochronological studies are required to define the age of these gneisses.We have chosen two areas for our studies: the Lantsevo anticline within the Bilotserkivka structure, and the Ivanivka area in the eastern part of the Saltycha anticline. The Bilotserkivka structure is composed of rocks of the Central Azov Series and highly deformed Archean formations. We have dated plagiogneisses of the Lantsevo anticline. These rocks contain large relics of metamorphic rocks of unknown age, including two-pyroxene and pyroxene crystalline schists, and pyroxenemagnetite quartzites (BIF). In terms of chemical composition, two-pyroxene crystalline schists correspond to tholeiitic basalts and basaltic komatiites. Ferruginous-siliceous rocks belong to the Algoma type typical for the Archean greenstone belts. Biotite gneisses are similar to the medium-pressure tonalite-trondhjemite-granodiorite rocks (TTGs). The U-Pb age of zircon crystallization from biotite gneisses is 3299 ± 11 Ma. At 30 km in the western part of the Bilotserkivka structure, we have previously identified quartz diorites having an age of 3297 ± 22 Ma. In terms of geochemical characteristics, they correspond to low-pressure TTGs. These data show that the Bilotserkivka structure is a block representing an ancient basement. In the Ivanivka area in the eastern part of the Saltycha anticline, the strike of the Archean rocks was reorientated from northwestern to latitudinal. The studied dislocated trondhjemites of the Ivanivka area correspond to TTGs in terms of the geochemical characteristics. They contain numerous relics of highly altered amphibolites. The U-Pb age of zircon crystallization from trondhjemite is 3013 ± 15 Ma. These rocks are of the same age as TTGs of the Shevchenko Complex cutting through the sedimentary-volcanogenic rocks of the greenstone structures of the Azov Domain. They share age and geochemical characteristics with biotite and amphibole-biotite gneisses of the “Kainkulak thickness” in Zrazkove village located at the Mokra Konka river (3.1-3.0 Ga) and with biotite gneisses in the lower reaches of the Kainkulak river (2.92 Ga). Thus, gneisses of the “Kainkulak thickness” in fact represent the Mesoarchean TTGs of the Shevchenko Complex, which were transformed in the Paleoproterozoic time due to the dislocation metamorphism. Late Paleoarchean (3.3 Ga) tonalites are known in the West Azov and the KMA domains; they probably also occur in the basement of the Middle Dnieper domains, where detrital zircons of this age have been reported. These data allow us to conclude the existence of a large Late Paleoarchean (3.3 Ga) protocraton, in which the Mesoarchean (3.2-3.0 Ga) greenstone belts and TTGs of the eastern part of the Ukrainian Shield and the KMA Domain were formed.

A LA-ICPMS zircon record of magmatic crystallization and compositional alteration in meta-igneous rocks of the eastern Kaapvaal Craton

Archaean zircons from the Kaapvaal Craton, South Africa, were analyzed by Laser Ablation (LA)-ICP-MS to obtain a coupled record of U-Th-Pb isotope ratios and selected trace elements with the aim to develop insights into physico-chemical conditions during igneous zircon crystallization and subsequent compositional alteration. Four rock samples previously dated by SIMS U-Pb using zircon were selected: 3.56 Ga Ngwane Gneiss, 3.55 Ga Theespruit felsic metavolcanic, 3.50 Ga Steynsdorp Gneiss and 2.98 Ga Nhlangano Gneiss. LA-ICP-MS U-Pb zircon ages agree with published SIMS U-Pb ages within analytical uncertainty. Assessment of the magmatic crystallization histories was based on near-concordant grains, and discordant grains were used to examine post-igneous element mobilization and alteration. Time-resolved laser drilling experiments allowed distinction of concordant and discordant zircon domains, but also revealed systematic changes in REE + Ti geochemistry, U + Th content, discordance and metamictization. Th/U and Zr/Hf, coupled with REE patterns, effectively distinguish compositional zircon types that reflect variable degrees of igneous differentiation and melt compositions. Eu/Eu* values indicate significant feldspar fractionation in some magmas. Averaged crystallization temperatures of magmatic zircons, as derived from the Ti-in-zircon thermometer, define a narrow range of 650 to 750°C for (near-)concordant grains, consistent with general constraints on temperatures at zircon saturation for felsic magmas, and testifying to a closed-system behavior of Ti (and other trace elements). Systematic deviations from primary igneous trace element signatures are strongly correlated with radiation damage. Specifically, Th/U and, to some extent, Zr/Hf decrease, and Ti increases with increasing U (+Th) content and isotopic disturbance (discordance).

Timing and distribution of the Los Chocoyos supereruption from Atitlán caldera (Guatemala) by zircon 238U-230Th and (U-Th)/He double-dating

<p>The climactic Los Chocoyos (LCY) rhyolitic eruption from Atitlán caldera (Guatemala) is a key chronostratigraphic marker for the Late Quaternary period that has been widely used for relative dating of paleoenvironmental, paleoclimate, and volcanic events throughout Central America and adjacent marine basins in the Pacific Ocean, the Caribbean Sea, and the Gulf of Mexico. Despite LCY tephra being an important marker horizon, a radioisotopic age for this eruption has remained elusive. LCY tephra has been dated at ca. 84 ka BP based on its occurrence in marine sediments with model δ<sup>18</sup>O ages, but this inferred age has not been independently confirmed through radioisotopic methods. This is due to the inherent limitations of radiocarbon dating (which is practically limited to ˂50 ka) and a lack of suitable materials for <sup>40</sup>Ar/<sup>39</sup>Ar analysis in LCY tephra. To overcome this limitation, we applied <sup>238</sup>U-<sup>230</sup>Th and (U-Th)/He zircon double-dating (ZDD). Due to zircon being alteration-resistant this method establishes absolute chronologies for and correlations between silicic tephra deposits, which are unaffected by glass alteration or complex compositional signatures within a single eruption. <sup>238</sup>U-<sup>230</sup>Th zircon crystallization rim ages were obtained from LCY proximal tephras (~17 km from Atitlán caldera) including sub-units that may bear distinct glass compositions (e.g., fallout, ignimbrite, surge) as well as ultra-distal fallout tephra samples (~300 km from source) collected from drill cores at Petén Itzá Lake (ICDP) and the Pacific Ocean (IODP). All samples yielded zircon with statistically indistinguishable <sup>238</sup>U-<sup>230</sup>Th zircon rim age spectra. These reveal continuous zircon crystallization from ca. 160 ka to ca. 74 ka, with peaks in zircon crystallization between 90-100 ka. ZDD eruption ages from two LCY fallout and one ignimbrite deposit are indistinguishable with error-weighted averages of 75.1 ± 3.2 ka (1σ; n = 16; MSWD = 4.1), 76.0 ± 2.5 ka (n = 16; MSWD = 2.5), and 72.8 ± 3.5 ka (n = 16; MSWD = 3.7). Considering all individual zircon results as a single population, a weighted average ZDD age of 74.8 ± 1.7 (1σ; n = 48; MSWD = 3.3) is obtained and considered as the best estimate for LCY eruption age. GIS-based reassessment of LCY eruptive volume uses thickness information from new 113 outcrops including 6–10 m thick pyroclastic density currents in Chiapas, Mexico (>130 km from the source) and suggests a minimum estimate volume of ~1200 km<sup>3</sup>, confirming the LCY eruption as the first‐ever recognized supereruption in Central America. The new ZDD age of 74.8 ± 1.7 ka for the LCY eruption is significantly younger than the commonly cited O-isotope stratigraphic age of 84 ± 5 ka. This age is close to the voluminous (2,800-5,600 km<sup>3</sup>) Young Toba Tuff (YTT) supereruption at ca. 73.8 ± 0.3 ka from Toba Caldera, Indonesia. Both YTT and LCY eruptions have been previously linked to prominent Quaternary climate excursions. Based on the new LCY eruption age, climate-forcing effects that are usually attributed to YTT may in fact be exacerbated by another supereruption occurring within a short time window of the YTT event.</p>

Recalibrating Rodinian rifting in the northwestern United States

A lack of precise age constraints for Neoproterozoic strata in the northwestern United States (Washington State), including the Buffalo Hump Formation (BHF), has resulted in conflicting interpretations of Rodinia amalgamation and breakup processes. Previous detrital zircon (DZ) studies identified a youngest ca. 1.1 Ga DZ age population in the BHF, interpreted to reflect mostly first-cycle sourcing of unidentified but proximal magmatic rocks intruded during the amalgamation of Rodinia at ca. 1.0 Ga. Alternatively, the ca. 1.1 Ga DZ population has been suggested to represent a distal source with deposition occurring during the early phases of Rodinia rifting, more than 250 m.y. after zircon crystallization. We combined conventional laser-ablation split-stream analyses of U-Pb/Lu-Hf isotopes in zircon with a method of rapid (8 s per spot) U-Pb analysis to evaluate these opposing models. Our study of ~2000 DZ grains from the BHF identified for the first time a minor (~1%) yet significant ca. 760 Ma population, which constrains the maximum depositional age. This new geochronology implies that the BHF records early rift deposition during the breakup of Rodinia and correlates with sedimentary rocks found in other late Tonian basins of southwestern Laurentia.

Long-term temperature cycling in a shallow magma reservoir: insights from sanidine megacrysts at Taápaca volcano, Central Andes

Hybrid dacite magmas from Taápaca volcano in the Central Andean volcanic zone (18ᵒ, N. Chile) contain sanidine crystals of unusual size (1 to 12 cm) and abundant mafic enclaves of variable composition throughout the entire eruptive history (1.5 Ma to recent) of the volcano. They are rich in mineral inclusions and strongly zoned in Ba with distinct growth bands separated by resorption interfaces. Resorption is followed by a sudden increase in Ba with compositional contrasts up to 2.3 wt% BaO. We argue that resorption and the sharp jumps in Ba-concentration reflect distinct heating and melting events, suggesting that different growth zones formed at different temperatures. Amphibole-plagioclase thermo-barometry based on mineral inclusions gives variable temperatures of ∼720 – 820 ᵒC at shallow pressures (0.1 – 0.3 GPa) for individual growth zones. Using these temperatures for diffusion modelling, Ba-profiles from x-ray scanning profiles and grey scale gradients based on accumulated BSE images across these interfaces allow to estimate crystal residence and reactivation times prior to eruption. This temperature control allowed the application of a “non-isothermal” diffusion algorithm to obtain diffusion times for individual diffusive boundaries that range from 0.4 to 490 ky and add up to total residence times of 9 to 499 ky for different crystals from different stages of eruption. A combination of temperatures, pressure, diffusion times and R-melts modeling of the parent rhyodacite suggests storage conditions for the Taápaca reservoir at near eutectic composition at shallow depth (4 – 10 km). Temperatures never fell below the magma solidus but frequently cycled between 720 °C and 820 °C, i.e. between eruptible and non-eruptible state with crystallinity circling around ∼40 – 50 vol%, for tens to hundreds of thousands of years. We define this as “Long-term Transitional Temperature Cycling” or LTTC storage. Frequent recharge events of basaltic andesite magma, as represented by abundant mafic enclaves, orchestrated the temperature cycling, resulted in multiple heating events that caused frequent resorptions and interrupted crystal growth, and kept the reservoir thermally ‘alive’. Recharge events became more frequent only ∼3 – 11 ky before the eventual eruption that carried a particular set of sanidine megacrysts to the surface. Thus, after many earlier recharge events that did not result in eruption, a final event involved mixing at a critical recharge rate to mobilize, entrain, and erupt a particular set of megacrysts from the resident rhyodacite in a hybrid dacite host. This process, happening not more than a few centuries before an eruption, has been repeated at similar timescales at different stratigraphic stages throughout the 1.5 My long history of Taápaca volcano. The observed mineral zonation patterns and size of sanidine crystals from the resident magma reservoir below Taápaca volcano are identical to those observed in the megacrysts from granite intrusions that also show typical age ranges of zircon crystallization which are comparable to the residence times extracted here from Ba zonation. Taápaca sanidines thus may represent an erupted equivalent and provide “smoking gun” evidence of temperature cycling during the formation of such K-feldspar megacrysts in granites.

Dating the Bushveld Complex: Timing of Crystallization, Duration of Magmatism, and Cooling of the World’s Largest Layered Intrusion and Related Rocks

The Paleoproterozoic Bushveld Complex, including the world’s largest layered intrusion and host to world-class stratiform chromium, platinum group element, and vanadium deposits, is a remarkable natural laboratory for investigating the timescales of magmatic processes in the Earth’s crust. A framework for the emplacement, crystallization, and cooling of the Bushveld Complex based on integrated U-Pb zircon-baddeleyite-titanite-rutile geochronology is presented for samples of different rock types from the Bushveld Complex, including ultramafic and mafic cumulates, mineralized horizons, granitic rocks from the roof, and a carbonatite from the nearby alkaline Phalaborwa Complex. The results indicate that (1) the Bushveld Complex was built incrementally over a ∼5 million-year interval from 2060 Ma to 2055 Ma with a peak in magma flux at c.2055–2056 Ma, (2) U-Pb zircon crystallization ages do not decrease in an uninterrupted systematic manner from the base to the top of the intrusion indicating that the Bushveld Complex does not represent the crystallized products of a single progressively filled and cooled magma chamber, and (3) U-Pb rutile dates constrain cooling of the intrusion at the level of the Critical Zone through ∼500 °C by 2053 Ma. The c.2060 Ma Phalaborwa Complex (pyroxenite, syenite, carbonatite + Cu-Fe-phosphate-vermiculite deposits) represents one of the earliest manifestations of widespread Bushveld-related magmatism in the northern Kaapvaal craton. The extended range and out-of-sequence U-Pb zircon dates determined for a harzburgite from the Lower Zone (c.2056 Ma), an orthopyroxenite from the Lower Critical Zone (c.2057 Ma), and orthopyroxenites from the Upper Critical Zone (c.2057–2060 Ma) are interpreted to indicate that the lower part of the Bushveld Complex developed through successive intrusions and accretion of sheet-like intrusions (sills), some intruded at different stratigraphic levels. Crystallization of the main volume of the Bushveld Complex, as represented by the thick gabbroic sequences of the Main Zone and Upper Zone, is constrained to a relatively narrow interval of time (∼1 million years) at c.2055–2056 Ma. Granites and granophyres in the roof, and a diorite in the uppermost Upper Zone, constitute the youngest igneous activity in the Bushveld Complex at c.2055 Ma. Collectively, these results contribute to an emerging paradigm shift for the assembly of some ultramafic-mafic magmatic systems from the conventional “big tank” model to an “amalgamated sill” model. The volume-duration relationship determined for magmatism in the Bushveld Complex, when compared to timescales established for the assembly of other layered intrusions and more silica-rich plutonic-volcanic systems worldwide, is distinct and equivalent to those determined for Phanerozoic continental and oceanic flood basalts that constitute large igneous provinces. Emplacement of the 2055–2060 Ma Bushveld Complex corresponds to the end of the Lomagundi-Jatuli Event, the largest magnitude positive carbon isotope excursion in Earth history, and this temporal correlation suggests that there may have been a contribution from voluminous Bushveld ultramafic-mafic-silicic magmatism to disruptions in the global paleoenvironment.