Geochronological and geochemical effects of zircon chemical abrasion: insights from single-crystal stepwise dissolution experiments

Chemical abrasion in hydrofluoric acid (HF) is routinely applied to zircon grains prior to U–Pb dating by isotope dilution thermal ionization mass spectrometry (IDTIMS) to remove radiation-damaged portions of grains affected by Pb loss. Still, many chemically abraded datasets exhibit evidence of residual Pb loss. Here we test how the temperature and duration of chemical abrasion affect zircon U–Pb and trace element systematics in a series of 4 h, single crystal stepwise dissolution experiments at 180 and 210 ◦C. Microtextural data for the zircon samples studied are presented in a companion paper by McKanna et al. (2023). We find that stepwise dissolution at 210 ◦C is more effective at eliminating material affected by open-system behavior and enriched in U, common Pb (Pbc), and light rare earth elements (LREEs); reduces the presence of leaching-induced artifacts that manifest as reverse discordance; and produces more consistent and concordant results in zircon from the three rocks studied. We estimate that stepwise dissolution in three 4 h steps is roughly equivalent to a single ∼ 8 h leaching step due to the insulating properties of the PTFE sleeve in the Parr pressure dissolution vessel, whereas traditionally labs utilize a single 12 h leaching step. We conclude that a single 8 h leaching step at 210 ◦C should remove Pb loss effects in the majority of zircon and that this can be used as an effective approach for routine analysis. Further, we calculate time-integrated alpha doses for leachates and residues from measured radionuclide concentrations to investigate (1) the alpha dose of the material dissolved under the two leaching conditions and (2) the apparent minimum alpha dose required for Pb loss susceptibility: ≥ 6 × 1017 α g −1.ISSN:2628-3697ISSN:2628-371

Modulation of zircon solubility by crystal–melt dynamics

Zircon dating is commonly used to quantify timescales of magmatic processes, but our appreciation of the consequences of internal magma body dynamics lags behind ever-increasing analytical capabilities. In particular, it has been shown that crystal accumulation and melting of cumulates by recharge-delivered heat may affect melt chemistry within magma bodies. We considered the effect of such processes on zircon solubility in highly evolved silicate melts of diverse chemical affinities. Our modeling shows that in most cases cumulate melting perpetuates the zircon saturation behavior of the first melts emplaced at shallow storage levels. Once cumulate melting is established, the ease of saturating in zircon is controlled by cumulate mineralogy, with a particular effect of the amount of cumulate zircon and its availability for resorption. The fidelity of zircon as a recorder of magma system history thus depends on both the system’s chemical affinity and mineralogy, and the history itself.Published versionThis work was supported by the Swiss National Science Foundation (grant 200021_166281 to Ellis)

Modulation of zircon solubility by crystal-melt dynamics

Zircon dating is commonly used to quantify timescales of magmatic processes, but our ap-preciation of the consequences of internal magma body dynamics lags behind ever-increasing analytical capabilities. In particular, it has been shown that crystal accumulation and melting of cumulates by recharge-delivered heat may affect melt chemistry within magma bodies. We considered the effect of such processes on zircon solubility in highly evolved silicate melts of diverse chemical affinities. Our modeling shows that in most cases cumulate melting perpetu-ates the zircon saturation behavior of the first melts emplaced at shallow storage levels. Once cumulate melting is established, the ease of saturating in zircon is controlled by cumulate mineralogy, with a particular effect of the amount of cumulate zircon and its availability for resorption. The fidelity of zircon as a recorder of magma system history thus depends on both the system's chemical affinity and mineralogy, and the history itself.ISSN:0091-7613ISSN:1943-268

Europium and barium enrichments in compositionally zoned felsic tuffs : a smoking gun for the origin of chemical and physical gradients by cumulate melting

Felsic pyroclastic deposits of overall low crystallinity erupted from caldera volcanoes frequently display internal gradients in composition and crystal content. The chemical gradients in the melt phase are consistent with differentiation paths and mineral/melt element partitioning predicted from the observed phenocryst assemblage. The same units typically show crystal-scale evidence for generation of eruptible magma by thermal rejuvenation of initially static, high-crystallinity (>50%) mush. Deposit-scale zoning can be reconciled with system rejuvenation by a model in which a high-crystallinity cumulate mush beneath its cognate supernatant liquid is melted by more mafic recharge to produce denser, remobilized magma of accumulative composition. In this model, zoning is a symptom of thermal rejuvenation, but requires a fusible cumulate, as provided by alkali feldspar-rich assemblages. We review existing data and present new whole-rock, glass and mineral compositions for nine examples of zoned felsic units, across the spectrum of alumina- and silica-saturation. We show that whole rocks and glasses in the late-erupted or least-evolved parts of these examples are strongly enriched in Ba (and, less consistently, Sr), and exhibit positive Eu anomalies, providing unequivocal evidence for the production of eruptible magma through melting of alkali feldspar cumulate mush. Hence, felsic volcanic rocks of low to moderate crystallinity may nonetheless have chemical signatures characteristic of cumulates. However, many other zoned tuffs show more subdued Ba-Eu enrichment and lack positive Eu anomalies. Enrichment of Eu and Ba in the melt is modulated by the extent and degree of equilibration during melting, and may be a transient signal that is quickly suppressed by new feldspar growth occurring between melting and eruption. In cases of very highly evolved rhyolites, the prior depletion of Ba, Sr and Eu by extensive alkali feldspar fractionation precludes development of any strong enrichment, although the patterns of relative variation are similar to those in the examples discussed here.We thank Will Starkel, Chris Henry, Paul Olin, and Joe Boro for discussion. Samples from Tenerife and McDermitt were collected under projects funded by NSF EAR-0001013 and the USGS EDMAP program respectively. BSE gratefully acknowledges support from the Swiss National Science Foundation (200021_166281). The paper was improved by helpful comments from Rebecca Williams and John C. Whit

Maturation and rejuvenation of a silicic magma reservoir: High-resolution chronology of the Kneeling Nun Tuff

Knowledge of the conditions of magma storage prior to volcanic eruptions is key to their forecasting, yet little is known about how melt compositions, crystallinity and intensive parameters within individual magma reservoirs evolve over time. To address this, we studied the Kneeling Nun Tuff, a voluminous (>900 km3) deposit of an Eocene caldera-forming eruption from the Mogollon–Datil volcanic field in New Mexico, USA. Whole-rock, feldspar and amphibole compositions were combined with zircon trace-element geochemistry and precise isotope dilution-thermal ionisation mass spectrometry (ID-TIMS) U–Pb zircon crystallisation ages to arrive at a detailed, time-resolved record of chemical and physical changes within the voluminous, upper-crustal (∼2.2 kbar) magma reservoir. Chemical compositions and zircon ages from the Kneeling Nun Tuff and from co-magmatic clasts hosted within it reveal prolonged (>1.5 million years) growth and maturation of the magma reservoir that was heterogeneous in terms of temperature, melt composition and crystallinity. This protracted storage at a dominant crystallinity in excess of 50% culminated in a period of ca. 50 ky of increase in recharge heat supply and related homogenisation, decrease in crystallinity to 40–50%, and potential increase in average melt temperature, leading up to eruption at 35.299 ± 0.039 Ma. Sampling of co-magmatic lithic clasts derived from early-cooled domains of the reservoir shows that the long, million year-scale maturation time is shared across all erupted domains of the magmatic system, irrespective of their final cooling history. This study provides key observations from a natural system against which thermal and mechanical models of upper-crustal magma reservoir construction can be validated.ISSN:0012-821XISSN:1385-013

Obsidian pyroclasts in the Yellowstone-Snake River Plain ignimbrites are dominantly juvenile in origin

Dense, glassy pyroclasts found in products of explosive eruptions are commonly employed to investigate volcanic conduit processes through measurement of their volatile inventories. This approach rests upon the tacit assumption that the obsidian clasts are juvenile, that is, genetically related to the erupting magma. Pyroclastic deposits within the Yellowstone-Snake River Plain province almost without exception contain dense, glassy clasts, previously interpreted as hyaloclastite, while other lithologies, including crystallised rhyolite, are extremely rare. We investigate the origin of these dense, glassy clasts from a coupled geochemical and textural perspective combining literature data and case studies from Cougar Point Tuff XIII, Wolverine Creek Tuff, and Mesa Falls Tuff spanning 10 My of silicic volcanism. These results indicate that the trace elemental compositions of the dense glasses mostly overlap with the vesiculated component of each deposit, while being distinct from nearby units, thus indicating that dense glasses are juvenile. Textural complexity of the dense clasts varies across our examples. Cougar Point Tuff XIII contains a remarkable diversity of clast appearances with the same glass composition including obsidian-within-obsidian clasts. Mesa Falls Tuff contains clasts with the same glass compositions but with stark variations in phenocryst content (0 to 45%). Cumulatively, our results support a model where most dense, glassy clasts reflect conduit material that passed through multiple cycles of fracturing and sintering with concurrent mixing of glass and various crystal components. This is in contrast to previous interpretations of these clasts as entrained hyaloclastite and relaxes the requirement for water-magma interaction within the eruptive centres of the Yellowstone-Snake River Plain province.ISSN:0258-8900ISSN:1432-081

U-Th zircon dating reveals a correlation between eruptive styles and repose periods at the Nisyros-Yali volcanic area, Greece

Water-rich silicic magmas are capable of erupting effusively and explosively, and this drastic change in eruptive styles, termed effusive-explosive transition, has important implications in managing volcanic hazards. Some volcanoes exhibit effusive-explosive transitions during the same eruptive event, while others show this behavior between different eruptions. In the latter case, magma chamber processes induce physical-chemical changes in the magma, which can favor either effusivity or explosivity. This is the case for the Nisyros-Yali volcanic center, from the South Aegean Sea. In the recent stages of activity (past 120 ky), the volcanic area generated eight rhyolitic effusive and explosive events (five on the island of Nisyros and three on the island of Yali), including two caldera-forming eruptions. Changes of water content, temperature and pre-eruptive water-saturation between effusive and explosive deposits point to a potential time-dependency between the two eruptive styles. We investigate this time-dependency by applying Usingle bondTh disequilibrium dating to zircon crystals. Our eruptive age estimates of the investigated units range from 118.7 ± 10 ka to 19.9 ± 1.5 ka for Nisyros, and from 40 ± 5.2 ka to 22.7 ± 1.6 ka for Yali. Yali volcano has developed after the two caldera-forming events on Nisyros, which occurred at 63.1 ± 4.7 ka and 58.4 ± 2.7 ka. Yali marks the transition to a more geometrically complex system, where the upper-crustal silicic mush hosts at least two eruptible magma chambers (one under Yali, and one under Nisyros). The eruptive styles at both volcanoes seem to be correlated with the length of the repose periods. Effusive events occur after longer periods of volcanic quiescence, while explosive events are generated after shorter periods of repose of ~5–10 ky, which can be extended based on eruption age uncertainty to <18 ky for Nisyros and <12 ky for Yali. This observation is explained by the physical state of the volatiles in the magma chamber, with longer repose periods favoring volatile build-up. This can lead to water-supersaturation at storage pressures which was shown to favor effusivity. Based on this interpretation, both Nisyros and Yali volcanoes are presently in the effusive time window, which makes it probable for the next eruptions to be non-explosive.ISSN:0009-2541ISSN:1872-683

A red bole zircon record of cryptic silicic volcanism in the Deccan Traps, India

Abstract Silicic magmas within large igneous provinces (LIPs) are understudied relative to volumetrically dominant mafic magmas despite their prevalence and possible contribution to LIP-induced environmental degradation. In the 66 Ma Deccan LIP (India), evolved magmatism is documented, but its geographic distribution, duration, and significance remain poorly understood. Zircons deposited in weathered Deccan lava flow tops (“red boles”) offer a means of indirectly studying potentially widespread, silicic, explosive volcanism spanning the entire period of flood basalt eruptions. We explored this record through analysis of trace elements and Hf isotopes in zircon crystals previously dated by U–Pb geochronology. Our results show that zircon populations within individual red boles fingerprint distinct volcanic sources that likely developed in an intraplate setting on cratonic Indian lithosphere. However, our red bole zircon geochemical and isotopic characteristics do not match those from previously studied silicic magmatic centers, indicating that they must derive from yet undiscovered or understudied volcanic centers associated with the Deccan LIP.ISSN:0091-7613ISSN:1943-268

ID-TIMS U-Pb geochronology at the 0.1‰ level using 1013 Ω resistors and simultaneous U and 18O/16O isotope ratio determination for accurate UO2 interference correction

ISSN:0267-9477ISSN:1364-554