Search

New geochemical data, including Sr–Nd–Pb isotopes for whole-rock and groundmass samples, are reported for edifice-forming eruptives at Tongariro volcano, New Zealand, which span its ~ 350 ka to late Holocene history. Tongariro eruptives are medium-K basaltic-andesites to dacites (53.0–66.2 wt% SiO2) that evolved via assimilation-fractional crystallisation (AFC) processes partly or mostly in the uppermost 15 km of the crust. When ordered chronologically using a high-resolution 40Ar/39Ar-dated eruptive stratigraphy, the compositional data show systematic 10–130 kyr cycles. Mafic replenishment events inferred from MgO values occurred at ~ 230, ~ 151, ~ 88 and ~ 56 ka and in the late Holocene, with high-MgO flank vents erupting at ~ 160, ~ 117, ~ 35 and ~ 17.5 ka. Cycles in Sm/Nd, 87Sr/86Sr, 143Nd/144Nd and Pb isotopic ratios, which are decoupled from MgO, K2O and Rb/Sr cycles, indicate periods of prolonged crustal residence of magmas from ~ 230 to ~ 100 ka and ~ 95 to ~ 30 ka. AFC modelling shows that intermediate and silicic melt compositions, with r-values between 0.1 and 1, are needed to reproduce Tongariro compositional arrays. AFC models also indicate that ~ 20% of the average Tongariro magma comprises assimilated (meta)sedimentary basement material. Locally, Tongariro and adjacent Ruapehu volcanoes attain their most crust-like 87Sr/86Sr and 143Nd/144Nd compositions at ~ 100 and ~ 30 ka, paralleling with zircon model-age crystallisation modes at the rhyolitic Taupō volcano ~ 50 km to the NNE. These coincidences suggest that the timing and tempo of magma assembly processes at all three volcanoes were contemporaneous and may have been tectonically influenced since at least 200 ka.

Volatile measurements in mineral-hosted sealed melt inclusions, and open-ended embayments, have previously been used to study magma ascent dynamics in large rhyolitic eruptions. However, despite occurring more frequently, smaller-volume explosive events remain under-studied. We present magmatic volatile data from quartz-hosted melt inclusions and embayments for eight post-25.4 ka rhyolitic eruptions at Ōkataina Volcanic Centre, Aotearoa New Zealand. Seven originated from within the main caldera, and the other erupted from the associated Ōkareka Structural Embayment. Melt inclusions preserve volatile contents of 2.92–5.82 wt% H2O and 13–126 ppm CO2, indicating pre-eruptive storage depths of 4.5–7.4 km, with younger eruptions being more shallow. The lack of correlation between H2O, CO2, inclusion size or distance to the crystal rim suggests magma bodies experienced variable degrees of degassing during magma storage, with some amount of post-entrapment volatile modification prior to and concurrent with final magma ascent. Diffusion modelling of measured H2O gradients in melt embayments indicates ascent rates of 0.10–1.67 m.s−1 over time spans of 20–230 min for the intra-caldera events. In contrast, ascent rates for the eruption from the Ōkareka Structural Embayment may be more rapid, at 1.59–4.4 m.s−1 over a time span of 22–34 min. Our findings imply that the final, pre-eruptive magma movement towards the surface could be less than a few hours. Comparisons with published data for caldera-forming explosive events reveal no clear relationships between final ascent rate, eruption size or initial volatile content, implying that other factors besides eruption volume control rhyolite magma ascent.

The transport and degassing pathways of volatiles through large silicic magmatic systems are central to understanding geothermal fluid compositions, ore deposit genesis, and volcanic eruption dynamics and impacts. Here, we document sulfur (S), chlorine (Cl), and fluorine (F) concentrations in a range of host materials in eruptive deposits from Taupō volcano (New Zealand). Materials analysed are groundmass glass, silicic melt inclusions, and microphenocrystic apatite that equilibrated in shallow melt-dominant magma bodies; silicic melt and apatite inclusions within crystal cores inferred to be sourced from deeper crystal mush; and olivine-hosted basaltic melt inclusions from mafic enclaves that represent the most primitive feedstock magmas. Sulfur and halogen concentrations each follow distinct concentration pathways during magma differentiation in response to changing pressures, temperatures, oxygen fugacities, crystallising mineral phases, the effects of volatile saturation, and the presence of an aqueous fluid phase. Sulfur contents in the basaltic melt inclusions (~ 2000 ppm) are typical for arc-type magmas, but drop to near detection limits by dacitic compositions, reflecting pyrrhotite crystallisation at ~ 60 wt. % SiO2 during the onset of magnetite crystallisation. In contrast, Cl increases from ~ 500 ppm in basalts to ~ 2500 ppm in dacitic compositions, due to incompatibility in the crystallising phases. Fluorine contents are similar between mafic and silicic compositions ( 130 Tg of S (390 Tg sulfate) and up to ~ 1800 Tg of Cl, with potentially global impacts on climate and stratospheric ozone.

Taupō volcano (New Zealand) is distinguished as the source of Earth's youngest supereruption (∼25.5 ka), with Lake Taupō occupying the resulting caldera. Taupō has also produced eruptions of a wide...

Generally, terrestrial rocks, martian and chondritic meteorites exhibit a relatively narrow range in bulk and apatite Cl isotope compositions, with δ37Cl (per mil deviation from standard mean ocean chloride) values between − 5.6 and + 3.8 ‰. Lunar rocks, however, have more variable bulk and apatite δ37Cl values, ranging from ∼ − 4 to + 40 ‰. As the Howardite-Eucrite-Diogenite (HED) meteorites represent the largest suite of crustal and sub-crustal rocks available from a differentiated basaltic asteroid (4 Vesta), studying them for their volatiles may provide insights into planetary differentiation processes during the earliest Solar System history.\ud Here the abundance and isotopic composition of Cl in apatite were determined for seven eucrites representing a broad range of textural and petrological characteristics. Apatite Cl abundances range from ∼ 25 to 4900 ppm and the δ37Cl values range from − 3.98 to + 39.2 ‰. Samples with lower apatite H2O contents were typically also enriched in 37Cl but no systematic correlation between δ37Cl and δD values was observed across samples. Modelled Rayleigh fractionation and a strong positive correlation between bulk δ66Zn and apatite δ37Cl support the hypothesis that Cl degassed as metal chlorides from eucritic magmas, in a hydrogen-poor environment. In the case of lunar samples, it has been noted that δ37Cl values of apatite positively correlate with bulk La/Yb ratio. Interestingly, most eucrites show a negative correlation with bulk La/Yb ratio. Recently, isotopically light Cl values have been suggested to record the primary solar nebular signature. If this is the case then 4 Vesta, which accreted rapidly and early in Solar System history, could also record this primary nebular signature corresponding to the lightest Cl values measured here. The significant variation in Cl isotope composition observed within the eucrites are likely related to degassing of metal chlorides.

We present new nucleosynthetic, radiogenic and stable Sr isotopic data from fifteen previously studied CAIs from the Allende CV3 meteorite, including the highly altered Curious Marie inclusion. We use double-spike TIMS techniques to determine the degrees of isotopic mass fractionation, and also present internally normalised data for the same sample digestions to permit comparisons with previous studies and couple these isotopic data with Rb, Sr, Eu and Th abundance data to consider the origins and relationships of the isotopic variations documented here. Analysed CAIs display elevated μ^(84)Sr anomalies of +58 ppm to +287 ppm, with variability far outside of analytical uncertainties (13 ppm 2 s.d.). We cannot tell at present whether these variations arise from heterogeneities in p-process ^(84)Sr or in the other non-radiogenic isotopes of Sr (^(86)Sr, ^(88)Sr) that are produced by the main s-process, weak s-process, and r-process. All inclusions fall on an offset mass-dependent fractionation line in three-isotope space (δ^(88/86)Sr vs δ^(84/86)Sr) identical within error to that previously defined by bulk undifferentiated meteorites, and have a total range of δ^(88/86)Sr of ∼5.3 ‰ (+1.67 ‰ to -3.67 ‰), reflecting kinetic isotope effects during partial condensation/evaporation and/or low-temperature alteration processes. CI-normalized Sr/Th ratios in our CAIs correlate with normalized Eu/Th ratios with a ∼1:1 relationship, regardless of texture or Sr-isotopic values. This indicates that Sr and Eu had similar condensation behaviors with Eu condensing as Eu^(2+) and having the same chemical behavior in minerals as Sr^(2+) under conditions relevant to CAI formation in the solar nebula. Rb/Th ratios are highly variable: fine-grained CAIs display elevated Rb/Th ratios, consistent with the introduction of Rb into the CAIs by alkali-rich secondary alteration fluids. The μ ^(84)Sr anomalies measured in our CAIs are similar (in magnitude) to those found in carbonaceous chondrites that formed in the outer part of the solar system. A way to reconcile this observation with the formation of CAIs near the Sun would be if the inventories of Sr and other refractory elements in carbonaceous chondrites are dominated by a cryptic refractory dust component (CRD) that was formed early and near the Sun, and was subsequently transported outwards to the carbonaceous chondrite-forming region.

We consider here the validity, accuracy, and precision of rhyolite-MELTS modelling in inferring the pre-eruptive magma storage conditions for the caldera-forming 25.5 ka Oruanui and 232 CE (1.72 ka) Taupō eruptions at Taupō volcano, New Zealand as proposed by Pamukcu et al. (2020: Contrib Mineral Petrol 175: 48). There are four major issues with the modelling as used. First, the model is inappropriately applied for the Taupō event as this magma does not contain phenocrystic quartz. Second, the products of both eruptions, as is typical for virtually all Taupō Volcanic Zone rhyolites, contain plagioclase but lack sanidine, leading to increased model errors beyond those stated. Third, temperatures utilised for modelling crystallisation histories for both magmas are in conflict with independent measures of magmatic temperatures for these rocks. Fourth, glass compositions for each of these eruptions individually fall within analytical uncertainty yet yield model pressures that vary over hundreds of MPa, in part due to contrasting analytical protocols. We conclude that rhyolite-MELTS is too imprecise (errors of ± ~ 100 MPa or more for the methods applied) for quartz + 1 feldspar systems like at Taupō volcano specifically and the Taupō Volcanic Zone in general to be applied with confidence to deriving relative or absolute depths of magma storage.

Andesites erupted from Tongariro volcano, North Island, New Zealand contain feldspathic and quartzose xenoliths derived from basement rocks. New major oxide, trace element and Sr-Nd-Pb isotopic data indicate that both the Waipapa and Kaweka (meta)sedimentary terranes are represented in erupted xenoliths, rather than only the Kaweka terrane as previously thought. Xenolith mineral assemblages differ from their likely source materials, notably through the lack of white mica, illite, chlorite and quartz, which is reflected in contrasting chemical and isotopic compositions. Major and trace element data indicate that most xenoliths underwent bulk mass decreases of about 50% when pyrometamorphosed at temperatures of ~800–980 °C, similar to typical Tongariro magma temperatures of ~800–1000 °C. Bulk Eu concentrations were retained (in restitic plagioclase); however, other rare earth elements are commonly lower in xenoliths than in protoliths. In xenoliths, the 143Nd/144Nd ratios of protoliths were also retained, which indicates that xenoliths were derived from the Kaweka and Waipapa terranes in subequal amounts. Reductions in 87Sr/86Sr ratios by up to 0.003 in xenoliths, relative to their likely protoliths, were accompanied by decreases in Rb/Sr ratios from 0.1–0.8 down to

Step leaching of fine-grained refractory inclusions from Allende reveals the presence of large 84Sr anomalies., The 87Rb-87Sr radiochronometer provides key insights into the timing of volatile element depletion in planetary bodies, yet the unknown nucleosynthetic origin of Sr anomalies in Ca-Al–rich inclusions (CAIs, the oldest dated solar system solids) challenges the reliability of resulting chronological interpretations. To identify the nature of these Sr anomalies, we performed step-leaching experiments on nine unmelted CAIs from Allende. In six CAIs, the chemically resistant residues (0.06 to 9.7% total CAI Sr) show extreme positive μ84Sr (up to +80,655) and 87Sr variations that cannot be explained by decay of 87Rb. The extreme 84Sr but more subdued 87Sr anomalies are best explained by the presence of a presolar carrier enriched in the p-nuclide 84Sr. We argue that this unidentified carrier controls the isotopic anomalies in bulk CAIs and outer solar system materials, which reinstates the chronological significance of differences in initial 87Sr/86Sr between CAIs and volatile-depleted inner solar system materials.

The 2·08 Ma, ∼2500 km3 Huckleberry Ridge Tuff (HRT) eruption, Yellowstone, generated two fall deposits and three ignimbrite members (A, B, C), accompanying a ∼95 x 65 km caldera collapse. Field data imply that the pre-A fall deposits took weeks to be erupted, then breaks of weeks to months occurred between members A and B, and years to decades between B and C. We present compositional and isotopic data from single silicic clasts (pumice or fiamme) in the three ignimbrite members, plus new data from co-eruptive mafic components to reconstruct the nature and evacuation history of the HRT crustal magmatic complex. Geochemical data, building on field characteristics, are used to group nine silicic clast types into seven compositional suites (A1-A3; B1; C1-C3) within their respective members A, B and C. Isotopic data are then added to define four magmatic systems that were tapped simultaneously and/or sequentially during the eruption. Systems 1 and 2 fed the initial fall deposits and then vented throughout member A, accompanied by trace amounts of mafic magma. In member A, volumetrically dominant system 1 is represented by a rhyolite suite (A1: 73·0–77·7 wt % SiO2, 450–1680 ppm Ba) plus a distinct low-silica rhyolite suite (A2: 69·2–71·6 wt % SiO2, >2500 ppm Ba). System 2 yielded only a low-Ba, high-silica rhyolite suite (A3: 76·7–77·4 wt % SiO2, ≤250 ppm Ba). Glass compositions in pumices from systems 1 and 2 show clustering, indicative of the same multiple melt-dominant bodies identified in the initial fall deposits and earliest ignimbrite. Member B samples define suite B1 (70·7–77·4 wt % SiO2, 540–3040 ppm Ba) derived from magmatic system 1 (but not 2) that had undergone mixing and reorganisation during the A: B time break, accompanying mafic magma inputs. Mafic scoriae erupted in upper member B cover similar compositions to the member A clasts, but extend over a much broader compositional range. Member C clast compositions reflect major changes during the B: C time break, including rejuvenation of magmatic system 2 (last seen in member A) as suite C3 (75·3–77·2 wt % SiO2, 100–410 ppm Ba), plus the appearance of two new suites with strong crustal signatures. Suite C2 is another rhyolite (74·7–77·6 wt % SiO2, with Ba decreasing with silica from 2840 to 470 ppm) that defines magmatic system 3. Suite C2 also shows clustered glass compositions, suggesting that multiple melt-dominant bodies were a repetitive feature of the HRT magmatic complex. Suite C1, in contrast, is dacite to rhyolite (65·6–75·0 wt % SiO2, with Ba increasing with silica from 750 to 1710 ppm) that defines magmatic system 4. Compositions from magmatic systems 1 and 2 dominantly reflect fractional crystallization, but include partial melting of cumulates related to earlier intrusions of the same mafic magmas as those syn-eruptively vented. Country rock assimilation was limited to minor amounts of a more radiogenic (with respect to Sr) evolved contaminant. In contrast, systems 3 and 4 show similar strongly crustal isotopic compositions (despite their differences in elemental composition) consistent with assimilation of Archean rocks via partial melts derived from cumulates associated with contrasting mafic lineages. System 3 links to the same HRT mafic compositions co-erupted in members A and B. In contrast, system 4 links to olivine tholeiite compositions erupted in the Yellowstone area before, sparsely during, and following the HRT itself. All four magmatic systems were housed beneath the HRT caldera area. Systems 1 and 2 were hosted in Archean crust that had been modified by Cretaceous/Eocene magmatism, whereas systems 3 and 4 were hosted within crust that retained Archean isotopic characteristics. The extreme compositional diversity in the HRT highlights the spatial and temporal complexities that can be associated with large-volume silicic magmatism.

The compositions of the first solar system solids were shaped by nonequilibrium condensation and evaporation., Equilibrium condensation of solar gas is often invoked to explain the abundance of refractory elements in planets and meteorites. This is partly motivated, by the observation that the depletions in both the least and most refractory rare earth elements (REEs) in meteoritic group II calcium-aluminum–rich inclusions (CAIs) can be reproduced by thermodynamic models of solar nebula condensation. We measured the isotopic compositions of Ce, Nd, Sm, Eu, Gd, Dy, Er, and Yb in eight CAIs to test this scenario. Contrary to expectation for equilibrium condensation, we find light isotope enrichment for the most refractory REEs and more subdued isotopic variations for the least refractory REEs. This suggests that group II CAIs formed by a two-stage process involving fast evaporation of preexisting materials, followed by near-equilibrium recondensation. The calculated time scales are consistent with heating in events akin to FU Orionis– or EX Lupi–type outbursts of eruptive pre–main-sequence stars.

Hydrothermal alteration zoning and processes provide insights into the evolution of heat source(s) and fluid compositions associated with geothermal systems. Traditional petrological techniques, combined with hydrothermal alteration studies, stable isotope analyses and geochronology can resolve the nature of the fluids involved in hydrothermal processes and their changes through time. We report here new findings along with previous unpublished works on alteration patterns, fluid inclusion measurements and stable isotope data to provide insights into the thermal and chemical evolution of the Kawerau geothermal system, New Zealand. These data indicate the presence of two hydrothermal events that can be coupled with chronological data. The earlier period of hydrothermal activity was initiated at ~400 ka, with the heat driving the hydrothermal system inferred to be from the magmatic system that gave rise to rhyolite lavas and sills of the Caxton Formation. Isotopic data fingerprint fluids attributed to this event as meteoric, indicating that the magma primarily served as a heat source driving fluid circulation, and was not releasing magmatic fluids in sufficient quantity to affect the rock mineralogy and thus inferred fluid compositions. The modern Kawerau system was initiated at ~16 ka with hydrothermal eruptions linked to shallow intrusion of magma at the onset of activity that gave rise to the Putauaki andesite cone. Likely associated with this later event was a pulse of magmatic CO2, resulting in large-scale deposition of hydrothermal calcite enriched in 18O. Meteoric water-dominated fluids subsequently overwhelmed the magmatic fluids associated with this 18O-rich signature, and both the fluid inclusion microthermometry and stable isotope data reflect a change to the present-day fluid chemistry of low salinity, meteoric-dominated waters.

International audience; Volatile elements play a key role in the dynamics of planetary evolution. Extensive work has been carried out to determine the abundance, distribution, and source(s) of volatiles in planetary bodies such as the Earth, Moon, and Mars. A recent study showed that the water in apatite from eucrites has similar hydrogen isotopic compositions compared to water in terrestrial rocks and carbonaceous chondrites, suggesting that water accreted very early in the inner solar system given the ancient crystallization ages (~4.5 Ga) of eucrites. Here, the measurements of water (reported as equivalent H2O abundances) and the hydrogen isotopic composition (δD) of apatite from five basaltic eucrites and one cumulate eucrite are reported. Apatite H2O abundances range from ~30 to ~3500 ppm and are associated with a weighted average δD value of −34 ± 67‰. No systematic variations or correlations are observed in H2O abundance or δD value with eucrite geochemical trend or metamorphic grade. These results extend the range of previously published hydrogen isotope data for eucrites and confirm the striking homogeneity in the H-isotopic composition of water in eucrites, which is consistent with a common source for water in the inner solar system.

Silicic volcanic systems provide timed snapshots at the Earth's surface of the magmatic processes that also build complementary plutons in the crust. Links between these two realms are considered here using three Quaternary (

The central part of the Taupo Volcanic Zone (TVZ), New Zealand, is notable for the number (23) and size of its high-temperature geothermal systems. Of these, the Wairakei-Tauhara geothermal system collectively represents the largest commercially developed example. Natural thermal output prior to utilisation, i.e. before 1950 was ∼530 MW. Since 1950, drilling of over 300 closely spaced wells for power generation has provided geological data for a comprehensive stratigraphic framework. Within this framework, the strata are dominantly rhyolitic pyroclastic rocks and lava bodies, with interbedded fluvial and lacustrine deposits. Until now, no subsurface units had been directly dated and their ages were constrained only by their positions relative to the surficial 25.4 ka Oruanui ignimbrite, or to buried ignimbrite that is correlated with the 349 ka Whakamaru Group. This paper presents 33 suites of U-Pb age data and a limited number of reconnaissance U-Th disequilibrium age data from magmatic zircon crystals (zircons) to date the rocks of the Wairakei-Tauhara system. The oldest units dated are intermediate lavas from ca. 1.7 Ma, while the youngest locally vented eruptives of Tauhara dacite are tentatively dated to ca. 60 ka. Placing the age data within the established drillhole record allows for the recognition of major volcano-tectonic events and spatially clustered local volcanism that represents magmatic heat sources for geothermal activity within the Wairakei-Tauhara area. In contrast to the Rotokawa and Ngatamariki geothermal systems 10–20 km to the northeast, the Wairakei-Tauhara area was affected by two episodes of caldera collapse associated with deposits dated at 349 ka and 310 ka, leading to major faulting and abrupt variations in thicknesses of units. The faulting and deposit thickness variations established in these two events remain major controls on present-day permeability of the geothermal system. The new age data and stratigraphy demonstrate development of distinct magma systems through time which may have stimulated previous periods of hydrothermal activity. However, from zircon age data from the rhyolite-andesite mixed Tauhara dacite, we propose that the current geothermal system was initiated at ca. 60 ka and is thermally maintained by continuing contributions from the same magmatic system that has sporadically vented distinctive rhyolite since.

Rubin et al . (Reports, 16 June 2017, p. 1154) proposed that gradients in lithium abundance in zircons from a rhyolitic eruption in New Zealand reflected short-lived residence at magmatic temperatures interleaved with long-term “cold” (

The stable strontium isotope system (δ88/86Sr) has recently been suggested to be a suitable proxy for determining variations in the strength of the marine carbonate system, the principal output flux of oceanic Sr. However, in order to be able to interpret carbonate-driven variations in δ88/86Srseawater a robust understanding of δ88/86Srinput is required. Surprisingly only a limited amount of δ88/86Sr data currently exists for rivers and hydrothermal fluids, thus this study assesses the variability of δ88/86Sr and 87Sr/86Sr in global rivers, hydrothermal fluids and porewaters, as well as minor marine Sr sources such as continental dust, rainwater and glacial ice. Our analyses broadly confirm the findings of Krabbenhoft et al. (2010), and reveal flux-weighted δ88/86Srriverine and 87Sr/86Srriverine compositions of 0.32‰ and 0.71299 respectively. The hydrothermal fluids analysed in this study are consistent with an end-member δ88/86Srhydrothermal composition that is the same as the oceanic crust at ∼0.24‰, although three samples that display δ88/86Sr compositions offset from the seawater-hydrothermal mixing trend suggest that the precipitation of alteration phases such as anhydrite may drive δ88/86Srhydrothermal to higher values. Porewater fluids obtained from sediment cores in the Atlantic and Pacific Oceans have δ88/86Sr compositions within error of seawater (0.39‰), implying that the diagenetic flux of Sr may not significantly affect the δ88/86Sr composition of seawater. Continental loess samples have δ88/86Sr compositions that are consistently lighter than, or equal to, terrestrial silicates, with their tendency to lower values thought to reflect the preferential removal of heavier Sr isotopes into solution during weathering. Finally, rainwater and glacial ice samples have δ88/86Sr compositions that are also isotopically lighter than their associated water sources, a factor that may be attributed to interaction with isotopically light loess and additional Sr contributions from the bedrock. Together, the principal marine inputs define flux-weighted oceanic δ88/86Srinput and 87Sr/86Srinput compositions of 0.32‰ and 0.71161. These values are consistent with an elevated supply of riverine Sr to the oceans due to increased post-glacial weathering, but require the enhanced weathering of exposed carbonate shelves during glacial periods or significant changes in the rate of carbonate burial to match observed changes in the 87Sr/86Sr ratio of seawater. Our results confirm that, providing a diagenetically robust proxy can be found, the δ88/86Sr and 87Sr/86Sr isotope systems should provide a useful proxy for investigating changes in the marine carbonate system through time.

Strontium isotopic anomalies in meteorites are important in assessing nucleosynthetic sources to, and measuring the timing of, early solar system processes. However, conventional use of a constant 88Sr/86Sr value in correcting for instrumental mass fractionation during analysis renders measurements ambiguous and removes information on mass-dependent fractionation variations. From double-spike techniques we obtain data for the four stable strontium isotopes free of this ambiguity, and report measurements from a range of meteoritic, lunar and terrestrial materials. The Earth, Moon, basaltic eucrites and feldspars from angrites (differentiated samples) follow a single mass-dependent fractionation line and have a common nucleosynthetic origin in terms of their strontium isotopes. In contrast, bulk rock CI, CV3, CM and CO chondrite samples serve to define another mass-dependent fractionation line, displaced by 94 ± 28 ppm to heavier 84Sr/86Sr and/or 88Sr/86Sr ratios than that for the differentiated samples. Our Sr-isotopic data are consistent with a primary contrast in early solar system composition between an outer zone of primitive, mostly undifferentiated, materials and an inner zone of (almost entirely) differentiated materials that accumulated to form the terrestrial planets.

New zircon U^Th model-age and trace element datasets are presented fromTaupo volcano (New Zealand), which are used to investigate the timescales and broad-scale magmatic processes involving zircon crystallization after the caldera-forming 25·4 ka Oruanui supereruption. Detailed C-based chronologies and controls on vent locations allow the timing and location of post-caldera eruptions to be spatially and temporally constrained to an extent not possible for any other supervolcano. After 5 kyr of post-Oruanui quiescence, Taupo erupted three dacitic units, followed by another 5 kyr break, and then a sequence of rhyolitic units in three subgroups (SG1^SG3) from 12 ka onwards. Despite overlapping vent sites and crustal source domains between the Oruanui and post-Oruanui eruptions, U^Th zircon model ages inTaupo SG1 rhyolites (erupted from 12 to 10 ka) indicate only minor inheritance of crystals from the Oruanui magma source. Post-Oruanui model-age spectra are instead typically centred close to eruption ages with subordinate older pre-300 ka equiline grains in some units. U^Pb dating of these older grains shows that both 300^450 ka plutonic-derived and pre100 Ma greywacke basement-derived zircons are present. The former largely coincide in age with zircons from the 350 ka Whakamaru eruption products, and are dominant over greywacke in young units that were vented within the outline of the Whakamaru caldera. Despite multiple ages and vent sites, trace element compositions are broadly similar in zircons, regardless of their ages. However, a small subset of zircons analysed from SG1 rhyolite (Units B and C) have notably high concentrations of U, Th, P, Yþ (REE)3þ and Nb but with only minor variations in Hf andTi. SG2 zircons typically have higher Sc contents, reflecting large-scale changes in melt chemistry and crystallizing mineral phases with time.The age spectra indicate that most Oruanui zircons were removed by thermally induced dissolution immediately following the supereruption. U^Th ages from single post-Oruanui eruptions show consistent inheritance of post-Oruanui grains with model ages that centre between the temporally separated but geographically overlapping eruption groups, generating model-age modes. Within the statistical limitations of the isotopic measurements, we interpret these repeated modes to be significant, resulting from incorporation of crystal populations from cyclic post-Oruanui periods of magmatic cooling and crystallization, acting within a crustal protolith chemically independent of that which was dominant in the Oruanui system.These periods of cooling and crystallization alternate with times of rejuvenation and eruption, sometimes

Crystallisation-age spectra have been obtained by SIMS techniques (SHRIMP-RG) on zircons from altered volcanic units penetrated by drillholes at Kawerau Geothermal Field in the central Taupo Volcanic Zone (TVZ), New Zealand. Drillholes penetrate 700–1300 m of volcanic rocks and sediments before reaching the basement Mesozoic greywacke. Twenty-seven samples of altered volcanic lithologies and two surficial, fresh rock units have been studied in order to constrain ages of the major stratigraphic units. Within the volcanic/sedimentary pile the oldest in-situ ignimbrites that can be widely correlated have ages of ~ 1.45 Ma. Between them and the basement greywacke is a variable thickness of sediments, mostly greywacke gravels and minor volcaniclastic units, reflecting localised basinal deposition associated with strike–slip faulting. Two ignimbrites within this sequence yield age estimates of c. 2.4 and 2.1 Ma, consistent with these being distal southern Coromandel Volcanic Zone deposits, pre-dating TVZ activity. Below the regional marker plane of the 0.32 Ma Matahina ignimbrite, three main ignimbrite groups occur, with ages around 1.45 Ma, 1.0 Ma and 0.6–0.5 Ma, which are separated by sediment-dominated intervals and andesite volcanics. All of these ignimbrites represent marker horizons from other volcanic centres and do not reflect the presence of local magmatic heat sources. Numerous bodies of coherent rhyolite, previous labelled as Caxton and Onepu rhyolites, have been intersected at all pre-Matahina ignimbrite levels (including within the basement greywacke) and reflect earlier local magmatic heat sources. Our geochronological data resolve these rock bodies into three packages. The youngest is represented by the surficial rhyodacite Onepu domes, 40 Ar/ 39 Ar dated at 0.138 ± 0.007 Ma. U–Pb ages on zircons from dome material yield a spectrum that can be matched (consistent with petrography) with two dikes intersected at 880 m and 2.67 km depth, and with an estimated age of 0.15 ± 0.01 Ma (Onepu Formation). The older two packages consist of older crystal rich (~ 15%) and younger crystal-poor (~ 5%) rhyolite, here grouped as Caxton Formation and with eruption/intrusion age of 0.36 ± 0.03 Ma. The shallowest Caxton rhyolite bodies are interpreted to be domes, whilst deeper intersections are inferred to be sills based on the lateral extents relative to thicknesses. Net subsidence rates inferred from depths to key units do not reflect the present-day situation. Modern rates of subsidence (2 ± 1 mm/yr) associated with TVZ rifting processes can have been active for no more than ~ 50,000 years, based on elevation differences of the Matahina ignimbrite top surface. An inferred change in intrusion geometry from sill (Caxton) to dike (Onepu) indicates a change in principal stress orientations reflecting onset of the modern Whakatane Graben. This change is dated at ~ 0.37 Ma in coastal sedimentary sequences 23 km to the north of Kawerau, consistent with our age data. Although previously interpreted to be a long-lived system, the modern Kawerau Geothermal Field is a Holocene entity reflecting the rejuvenation of magmatic heat flux associated with Putauaki volcano superimposed on an area of multiple reactivated fault structures, sporadic magmatism and variable rates of subsidence.

Trace concentrations of Ti in quartz are used to indicate the pressure and temperature conditions of crystallization in the ‘TitaniQ’ geothermobarometer of Thomas et al. (Contrib Miner Petrol 160:743–759, 2010). It utilises the partitioning of Ti into quartz as an indicator of the pressures and/or temperatures of crystal growth. For a given value of TiO2 activity in the system, if temperatures are inferred to ±20 °C, pressure is constrained to ±1 kbar and vice versa. There are significant contrasts, however, between the conclusions from TitaniQ and those for natural quartz (as well as other mineral phases) in volcanic rocks. Application of the TitaniQ model to quartz from the 27 ka Oruanui and 760 ka Bishop high-silica rhyolites, where the values of T, P and TiO2 activity are constrained by other means (Fe–Ti oxide equilibria, melt inclusion entrapment pressures in gas-saturated melts, melt and amphibole compositions), yields inconsistent results. If realistic values are given to any two of these three parameters, then the value of the third is wholly unrealistic. The model yields growth temperatures at or below the granite solidus, pressures in the lower crust or upper mantle, or TiO2 activities inconsistent with the mineralogical and chemical compositions of the magmas. CL imagery and measurements of Ti (and other elements) in quartz are of great value in showing the growth histories and changes in conditions experienced by crystals, but direct linkages to P, T conditions during crystal growth cannot be achieved.

This study presents comprehensive strontium stable isotope (88Sr/86Sr) data, measured by multiple-collector inductively-coupled plasma mass spectrometry (MC–ICP-MS), for a suite of carbonaceous chondrites, differentiated meteorites, lunar, martian and terrestrial samples. Carbonaceous chondrites comprise a mixture of refractory inclusions and chondrules that have light δ88Sr values between − 0.35 to + 0.05‰ and matrix material that possesses a heavy δ88Sr composition of 0.65‰, confirming the results of earlier studies. Consequently, bulk carbonaceous chondrites are relatively heterogeneous in composition ranging from + 0.12 to + 0.35‰, most likely reflecting clast–matrix variability. The light δ88Sr compositions of the refractory inclusions are consistent with mass dependent fractionation of other refractory elements (Ca and Eu) and are most likely produced by non-equilibrium fractionation (undercooling in the nebula gas) during condensation of hibonite from the solar nebula (Simon and DePaolo, 2010. Stable calcium isotopic composition of meteorites and rocky planets. Earth Planet. Sci. Lett. 289, 457–466). Carbonaceous chondrites, angrites and martian meteorites have indistinguishable compositions at the level of analytical uncertainty of this study. However, statistical analysis indicates that melts derived from the Earth's mantle have heavier δ88Sr values than bulk carbonaceous chondrites and martian meteorites, but compositions indistinguishable from eucrites (δ88Sr = + 0.26 ± 0.12‰). Moreover, terrestrial basalts and andesites have restricted δ88Sr values (+ 0.30 ± 0.07‰), suggesting that mantle melting delivers rather homogenous melts to the Earth's surface with respect to δ88Sr. In contrast, glasses from evolved terrestrial rocks and lunar basalts extend to very light δ88Sr values ~−0.20‰. The Sr stable isotope composition covaries with europium anomaly (Eu/Eu*), as an index of plagioclase fractionation, and δ88Sr can be successfully modelled by the heavy isotopes of Sr being preferentially partitioned into plagioclase with a fractionation factor of ~ 1.0007 for 88Sr/86Sr. Our results demonstrate that Sr stable isotopes may be significantly fractionated at high temperatures and their measurement can provide insights into planetary evolution and magmatic processes.

Pre- and syn-eruptive time-scales of magmatic processes in large-scale explosive eruptions can be quantified from compositional gradients established between (and within) crystals and their host melt using models of diffusive relaxation. The faster the elemental diffusion rate, the shorter the time periods that are measurable. Here we document Li compositional gradients from crystals in the rhyolitic magma of the ~ 27 ka Oruanui supereruption (Taupo, New Zealand). In plagioclase feldspar and quartz from pumices in the first-erupted material, and loose feldspar crystals from late-erupted ignimbrite, the crystal rims display a ~ 50% increase in Li concentration over equilibrium values in the crystal cores. At appropriate magmatic temperatures, these gradients represent time-scales of 125 to 720 s, equivalent to decompression rates of 30–180 kPa/s and rise rates of frothy magma of 4–21 m/s. We infer that these short time-scales reflect changes in lithium partitioning behaviour during decompression, and cannot be due to changes in Li concentration accompanying degassing and the growth of bubbles (which act in the opposite sense). The Li partitioning changes are due to the breakdown of the liquid–vapour equilibrium at the critical pressure of 22 MPa, where the vapour phase transitions from a supercritical to a subcritical state. This breakdown causes Li to partition from melt into crystals, inducing a short-lived increase in effective Li activity of about 50%. The system is then quenched rapidly by cooling in air or water on eruption. These results capture syn-eruptive processes on unprecedentedly short time-scales in a type and size of eruption where information concerning such late-stage processes has never before been obtainable.

U-Pb zircon age spectra from a metasedimentary xenolith and a young dacite provide evidence for rapid episodes of crustal melting and eruption at Taupo volcano, as well as unexpected crustal structure beneath the Taupo Volcanic Zone. Ages from the xenolith in a 28 ka rhyolite dome match those from Early Cretaceous Pahau Terrane graywackes that crop out >75 km east of the volcano and were underthrust and partially melted during the penecontemporaneous accretion process. Boundaries between graywacke terranes in the North Island are thus more complex than implied from map views. In contrast, ages from zircons in the 20 ka Omega dacite match the nearby surficial graywacke of the Jurassic Kaweka Terrane (55% of grains), Quaternary plutonic sources (39%), and Pahau Terrane graywacke (6%). Five of 72 grains analyzed contain graywacke cores and Pleistocene rims. Survival of euhedral xenocrystic zircons through the generation processes for Omega dacite magma reflects wholesale melting of crustal protoliths (including varieties not previously considered for petrogenetic modeling), open-system behavior, and crustal melts being generated and erupted within ∼1–10 yr.

U–Th disequilibrium model-age data are presented for zircons from four young eruptive units from Okataina volcano, New Zealand. These data highlight contrasts in the time-scales over which eruptible silicic magma bodies are generated and accumulated below a highly active rhyolite volcano prior to and following the ~61 ka caldera-forming Rotoiti eruption (80 – 120 km 3 magma). The Rotoiti event was followed by ≥12 explosive eruptions of the Mangaone Subgroup between ~45 and 30 ka. A change in eruptive styles between ~30 and 25 ka brackets the major Oruanui eruption of Taupo volcano ~80 km away; subsequently eight rhyolitic, lava-dominated and two basaltic explosive eruptions occurred between 25 ka and 1886 CE. We present (238U–230Th) zircon model-age data determined by secondary-ion mass spectrometry (SIMS) and thermal ionization mass spectrometry (TIMS) from the Rotoiti, Ngamotu (Unit B) (~45 ka), Mangaone (Unit I) (33 ka) and Rotorua (15•4 ka) eruptive units. We couple these data with published and new compositional information to trace magma crystallization and storage patterns. Population density curves of SIMS model ages from zircons in the two pumice types (biotite-free and biotite-bearing) from the Rotoiti eruption differ. Zircons from the former yield a model-age peak coincident with eruption age, whereas zircons from the latter show a peak at 70–90 ka and little variation in TIMS model-age values from different crystal size fractions. Concentration weighted means of model ages from the two pumices, however, are the same within 1 SD error, and their Sr isotopic values overlap at 2 SD precision, suggesting that they are genetically linked. Model-age spectra for the Ngamotu, Mangaone and Rotorua pumices are complex, indicating recycling of crystals from multiple older populations that largely pre-date the 61 ka caldera-forming eruption. Superimposed on the older age spectra are variably developed younger pre-eruptive suites of ages reflecting varying amounts of crystallization prior to each eruption. A lack of commonality in these younger peaks in the post-caldera eruptive rocks, along with compositional and isotopic differences between (and sometimes within) the eruptive units, collectively precludes their origin from a single melt-bearing mush system. Okataina contrasts with Taupo, where comparable-age eruption deposits have simpler age spectra, consistent with larger-scale crystallization cycles and thermal events in the magma chambers there. When compared with other caldera-related silicic systems for which suitable data are available, Okataina differs in lacking a simple pre-eruptive history prior to its caldera-forming event and having a complex, non-coherent magmatic history of post-caldera eruptions.

Recognising and correlating hydrothermally altered rock units within buried volcanic sequences in the Taupo Volcanic Zone (TVZ) in New Zealand is difficult. This is because of broad similarities in the lithologies of many major ignimbrite units, and the destruction by hydrothermal alteration of distinctive chemical and mineralogical characteristics. However, magmatic zircons are commonly present, are highly resistant to hydrothermal alteration and yield crystallisation ages in intensely altered rocks. Crystallisation-age spectra have been obtained by SIMS techniques (SHRIMP-RG) on zircons extracted from cores from altered ignimbrites penetrated by drillholes at the Waiotapu, Te Kopia and Orakei Korako geothermal fields in the central TVZ. At Waiotapu, the thick (up to 350 m) densely welded Waiotapu Ignimbrite returned a zircon age spectrum with a probability density function (pdf) peak of 0.79 Ma, consistent with an eruption age (from 40Ar/39Ar techniques) of 0.71 ± 0.06 (1 s.d.) Ma. Three older ignimbrite sheets yielded age spectra that were consistent stratigraphically. The shallowest of the three yielded sparse zircons that gave a pdf peak of 1.24 Ma and it may correlate with the 1.18 ± 0.02 Ma Ahuroa ignimbrite. The middle sheet, although 220 m thick, yielded an age spectrum identical to that obtained from pumice in the widespread 1.21 ± 0.04 Ma Ongatiti ignimbrite, extending earlier estimates of the likely volume of this large deposit. The deepest sheet has a spectrum consistent with an eruption age of 1.45 ± 0.05 Ma; it has no surficial correlative, but its likely coeruptive ash forms part of a concentrated group of primary or secondary tephra in sediments on the ocean floor east of New Zealand and in sedimentary basins across the North Island. These three ignimbrites were previously correlated with either major ignimbrites exposed on the Paeroa Fault scarp, 10 km to the west, or the Akatarewa Ignimbrite that occurs in drillholes at Te Kopia and Orakei Korako, but these correlations are disproved from our age data. Drillholes at Te Kopia (TK) and Orakei Korako (OK), reach, but do not penetrate the base of, one or more deposits collectively termed the Akatarewa Ignimbrite. Samples from 62 (TK) and 165 m (OK) below the top contact of this unit yielded closely similar age spectra and pdf maxima of 1.00 (TK) and 1.02 Ma (OK), implying that the same deposit was penetrated at both fields. This ignimbrite is not correlated with a specific surface equivalent; several candidate deposits exist, but all are areally restricted. The Akatarewa Ignimbrite at TK and OK is, however, not the same deposit as those earlier correlated with it at Waiotapu. The age data are consistent with there being two zones of subsidence on both sides of a horst aligned with the three geothermal fields sampled. The eastern zone is the Reporoa Basin, which has high heat flow but little surface faulting, and the western one is the axis of the Taupo Rift, currently with low heat flow but abundant surface faulting. Overall subsidence rates at the three geothermal fields studied vary between 2 and

New and/or enlarged datasets of U–Th disequilibrium model ages from secondary ionization mass spectrometry (SIMS) analyses of zircons in eight eruptive units from the area of Taupo volcano, New Zealand, highlight the behavioural contrasts of two closely adjacent, contemporaneous but independent magma chambers. One yielded closely similar crystal-poor (‘Oruanui-type’) rhyolites, sampled in three small precursor eruptions (Tihoi, ‘New plinian’, Okaia) from ∼45 to 30 ka, then the major 27 ka Oruanui eruption. Three of the four eruptions had vents within the modern Lake Taupo, whereas the fourth (‘New plinian’) was sourced ∼20 km NNE of the other vents, fed by lateral magma migration. Samples from all four eruptions share a common model-age peak at ∼95 ka of antecrystic zircons. However, three of the four differ in younger pre-eruptive model-age peaks that require their parental melt-dominant bodies to have been physically extracted independently from a common mush zone represented by the ∼95 ka peak. A sample from a fifth eruption (‘New phreatoplinian’, also at ∼45 ka) shares an older 80–100 ka peak but has numerous older grains and distinctly contrasting Sr-isotopic characteristics to the ‘Oruanui-type’ magmas. The 530 km 3 Oruanui melt-dominant body was produced in at most ∼3000 years as shown by differences in zircon model-age spectra and average ages between it and the 30 ka Okaia eruption, despite their coincidence in vent locations. The second suite of eruptions at ∼47, 28 and 16 ka ejected moderately crystal-rich biotite rhyolites from a second source chamber, which vented over a 15 km wide area NE of Taupo (overlapping with Maroa volcano). This second chamber is inferred to have comparable horizontal dimensions to the vent spacing. The three biotite rhyolites show unimodal model-age spectra that peak at 30, 15–25 and 6 kyr prior to each eruption, respectively, and underwent single cycles of melt generation and eruption with no recycling of significantly older antecrysts or xenocrysts ( 5 m 3 /s (Oruanui) and effectively drained the mush of melt in doing so (Oruanui vs post-Oruanui activity), probably mediated by active rifting processes and tectonic disruption of the mush pile. Comparisons of ‘magma residence times’ and discussion of the growth histories of large silicic chambers represented by volcanic or plutonic rocks are self-limited by the uncertainties in the respective SIMS analyses. Growth times of Miocene and older plutons dated by SIMS U–Pb techniques are comparable with the 2 Myr lifetime of the whole Taupo Volcanic Zone, and the associated 1σ SIMS analytical uncertainties exceed the lifetime of a volcano such as Taupo. Subtle details that indicate the rapidity of magma accumulation and recycling of crystals in the young Taupo system cannot be discerned in most pre-300 ka silicic systems. Averaging of SIMS model-age data further obscures subtle details that would allow discrimination of newly crystallized versus recycled zircons. Discussions of volcano–plutonic relationships and accumulation rates for large silicic melt-dominant bodies cannot rely on age data in isolation, but require knowledge of the stratigraphic and compositional settings.

Recognition and correlation of rock units within geothermal fields is often hampered by high degrees of alteration that obscure primary mineralogies and lithological boundaries, and preclude direct dating by radiometric techniques. Magmatic zircons are commonly present in silicic volcanic rocks, where zircon saturation was achieved and zircons crystallized up to the point of eruption. Young zircons are highly resistant to hydrothermal alteration and can yield a record of their crystallization ages in otherwise heavily altered rocks. Zircon crystallization-age spectra have been obtained by SIMS techniques (SHRIMP-RG) from three samples of cuttings and a core sample from ignimbrite penetrated in 3 drillholes up to ~ 3.2 km deep at the Mangakino geothermal field in New Zealand. The crystallization ages are similar between the drillcore and cutting samples, indicating that downhole mixing of cuttings has not been important, and showing collectively that volcanic units of closely similar ages are represented between ~ 1.4 and ~ 3.2 km depth. This is despite apparent changes in the inferred primary volcanic lithology that had led to earlier inferences that multiple ignimbrites of contrasting age were present in this depth interval. Comparisons of zircon crystallization-age spectra and inferred primary mineralogical characteristics from the drillhole samples with surficial ignimbrites that crop out west of Mangakino suggest that the boreholes have entered a > 1.8-km-thick intracaldera fill of ignimbrite generated in the closely-spaced Kidnappers and Rocky Hill eruptions at ~ 1 Ma.

Rhyolitic pumices in the 26.5 ka Oruanui eruption (Taupo volcano, New Zealand) contain an average of 10 wt% crystals. About 2 wt% of the crystal population is feldspar crystals that display bluish–grey cloudy cores, the colour being imparted by exsolved needles of rutile. The volume of cloudy-cored feldspars thus amounts to ~1.0 km3 in a total magma volume of ~530 km3. The cored feldspars show great variability in detail, but in general have a rounded cloudy core bounded by a zone rich in glass and mineral inclusions, that was then overgrown by a euhedral clear rim. Sr-isotopic variations in eight representative crystals were measured on micromilled samples of selected growth zones in the cores and rims, and linked to feldspar compositions through microprobe traverses. The cloudy cores range from 87Sr/86Sr = 0.70547 to 0.70657, with compositions of An43 to An78. The overgrowth rims display wider variations: inner parts show extreme ranges in composition (maxima 87Sr/86Sr = 0.70764 and An78), while outer parts in seven of eight crystals are zoned, with outward-decreasing Sr-isotopic and An values to figures that are in accord with the bulk pumice and other, clear-feldspar values, respectively. The three parts of the crystals represent distinct regimes. The cloudy cores are inherited from an intermediate plutonic protolith that has been subjected to melting. The inner overgrowth rims were crystallised from a high temperature, relatively radiogenic melt derived from Mesozoic-Palaeozoic metasedimentary rocks (“greywacke”). The outer euhedral rims reflect mixing into and continued growth within the growing Oruanui magma body. The cloudy-cored feldspars also contain rare zircon inclusions. Twenty one zircons were recovered by HF digestion of a bulk sample of cloudy feldspars and analysed by SHRIMP for U–Th isotopes with which to calculate model ages. Eighteen of 21 crystals returned finite ages, the model-age spectrum of which is similar to the age spectra from free zircons in Oruanui pumices. Assembly of the Oruanui magma body was not only rapid (over ~40 kyr, as shown by other data) but involved a wide open system, with significant contributions from partly-melted intermediate-composition igneous intrusions (cloudy cores) and greywacke melts (inner overgrowths) being introduced into the magma body up to the point of eruption. Such open system behaviour contrasts with that proposed in models for comparably voluminous silicic magmas derived dominantly by fractionation (such as the Bishop Tuff) where the magma and its crystal cargo were better insulated thermally and chemically from country-rock interaction.

Batholith-sized bodies of crystal-rich magmatic 'mush' are widely inferred to represent the hidden sources of many large-volume high-silica rhyolite eruptive units. Occasionally these mush bodies are ejected along with their trapped interstitial liquid, forming the distinctive crystal-rich ignimbrites known as 'monotonous intermediates'. These ignimbrites are notable for their combination of high crystal contents (35-55%), dacitic bulk compositions with interstitial high-silica rhyolitic glass, and general lack of compositional zonation. The 5000 km 3 Fish Canyon Tuff is an archetypal eruption deposit of this type, and is the largest known silicic eruption on Earth. Ejecta from the Fish Canyon magmatic system are notable for the limited compositional variation that they define on the basis of whole-rock chemistry, whereas similar to 45 vol.% crystals in a matrix of high-silica rhyolite glass together span a large range of mineral-scale isotopic variability ( microns to millimetres). Rb/Sr isotopic analyses of single crystals (sanidine, plagioclase, biotite, hornblende, apatite, titanite) and sampling by micromilling of selected zones within glass plus sanidine and plagioclase crystals document widespread isotopic disequilibrium at many scales. High and variable 87 Sr/ 86 Sr i values for euhedral biotite grains cannot be explained by any model involving closed-system radiogenic ingrowth, and they are difficult to rationalize unless much of this radiogenic Sr has been introduced at a late stage via assimilation of local Proterozoic crust. Hornblende is the only phase that approaches isotopic equilibrium with the surrounding melt, but the melt ( glass) was isotopically heterogeneous at the millimetre scale, and was therefore apparently contaminated with radiogenic Sr shortly prior to eruption. The other mineral phases (plagioclase, sanidine, titanite, and apatite) have significantly lower 87 Sr/ 86 Sr i values than whole-rock values ( as much as - 0.0005). Such isotopic disequilibrium implies that feldspars, titanite and apatite are antecrysts that crystallized from less radiogenic melt compositions at earlier stages of magma evolution, whereas highly radiogenic biotite xenocrysts and the development of isotopic heterogeneity in matrix melt glass appear to coincide with the final stage of the evolution of the Fish Canyon magma body in the upper crust. Integrated petrographic and geochemical evidence is consistent with pre- eruptive thermal rejuvenation of a near-solidus mineral assemblage from similar to 720 to 760 oC (i.e. partial dissolution of feldspars+quartz while hornblende+titanite+biotite were crystallizing). Assimilation and blending of phenocrysts, antecrysts and xenocrysts reflects chamber-wide, low Reynolds number convection that occurred within the last ~10 000 years before eruption.

Radiogenic isotope ratios can be used as a kind of petrogenetic "DNA" to identify the source components of magmas. Technical advances allowing us to measure isotopic compositions at the sub-crystal scale have led to the realisation that many magmatic rocks are isotopically heterogeneous. Crystals traditionally regarded as phenocrysts grown from the host magma have now been shown to be wholly or partly out of isotopic equilibrium with the glass or groundmass in which they are contained. Many of these crystals are likely to be recycled from earlier cumulates. Combining these fingerprinting techniques with the other approaches described in this issue offers an unprecedented opportunity to understand the processes and timescales through which magmas are assembled, differentiated and delivered to sites of eruption or emplacement.

RECEIVED SEPTEMBER 20, 2005; ACCEPTED JUNE 14, 2006;ADVANCE ACCESS PUBLICATION JULY 14, 2006Rhyolite pumices and co-erupted granophyric (granite) xenolithsyield evidence for rapid magma generation and crystallization priorto their eruption at 15.2±2.9 ka at the Alid volcanic center inthe Danikil Depression, Eritrea. Whole-rock U and Th isotopicanalyses show

The caldera-forming 26•5 ka Oruanui eruption (Taupo, New Zealand) erupted ~530 km3 of magma, >99% rhyolitic

Young (

The timescales over which moderate to large bodies of silicic magma are generated and stored are addressed here by studies of two geographically adjacent, successive eruption deposits in the Taupo Volcanic Zone, New Zealand. The earlier, caldera-forming Rotoiti eruption (>100 km3 magma) at Okataina volcano was followed, within months at most, by the Earthquake Flat eruption (∼10 km3 magma) from nearby Kapenga volcano; both generated non-welded ignimbrite and coeval widespread fall deposits. The Rotoiti and Earthquake Flat deposits are both crystal-rich high-silica rhyolites, with sparse glass-bearing granitoid fragments also occurring in Rotoiti lag breccias generated during caldera collapse. Here we report 238U–230Th disequilibrium data on whole rocks and mineral separates from representative Rotoiti and Earthquake Flat pumices and the co-eruptive Rotoiti granitoid fragments using TIMS and in situ zircon analyses by SIMS. Multiple-grain zircon-controlled crystallisation ages measured by TIMS from the Rotoiti pumice range from 69±3 ka ( 350 ka, with a pronounced peak at 70–90 ka. The weighted mean of isochrons is 83±14 ka, in accord with the TIMS data. One glass-bearing Rotoiti granitoid clast yielded an age of 57±8 ka by TIMS (controlled by Th-rich phases that, however, are not apparently present in the juvenile pumices). Another glass-bearing Rotoiti granitoid yielded SIMS zircon model ages peaking at 60–90 ka, having a similar age distribution to the pumice. Age data from pumices are consistent with a published 64±4 ka eruptive age (now modified to 62±2 ka), but chemical and/or mineralogical data imply that the granitoid lithics are not largely crystalline Rotoiti rhyolite, but instead represent contemporaneous partly molten intrusions reflecting different sources in their chemistries and mineralogies. Similarly, although the Earthquake Flat eruption immediately followed (and probably was triggered by) the Rotoiti event, age data from juvenile material are significantly different. A multiple-grain zircon-controlled crystallisation age measured by TIMS from a representative pumice is 173±5 ka, while SIMS model ages range from 70−26+34 ka to >350 ka, with a peak at 105 ka. These age data coupled with previously published geochemical and isotopic data show that the Rotoiti and Earthquake Flat deposits were erupted from independent, unconnected magma bodies.

Mangakino, the oldest rhyolitic caldera centre delineated in the Taupo Volcanic Zone of New Zealand, generated two very large (super-sized) ignimbrite eruptions, the 1.21 ± 0.04 Ma >500 km3 Ongatiti and ~1.0 Ma ~1,200 km3 Kidnappers events, the latter of which was followed after a short period of erosion by the ~200 km3 Rocky Hill eruption. We present U/Pb ages and trace-element analyses on zircons from pumice clasts from these three eruptions by Secondary Ion Mass Spectrometry (SIMS) using SHRIMP-RG instruments to illustrate the evolution of the respective magmatic systems. U–Pb age spectra from the Ongatiti imply growth of the magmatic system over ~250 kyr, with a peak of crystallisation around 1.32 Ma, ~100 kyr prior to eruption. The zircons are inferred to have then remained stable in a mush with little crystallisation and/or dissolution before later rejuvenation of the system at the lead-in to eruption. The paired Kidnappers and Rocky Hill eruptions have U–Pb zircon ages and geochemical signatures that suggest they were products of a common system grown over ~200 kyr. The Kidnappers and Rocky Hill samples show similar weakly bimodal age spectra, with peaks at 1.1 and 1.0 Ma, suggesting that an inherited antecrystic population was augmented by crystals grown at ages within uncertainty of the eruption age. In the Kidnappers, this younger age peak is dominantly seen in needle-shaped low U grains with aspect ratios of up to 18. In all three deposits, zircon cores show larger ranges and higher absolute concentrations of trace elements than zircon rims, consistent with zircon crystallisation from evolving melts undergoing crystal fractionation involving plagioclase and amphibole. Abundances and ratios of many trace elements frequently show variations between different sectors within single grains, even where there is no visible sector zoning in cathodoluminescence (CL) imaging. Substitution mechanisms, as reflected in the molar (Sc + Y + REE3+)/P ratio, differ in the same growth zone between the sides (along a-axis and b-axis: values approaching 1.0) and tips (c-axis: values between 1.5 and 5.0) of single crystals. These observations have implications for the use of zircons for tracking magmatic processes, particularly in techniques where CL zonation within crystals is not assessed and small analytical spot sizes cannot be achieved. These observations also limit applicability of the widely used Ti-in-zircon thermometer. The age spectra for the Ongatiti and Kidnappers/Rocky Hill samples indicate that both magmatic systems were newly built in the time-breaks after respective previous large eruptions from Mangakino. Trace element variations defining three-component mixing suggest that zircons, sourced from multiple melts, contributed to the population in each system.

Mineral isochron dating is a frequently used geochronological tool. One of its assumptions is that the minerals grow over a time period that is small compared to the half-life of the radiogenic isotope system used. In recent years, increasing analytical precision has promoted the use of the short-lived U-series isotope system in order to date young crystallisation events. Three whole-rock zircon U–Th isochrons from the 26.5 ka Oruanui eruption in the Taupo Volcanic Zone, New Zealand, yield pre-eruptive model ages of 5.5±0.8 ka, 9.7±1.7 ka and 12.3±0.8 ka for the sub-63 μm, 63–125 μm and 125–250 μm zircon size fractions, respectively. This suggests that in this case the assumption of instantaneous crystal growth breaks down. Instead, the U–Th data may be explained by continuous zircon growth over a period of ∼90 ka. However, cathodoluminescence shows that crystals are typically composed of an euhedral core surrounded by a sector-zoned euhedral rim, and the U–Th data can also be modelled by mixing an older (∼27 ka model age) population of zircon crystals with a young zircon rim that formed shortly prior to eruption of the Oruanui rhyolite. This indicates that detailed petrographic studies are critical for deciphering the histories of prolonged crystallisation in the magmatic environment. It is concluded that conventional U-series mineral isochrons may underestimate the age of the onset of crystallisation by more than an order of magnitude. In future, microanalytical techniques will lead to significant advances in the understanding of crystallisation processes and timescales.

Taupo volcanic centre has been active for c. 300 000 years. Since the c. 26.5 ka caldera‐forming Oruanui eruption 28 eruptions have occurred from Taupo, varying between 0.1 and >45 km 3 in minimum bulk volume, and with repose periods ranging from c. 20 to 6000 years. All magma erupted post‐26.5 ka is compositionally and mineralogically distinct from pre‐Oruanui and Oruanui eruptives, and is inferred to have formed at or after 26.5 ka. Four post‐Oruanui magma types are identified on the basis of whole rock and mineral compositions: one dacitic, forming three eruptions between 20.5 ka and 17 ka, and three subtly distinct rhyolite compositions erupted in discrete periods from 11.8 to 9.95, 7.05 to 2.75 and 2.15 to 1.74 ka. Stepwise compositional variations between, and limited variation within, rhyolite groups suggest emplacement of three petrogenetically separate batches of magma within only 10 000 years. The 15–35 km 3 of magma erupted at 1.77 ka evidently appeared in 3 years; this short residence time may have contributed to the lack of zonation within this magma chamber. Taupo is unusual amongst large rhyolite volcanoes in terms of the high frequency of activity since 26.5 ka, rapid stepwise changes in rhyolite compositions, and insignificant differentiation within individual subgroups. These traits are attributed to the combined effects of the extensional arc setting, thermal energy from mafic magma, and the shallow slope of the plagioclase‐saturated rhyolite liquidus.

International audience; Isotopic fingerprinting has long been used to trace magmatic processes and the components that contribute to magmas. Recent technological improvements have provided an opportunity to analyze isotopic compositions on the scale of individual crystals, and consequently to integrate isotopic and geochemical tracing with textural and petrographic observations. It has now become clear that mineral phases are commonly not in isotopic equilibrium with their host glass/groundmass. Isotopic ratios recorded from core to rim of a mineral grain reflect the progressive changes in the magma composition from which the mineral crystallized. The sense of these changes and the relationship between isotopic composition and petrographic features, such as dissolution surfaces, can be used to constrain magma evolution pathways involving open system processes such as magma mixing, contamination and recharge.

Isotope ratios of elements such as Sr, Nd, Pb and Hf can be used as tracers of magmatic sources and processes. Analytical capabilities have evolved so that isotope ratios can now be analysed in situ, and isotopic tracers can therefore be used within single minerals to track the changing magmatic environment in which a given mineral grew. This contribution shows that Sr isotope ratios in feldspars that make up plutonic rocks will typically preserve initial isotopic variations, provided precise and accurate age corrections can be applied. Variations in initial isotope ratio can give a core-to-rim record of magmatic evolution and can be used to diagnose open system events such as contamination and magma recharge and mixing.New single grain Sr isotope data are presented from the Dais Intrusion, Antarctica, which reflect an open system origin for the crystals. The crystal cargo appears to be aggregated and assembled during transport and emplacement. This model, as opposed to a magma body crystallising post emplacement, may be more applicable to plutonic rocks in general, and is testable using the in situ isotopic determination methods described here.

There is lively debate on whether Asian plate material was involved in southward flow of mid-lower crust in a ductile channel beneath southern Tibet. One argument against such involvement is the apparent absence of material derived from Asian lithosphere within the High Himalayan Series (Indian plate) that could represent the putative channel. A north-south–trending mid-Miocene dike swarm that intrudes the Tethyan sedimentary cover of the Sakya gneiss dome (Indian plate) yields new Sr-Nd isotopic data (87Sr/86Sr = 0.7071–0.7079; ϵNd −4 to −6) indicating that these melts share the same source as Miocene dacitic dikes from north of the Indus-Tsangpo suture. Moreover, dikes on both sides of this suture represent crustal melts derived largely from mid-lower crust of the Asian plate, exposed today as the Nyainqentanglha gneisses that underlie the Gangdese batholith. We infer that melting of the Asian lithosphere extended south of the surface trace of the suture, requiring southward propagation of anatectic Asian middle crustal material during the Miocene. The emplacement ages of the southern dike swarm (12–9 Ma) thus delimit the timing of active southward ductile flow of Asian material.

In contrast to most large-volume silicic magmas in continental arcs, which are thought to evolve as open systems with significant assimilation of preexisting crust, the Kos Plateau Tuff magma formed dominantly by crystal fractionation of mafic parents. Deposits from this ∼60 km3 pyroclastic eruption (the largest known in the Aegean arc) lack xenocrystic zircons [secondary ion mass spectrometry (SIMS) U-Pb ages on zircon cores never older than 500 ka] and display Sr-Nd whole-rock isotopic ratios within the range of European mantle in an area with exposed Paleozoic and Tertiary continental crust; this evidence implies a nearly closed-system chemical differentiation. Consequently, the age range provided by zircon SIMS U-Th-Pb dating is a reliable indicator of the duration of assembly and longevity of the silicic magma body above its solidus. The age distribution from 160 ka (age of eruption by sanidine 40Ar/39Ar dating; [Smith et al., 1996][1]) to ca. 500 ka combined with textural characteristics (high crystal content, corrosion of most anhydrous phenocrysts, but stability of hydrous phases) suggest (1) a protracted residence in the crust as a crystal mush and (2) rejuvenation (reduced crystallization and even partial resorption of minerals) prior to eruption probably induced by new influx of heat (and volatiles). This extended evolution chemically isolated from the surrounding crust is a likely consequence of the regional geodynamics because the thinned Aegean microplate acts as a refractory container for magmas in the dying Aegean subduction zone (continent-continent subduction). [1]: #ref-32

The determination of accurate and precise isochron ages for igneous rocks requires that the initial isotope ratios of the analyzed minerals are identical at the time of eruption or emplacement. Studies of young volcanic rocks at the mineral scale have shown this assumption to be invalid in many instances. Variations in initial isotope ratios can result in erroneous or imprecise ages. Nevertheless, it is possible for initial isotope ratio variation to be obscured in a statistically acceptable isochron. Independent age determinations and critical appraisal of petrography are needed to evaluate isotope data. If initial isotope ratio variability can be demonstrated, however, it can be used to constrain petrogenetic pathways.