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Ilya N. Bindeman

Publications and source records attributed to Ilya N. Bindeman.

16 recordsLinked to original sources

Rhenium-osmium and oxygen isotope homogeneity during the 2022 Mauna Loa eruption and implications for basaltic magma storage

Mauna Loa is one of the largest and most active volcanoes on Earth. The most recent eruption of Mauna Loa started on 27 November 2022, lasted for 13 days, and was preceded by the longest repose time of 38 years in its modern history. In this contribution, new trace- and highly siderophile-element (HSE: Os, Ir, Ru, Pt, Pd, Re) abundances, 187 Re- 187 Os, and 18 O/ 16 O data are reported for the 2022 lavas. These lavas have a limited range of MgO (6.2 ± 0.1 wt.%) and Ni (83 ± 2 µg/g), with a broader range of Re (0.3 to 1.3 ng/g) and consistent Os (0.031 to 0.080 ng/g) contents. They have 187 Os/ 188 Os ratios (0.1345 to 0.1385) which are, on average, more radiogenic than Mauna Loa picrites (0.1331 to 0.1349) and are similar in composition to more differentiated Mauna Loa tholeiite lavas (0.1340 to 0.1381). The oxygen isotope compositions of glassy samples are 5.35 ± 0.15‰ ( n = 13) and span a range in δ 18 O of + 5.0 to + 5.5‰, with an average composition 0.2 to 0.3‰ lower than MORB. The δD value is − 81 ± 11‰ ( n = 5) at very low (0.03 ± 0.015 wt.%) H 2 O concentrations. The 2022 Mauna Loa eruption is similar in terms of δ 18 O but contrasts in terms of 187 Os/ 188 Os variability, with the recent longer-lived eruptions on La Palma (Canary Islands; 85 days) in 2021 and on the Reykjanes Peninsula (Iceland) that began in 2021 and are still ongoing. Initial lavas were more fractionated for both the Canary Islands and Iceland eruptions, producing more radiogenic Os isotope compositions than later erupted products. The 2022 Mauna Loa eruption showed no such trends. The limited range in isotope compositions of the 2022 Mauna Loa lavas and their strongly fractioned HSE patterns reflect long-term storage, crystal fractionation, and assimilation of related basaltic volcanic edifice materials by the parent magma beneath the volcano prior to eruption triggering. Eruption of differentiated and homogeneous tholeiite lavas at the summit caldera and high on the volcano’s flank, with emplacement of accumulative picrites lower on the volcano, are consistent with neutral buoyancy arguments.

Hawaii

Geochemical and geochronologic evidence for a contiguous northeastern Wyoming Province

The extent and nature of the Wyoming Province, an Archean craton in southwestern Laurentia, are poorly understood due to limited exposure between spatially isolated basement-cored uplifts. This lack of exposure has led to debate about whether the northeastern Wyoming Province is underlain by contiguous Archean crust or Proterozoic rocks and suture zone associated with the Trans-Hudson orogeny. To assess these models we analyzed samples recovered from drill cores in the buried northeastern Wyoming Province that straddle the proposed Proterozoic suture. Whole-rock geochemical and Nd-Pb-O isotopic data suggest the rocks formed by partial melting of > 3.5 Ga hydrated mafic to tonalitic sources similar to elsewhere in the northern Wyoming Province. Zircon U-Pb dates record Mesoarchean magmatism and metamorphism (3.0–2.8 Ga). Published whole-rock Rb-Sr, hornblende and biotite K-Ar, and apatite fission track dates suggest these rocks have not been heated above 300 °C since 2.5–2.1 Ga. Geophysical potential field data are consistent across northeastern Wyoming contrasting with major discontinuities associated with documented Proterozoic orogens on all other margins of the Wyoming Province. Hence, geochemical, isotopic, and geochronologic data along with geophysical imaging can be most simply interpreted in terms of continuous Archean crust in the northeastern Wyoming Province. A geophysically-imaged reflector east of the Bighorn Mountains may juxtapose Archean terranes with similar ages and sources, similar to the boundary between the Montana metasedimentary terrane and Beartooth-Bighorn magmatic zone in the northwestern Wyoming Province. This work emphasizes the value of integrating geologic and geophysical constraints to constrain Archean provinces and their tectonic evolution.

Colorado, Idaho, Montana, Nebraska, North Dakota,

Hydrogen isotope behavior during rhyolite glass hydration under hydrothermal conditions

The diffusion of molecular water (H 2 O m ) from the environment into volcanic glass can hydrate the glass up to several wt% at low temperature over long timescales. During this process, the water imprints its hydrogen isotope composition (δD H2O ) to the glass (δD gl ) offset by a glass-H 2 O fractionation factor (ΔD gl-H2O = δD gl – δD H2O ) which is approximately −33‰ at Earth surface temperatures. Glasses hydrate much more rapidly at higher, sub-magmatic temperatures as they interact with H 2 O during eruption, transport, and emplacement. To aid in the interpretation of δD gl in natural samples, we present hydrogen isotope results from vapor hydration experiments conducted at 175–375 °C for durations of hours to months using natural volcanic glasses. The results can be divided into two thermal regimes: above 250 °C and below 250 °C. Lower temperature experiments yield raw ΔD gl-H2O values in the range of −33 ± 11‰. Experiments at 225 °C using both positive and negative initial ΔD gl-H2O values converge on this range of values, suggesting this range represents the approximate equilibrium fractionation for H isotopes between glass and H 2 O vapor (10 3 lnα gl-H2O ) below 250 °C. Variation in ΔD gl-H2O (−33 ± 11‰) between different experiments and glasses may arise from incomplete hydration, analytical uncertainty, differences in glass chemistry, and/or subordinate kinetic isotope effects. Experiments above 250 °C yield unexpectedly low δD gl values with ΔD gl-H2O values of ≤–85‰. While alteration alone is incapable of explaining the data, these run products have more extensive surface alteration and are not interpreted to reflect equilibrium fractionation between glass and H 2 O vapor. Fourier transform infrared spectroscopy (FTIR) shows that glass can hydrate with as much as 5.9 wt% H 2 O m and 1.0 wt% hydroxl (OH − ) in the highest P-T experiment at 375 °C and 21.1 MPa. Therefore, we employ a 1D isotope diffusion–reaction model of glass hydration to evaluate the roles of equilibrium fractionation, isotope diffusion, water speciation reactions internal to the glass, and changing boundary conditions (e.g. alteration and dissolution). At lower temperatures, the best fitting model results to experimental data for low silica rhyolite (LSR) glasses require only an equilibrium fractionation factor and yield 10 3 lnα gl-H2O values of −33‰ ± 5‰ and −25‰ ± 5‰ at 175 °C and 225 °C, respectively. At higher temperatures, ΔD gl-H2O is dominated by boundary layer effects during glass hydration and glass surface alteration. The modeled bulk δD gl value is highly responsive to changes in the δD gl boundary condition regardless of the magnitude of other kinetic effects. Observed glass dissolution and surficial secondary mineral formation are likely to impose a disequilibrium boundary layer that drives extreme δD gl fractionation with progressive glass hydration. These results indicate that the observed ΔD gl-H2O of ∼−33 ± 11‰ can be cautiously applied as an equilibrium 10 3 lnα gl-H2O value to natural silicic glasses hydrated below 250 °C to identify hydration sources. This approximate ΔD gl-H2O may be applicable to even higher temperature glasses hydrated on short timescales (of seconds to minutes) in phreatomagmatic or submarine eruptions before H 2 O in the glass is primarily affected by boundary layer effects associated with alteration on the glass surface.

Geochimica et Cosmochimica Acta

Syn-eruptive hydration of volcanic ash records pyroclast-water interaction in explosive eruptions

Magma-water interaction can dramatically influence the explosivity of volcanic eruptions. However, syn- and post-eruptive diffusion of external (non-magmatic) water into volcanic glass remains poorly constrained and may bias interpretation of water in juvenile products. Hydrogen isotopes in ash from the 2009 eruption of Redoubt Volcano, Alaska, record syn-eruptive hydration by vaporized glacial meltwater. Both ash aggregation and hydration occurred in the wettest regions of the plume, which resulted in the removal and deposition of the most hydrated ash in proximal areas <50 km from the vent. Diffusion models show that the high temperatures of pyroclast-water interactions (>400°C) are more important than the cooling rate in facilitating hydration. These observations suggest that syn-eruptive glass hydration occurred where meltwater was entrained at high temperature, in the plume margins near the vent. Ash in the drier plume interior remained insulated from entrained meltwater until it cooled sufficiently to avoid significant hydration.

Geophysical Research Letters

Oxygen isotopic investigation of silicic magmatism in the Stillwater caldera complex, Nevada: Generation of large-volume, low-δ18O rhyolitic tuffs and assessment of their regional context in the Great Basin of the western United States

Successive caldera-forming eruptions from ca. 30 to 25 Ma generated a large nested caldera complex in western Nevada that was subsequently dissected by Basin and Range extension, providing extraordinary cross-sectional views through diverse volcanic and plutonic rocks. A high-resolution oxygen isotopic study was conducted on units that represent all major parts of the Job Canyon, Louderback Mountains, Poco Canyon, and Elevenmile Canyon caldera cycles (29.2−25.1 Ma), and several Cretaceous plutons that flank the Stillwater caldera complex. We provide new oxygen and strontium isotope data for 12 additional caldera centers in the Great Basin, which are synthesized with >150 published oxygen and strontium isotope analyses for regional Mesozoic basement rocks. Stillwater zircons span a large isotopic range (δ 18 O zircon of 3.6‰−8.2‰), and all caldera cycles possess low-δ 18 O zircons. In some cases, they are a small proportion of the total populations, and in others, they dominate, such as in the low-δ 18 O rhyolitic tuffs of Job Canyon and Poco Canyon (δ 18 O zircon = 4.0‰−4.3‰; δ 18 O magma = 5.5‰−6‰). These are the first low-δ 18 O rhyolites documented in middle Cenozoic calderas of the Great Basin, adding to the global occurrence of these important magma types that fingerprint recycling of shallow crust altered by low-δ 18 O meteoric waters. The appearance of low-δ 18 O rhyolites in the Stillwater caldera complex is overprinted on a Great Basin−wide trend of miogeoclinal sediment contribution to silicic magmas that elevates δ 18 O compositions, making identification of 18 O depletions difficult. Though not a nominally low-δ 18 O rhyolite, the tuff of Elevenmile Canyon possesses both low-δ 18 O and high-δ 18 O zircon cores that are overgrown by homogenized zircon rims that approximate the bulk zircon average, pointing to batch assembly of isotopically diverse upper crustal melts to generate one of the most voluminous (2500−5000 km 3 ) tuff eruptions in the Great Basin. Despite overlapping in space and time, each caldera-forming cycle of the Stillwater complex has a unique oxygen isotope record as retained in single zircons. Most plutons that were spatially and temporally coincident with calderas have isotopic compositions that diverge from the caldera-forming tuffs and cannot be their cogenetic remnants.

Nevada

Isotopic and petrologic investigation, and a thermomechanical model of genesis of large-volume rhyolites in arc environments: Karymshina Volcanic Complex, Kamchatka, Russia

The Kamchatka Peninsula of eastern Russia is currently one of the most volcanically active areas on Earth where a combination of >8 cm/yr subduction convergence rate and thick continental crust generates large silicic magma chambers, reflected by abundant large calderas and caldera complexes. This study examines the largest center of silicic 4-0.5 Ma Karymshina Volcanic Complex, which includes the 25 × 15 km Karymshina caldera, the largest in Kamchatka. A series of rhyolitic tuff eruptions at 4 Ma were followed by the main eruption at 1.78 Ma and produced an estimated 800 km 3 of rhyolitic ignimbrites followed by high-silica rhyolitic post-caldera extrusions. The postcaldera domes trace the 1.78 Ma right fracture and form a continuous compositional series with ignimbrites. We here present results of a geologic, petrologic, and isotopic study of the Karymshina eruptive complex, and present new Ar-Ar ages, and isotopic values of rocks for the oldest pre- 1.78 Ma caldera ignimbrites and intrusions, which include a diversity of compositions from basalts to rhyolites. Temporal trends in δ 18 O, 87 Sr/ 86 Sr, and 144 Nd/ 143 Nd indicate values comparable to neighboring volcanoes, increase in homogeneity, and temporal increase in mantle-derived Sr and Nd with increasing differentiation over the last 4 million years. Data are consistent with a batholithic scale magma chamber formed by primarily fractional crystallization of mantle derived composition and assimilation of Cretaceous and younger crust, driven by basaltic volcanism and mantle delaminations. All rocks have 35–45% quartz, plagioclase, biotite, and amphibole phenocrysts. Rhyolite-MELTS crystallization models favor shallow (2 kbar) differentiation conditions and varying quantities of assimilated amphibolite partial melt and hydrothermally-altered silicic rock. Thermomechanical modeling with a typical 0.001 km 3 /yr eruption rate of hydrous basalt into a 38 km Kamchatkan arc crust produces two magma bodies, one near the Moho and the other engulfing the entire section of upper crust. Rising basalts are trapped in the lower portion of an upper crustal magma body, which exists in a partially molten to solid state. Differentiation products of basalt periodically mix with the resident magma diluting its crustal isotopic signatures. At the end of the magmatism crust is thickened by 8 km. Thermomechanical modeling show that the most likely way to generate large spikes of rhyolitic magmatism is through delamination of cumulates and mantle lithosphere after many millions of years of crustal thickening. The paper also presents a chemical dataset for Pacific ashes from ODDP 882 and 883 and compares them to Karymshina ignimbrites and two other Pleistocene calderas studied by us in earlier works.

Kamchatka

Hydrogen isotopes in high 3He/4He submarine basalts: Primordial vs. recycled water and the veil of mantle enrichment

The hydrogen isotope value ( δ D) of water indigenous to the mantle is masked by the early degassing and recycling of surface water through Earth's history. High 3 He/ 4 He ratios in some ocean island basalts, however, provide a clear geochemical signature of deep, primordial mantle that has been isolated within the Earth's interior from melting, degassing, and convective mixing with the upper mantle. Hydrogen isotopes were measured in high 3 He/ 4 He submarine basalt glasses from the Southeast Indian Ridge (SEIR) at the Amsterdam–St. Paul (ASP) Plateau ( δ D = −51 to −90‰, 3 He/ 4 He = 7.6 to 14.1 R A ) and in submarine glasses from Loihi seamount south of the island of Hawaii ( δ D = −70 to −90‰, 3 He/ 4 He = 22.5 to 27.8 R A ). These results highlight two contrasting patterns of δ D for high 3 He/ 4 He lavas: one trend toward high δ D of approximately −50‰, and another converging at δ D = −75‰. These same patterns are evident in a global compilation of previously reported δ D and 3 He/ 4 He results. We suggest that the high δ D values result from water recycled during subduction that is carried into the source region of mantle plumes at the core–mantle boundary where it is mixed with primordial mantle, resulting in high δ D and moderately high 3 He/ 4 He. Conversely, lower δ D values of −75‰, in basalts from Loihi seamount and also trace element depleted mid-ocean ridge basalts, imply a primordial Earth hydrogen isotopic value of −75‰ or lower. δ D values down to −100‰ also occur in the most trace element-depleted mid-ocean ridge basalts, typically in association with 87 Sr/ 86 Sr ratios near 0.703. These lower δ D values may be a result of multi-stage melting history of the upper mantle where minor D/H fractionation could be associated with hydrogen retention in nominally anhydrous residual minerals. Collectively, the predominance of δ D around −75‰ in the majority of mid-ocean ridge basalts and in high 3 He/ 4 He Loihi basalts is consistent with an origin of water on Earth that was dominated by accretion of chondritic material.

Earth and Planetary Science Letters

Isotopic insights into the degassing and secondary hydration of volcanic glass from the 1980 eruptions of Mount St. Helens

The magmatic degassing history of newly erupted volcanic glass is recorded in its remaining volatile content. However, this history is subsequently overprinted by post-depositional (secondary) hydration, the rates and origins of which are not yet adequately constrained. Here, we present the results of a natural experiment using products of the 1980 eruptions of Mount St. Helens. We measured water concentration, δD glass , and δ 18 O BSG (δ 18 O of the bulk silicate glass) of samples collected during the dry summer months of 1980 and compared them with material resampled in 2015 from the same deposits. Samples collected from the subsurface near gas escape pipes show elevated water concentrations (near 2.0 wt%), and these are associated with lower δD glass (− 110 to − 130‰) and δ 18 O BSG (6.0 to 6.6‰) values than the 1980 glass (− 70 to − 100‰ and 6.8 to 6.9‰, respectively). Samples collected in 2015 from the surface to 10-cm subsurface of the 1980 summer deposits have a small increase in average water contents of 0.1–0.2 wt% but similar δ 18 O BSG (6.8–6.9‰) values compared to the 1980 glass values. These samples, however, show 15‰ higher δD glass values; exchange with meteoric water is expected to yield lower δD glass values. We attribute higher δD glass values in the upper portion of the 1980 deposits collected in 2015 to rehydration by higher δD waters that were degassed for several months to a year from the hot underlying deposits, which hydrated the overlying deposits with relatively high δD gases. Our data also contribute to magmatic degassing of crystal-rich volcanoes. Using the 1980 samples, our reconstructed δD-H 2 O trends for the dacitic Mount St. Helens deposits with rhyolitic groundmass yield a trend that overlaps with the degassing trend for crystal-poor rhyolitic eruptions studied previously elsewhere, suggesting similar behavior of volatiles upon exsolution from magma. Furthermore, our data support previous studies proposing that exsolved volatiles were trapped within a rapidly rising magma and started degassing only at shallow depths during the 1980 eruptions.

Washington

Opal-A in glassy pumice, acid alteration, and the 1817 phreatomagmatic eruption at Kawah Ijen (Java), Indonesia

At Kawah Ijen (Indonesia), vigorous SO 2 and HCl degassing sustains a hyperacid lake (pH ~0) and intensely alters the subsurface, producing widespread residual silica and advanced argillic alteration products. In 1817, a VEI 2 phreatomagmatic eruption evacuated the lake, depositing a widespread layer of muddy ash fall, and sending lahars down river drainages. We discovered multiple types of opaline silica in juvenile low-silica dacite pumice and in particles within co-erupted laharic sediments. Most spectacular are opal-replaced phenocrysts of plagioclase and pyroxene adjacent to pristine matrix glass and melt inclusions. Opal-bearing pumice has been found at numerous sites, including where post-eruption infiltration of acid water is unlikely. Through detailed analyses of an initial sampling of 1817 eruption products, we find evidence for multiple origins of opaline materials in pumice and laharic sediments. Evidently, magma encountered acid-altered materials in the subsurface and triggered phreatomagmatic eruptions. Syn-eruptive incorporation of opal-alunite clasts, layered opal, and fragment-filled vesicles of opal and glass, all suggest magma-rock interactions in concert with vesiculation, followed by cooling within minutes. Our experiments at magmatic temperature confirm that the opaline materials would show noticeable degradation in time periods longer than a few tens of minutes. Some glassy laharic sedimentary grains are more andesitic than the main pumice type and may represent older volcanic materials that were altered beneath the lake bottom and were forcefully ejected during the 1817 eruption. A post-eruptive origin remains likely for most of the opal-replaced phenocrysts in pumice. Experiments at 25°C and 100°C reveal that when fresh pumice is bathed in Kawah Ijen hyperacid fluid for 6 weeks, plagioclase is replaced without altering either matrix glass or melt inclusions. Moreover, lack of evidence for high-temperature annealing of the opal suggests that post-eruption alteration of pumice is more likely than pre-eruption envelopment of euhedral opal-replaced phenocrysts in dacitic melt. At Ijen and elsewhere, the ascent of magma into hydrous acid-altered mineral assemblages (e.g., opal, kaolinite, alunite) could induce rapid dehydration of hydrous minerals and amorphous materials, generating considerable steam and contributing to magmatic-hydrothermal and phreatomagmatic explosions.

Kawah Ijen

A field trip guide to the petrology of Quaternary volcanism on the Yellowstone Plateau

The Yellowstone Plateau is one of the largest manifestations of silicic volcanism on Earth, and marks the youngest focus of magmatism associated with the Yellowstone Hot Spot. The earliest products of Yellowstone Hot Spot volcanism are from ~17 million years ago, but may be as old as ~32 Ma, and include contemporaneous eruption of voluminous mafic and silicic magmas, which are mostly located in the region of northwestern Nevada and southeastern Oregon. Since 17 Ma, the main locus of Yellowstone Hot Spot volcanism has migrated northeastward producing numerous silicic caldera complexes that generally remain active for ~2–4 million years, with the present-day focus being the Yellowstone Plateau. Northeastward migration of volcanism associated with the Yellowstone Hot Spot resulted in the formation of the Snake River Plain, a low relief physiographic feature extending ~750 kilometers from northern Nevada to eastern Idaho. Most of the silicic volcanic centers along the Snake River Plain have been inundated by younger basalt volcanism, but many of their ignimbrites and lava flows are exposed in the extended regions at the margins of the Snake River Plain .

Wyoming

New biotite and muscovite isotopic reference materials, USGS57 and USGS58, for δ2H measurements–A replacement for NBS 30

The advent of continuous-flow isotope-ratio mass spectrometry (CF-IRMS) coupled with a high temperature conversion (HTC) system enabled faster, more cost effective, and more precise δ 2 H analysis of hydrogen-bearing solids. Accurate hydrogen isotopic analysis by on-line or off-line techniques requires appropriate isotopic reference materials (RMs). A strategy of two-point calibrations spanning δ 2 H range of the unknowns using two RMs is recommended. Unfortunately, the supply of the previously widely used isotopic RM, NBS 30 biotite, is exhausted. In addition, recent measurements have shown that the determination of δ 2 H values of NBS 30 biotite on the VSMOW-SLAP isotope-delta scale by on-line HTC systems with CF-IRMS may be unreliable because hydrogen in this biotite may not be converted quantitatively to molecular hydrogen. The δ 2 H VSMOW-SLAP values of NBS 30 biotite analyzed by on-line HTC systems can be as much as 21 mUr (or ‰) too positive compared to the accepted value of − 65.7 mUr, determined by only a few conventional off-line measurements. To ensure accurate and traceable on-line hydrogen isotope-ratio determinations in mineral samples, we here propose two isotopically homogeneous, hydrous mineral RMs with well-characterized isotope-ratio values, which are urgently needed. The U.S. Geological Survey (USGS) has prepared two such RMs, USGS57 biotite and USGS58 muscovite. The δ 2 H values were determined by both glassy carbon-based on-line conversion and chromium-based on-line conversion, and results were confirmed by off-line conversion. The quantitative conversion of hydrogen from the two RMs using the on-line HTC method was carefully evaluated in this study. The isotopic compositions of these new RMs with 1-σ uncertainties and mass fractions of hydrogen are: USGS57 (biotite) δ 2 H VSMOW-SLAP = − 91.5 ± 2.4 mUr ( n = 24) Mass fraction hydrogen = 0.416 ± 0.002% ( n = 4) Mass fraction water = 3.74 ± 0.02% ( n = 4) USGS58 (muscovite) δ 2 H VSMOW-SLAP = − 28.4 ± 1.6 mUr ( n = 24) Mass fraction hydrogen = 0.448 ± 0.002% ( n = 4) Mass fraction water = 4.03 ± 0.02% ( n = 4). These δ 2 H VSMOW-SLAP values encompass typical ranges for solid unknowns of crustal and mantle origin and are available to users for recommended two-point calibration.

Chemical Geology

Iron and oxygen isotope signatures of the Pea Ridge and Pilot Knob magnetite-apatite deposits, southeast Missouri, USA

New O and Fe stable isotope ratios are reported for magnetite samples from high-grade massive magnetite of the Mesoproterozoic Pea Ridge and Pilot Knob magnetite-apatite ore deposits and these results are compared with data for other iron oxide-apatite deposits to shed light on the origin of the southeast Missouri deposits. The δ 18 O values of magnetite from Pea Ridge ( n = 12) and Pilot Knob ( n = 3) range from 1.0 to 7.0 and 3.3 to 6.7‰, respectively. The δ 56 Fe values of magnetite from Pea Ridge ( n = 10) and Pilot Knob ( n = 6) are 0.03 to 0.35 and 0.06 to 0.27‰, respectively. These δ 18 O and the δ 56 Fe values suggest that magnetite crystallized from a silicate melt (typical igneous δ 56 Fe ranges 0.06–0.49‰) and grew in equilibrium with a magmatic-hydrothermal aqueous fluid. We propose that the δ 18 O and δ 56 Fe data for the Pea Ridge and Pilot Knob magnetite-apatite deposits are consistent with the flotation model recently proposed by Knipping et al. (2015a) , which invokes flotation of a magmatic magnetite-fluid suspension and offers a plausible explanation for the igneous (i.e., up to ~15.9 wt % TiO 2 in magnetite) and hydrothermal features of the deposits.

Economic Geology

Low-δD hydration rinds in Yellowstone perlites record rapid syneruptive hydration during glacial and interglacial conditions

Hydration of silicic volcanic glass forms perlite, a dusky, porous form of altered glass characterized by abundant “onion-skin” fractures. The timing and temperature of perlite formation are enigmatic and could plausibly occur during eruption, during post-eruptive cooling, or much later at ambient temperatures. To learn more about the origin of natural perlite, and to fingerprint the hydration waters, we investigated perlitic glass from several synglacial and interglacial rhyolitic lavas and tuffs from the Yellowstone volcanic system. Perlitic cores are surrounded by a series of conchoidal cracks that separate 30- to 100-µm-thick slivers, likely formed in response to hydration-induced stress. H 2 O and D/H profiles confirm that most D/H exchange happens together with rapid H 2 O addition but some smoother D/H variations may suggest separate minor exchange by deuterium atom interdiffusion following hydration. The hydrated rinds (2–3 wt% H 2 O) transition rapidly (within 30 µm, or by 1 wt% H 2 O per 10 µm) to unhydrated glass cores. This is consistent with quenched “hydration fronts” where H 2 O diffusion coefficients are strongly dependent on H 2 O concentrations. The chemical, δ 18 O, and δD systematics of bulk glass records last equilibrium between ~110 and 60 °C without chemical exchange but with some δ 18 O exchange. Similarly, the δ 18 O of water extracted from glass by rapid heating suggests that water was added to the glass during cooling at <200 °C. Our observations support fast hydration at temperatures as low as 60 °C; prolonged exposure to high temperature of 175°–225° during water addition is less likely as the glass would lose alkalies and should alter to clays within days. A compilation of low-temperature hydration diffusion coefficients suggests ~2 orders of magnitude higher rates of diffusion at 60–110 °C temperatures, compared with values expected from extrapolation of high-temperature (>400 °C) experimental data. The thick hydration rinds in perlites, measuring hundreds of microns, preserve the original D/H values of hydrating water as a recorder of paleoclimate conditions. Measured δD values in perlitic lavas are −150 to −191 or 20–40 ‰ lower than glass hydrated by modern Yellowstone waters. This suggests that Yellowstone perlites record the low-δD signature of glacial ice. Cooling calculations, combined with the observed high water diffusion coefficients noted for 60–150 °C, suggest that if sufficient hot water or steam is available, any rhyolite flow greater than ~5 m thick can develop the observed ~250-µm hydration rinds within the expected timescale of cooling (weeks–years). As the process of hydration involves shattering of 30- to 100-µm-thick slivers to expose unhydrated rhyolite glass, the time required for hydration may be even shorter. Rapid hydration and formation of relatively thick-walled glass shards allow perlites to provide a snapshot view of the meteoric water (and thus climate) at the time of initial alteration. Perlites retain their initial hydration D/H signal better than thin-walled ash, which in contrast hydrates over many thousands of years with time-averaged precipitation.

Contributions to Mineralogy and Petrology

Probing the volcanic-plutonic connection and the genesis of crystal-rich rhyolite in a deeply dissected supervolcano in the Nevada Great Basin: Source of the late Eocene Caetano Tuff

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

Journal of Petrology

Revised Wonoka isotopic anomaly in South Australia and Late Ediacaran mass extinction

The global Late Ediacaran Shuram–Wonoka carbon isotope anomaly has been regarded as the largest and longest known isotopic anomaly in the ocean, assuming that all Ediacaran carbonate is marine. Disregarding carbonate in South Australia shown here to be palaeosol or palaeokarst, the synchronous marine organic–carbonate excursion is only −8‰ for δ 13 C organic and −6‰ for δ 13 C carbonate, and lasted less than a million years. This revised magnitude and duration is comparable with perturbations across the Permian–Triassic boundary, and correlative with a global Late Ediacaran acritarch mass extinction. Like Permian–Triassic isotopic excursions, the revised organic–carbonate Wonoka excursion may also have been a greenhouse palaeoclimatic warm spike, which terminated valley incision and glacioeustatic drawdown during the mid-Ediacaran Fauquier Glaciation, and preceded chill of the Late Ediacaran Billy Springs Glaciation.

Flinders Ranges

Crustal-scale recycling in caldera complexes and rift zones along the Yellowstone hotspot track: O and Hf isotopic evidence in diverse zircons from voluminous rhyolites of the Picabo volcanic field, Idaho

Rhyolites of the Picabo volcanic field (10.4–6.6 Ma) in eastern Idaho are preserved as thick ignimbrites and lavas along the margins of the Snake River Plain (SRP), and within a deep (>3 km) borehole near the central axis of the Yellowstone hotspot track. In this study we present new O and Hf isotope data and U–Pb geochronology for individual zircons, O isotope data for major phenocrysts (quartz, plagioclase, and pyroxene), whole rock Sr and Nd isotope ratios, and whole rock geochemistry for a suite of Picabo rhyolites. We synthesize our new datasets with published Ar–Ar geochronology to establish the eruptive framework of the Picabo volcanic field, and interpret its petrogenetic history in the context of other well-studied caldera complexes in the SRP. Caldera complex evolution at Picabo began with eruption of the 10.44±0.27 Ma (U–Pb) Tuff of Arbon Valley (TAV), a chemically zoned and normal-δ 18 O (δ 18 O magma=7.9‰) unit with high, zoned 87 Sr/ 86 Sr i (0.71488–0.72520), and low-ε Nd (0) (−18) and ε Hf (0) (−28). The TAV and an associated post caldera lava flow possess the lowest ε Nd (0) (−23), indicating ∼40–60% derivation from the Archean upper crust. Normal-δ 18 O rhyolites were followed by a series of lower-δ 18 O eruptions with more typical (lower crustal) Sr–Nd–Hf isotope ratios and whole rock chemistry. The voluminous 8.25±0.26 Ma West Pocatello rhyolite has the lowest δ 18 O value (δ 18 O melt =3.3‰), and we correlate it to a 1,000 m thick intracaldera tuff present in the INEL-1 borehole (with published zircon ages 8.04–8.35 Ma, and similarly low-δ 18 O zircon values). The significant (4–5‰) decrease in magmatic-δ 18 O values in Picabo rhyolites is accompanied by an increase in zircon δ 18 O heterogeneity from ∼1‰ variation in the TAV to >5‰ variation in the late-stage low-δ 18 O rhyolites, a trend similar to what is characteristic of Heise and Yellowstone, and which indicates remelting of variably hydrothermally altered tuffs followed by rapid batch assembly prior to eruption. However, due to the greater abundance of low-δ 18 O rhyolites at Picabo, the eruptive framework may reflect an intertwined history of caldera collapse and coeval Basin and Range rifting and hydrothermal alteration. We speculate that the source rocks with pre-existing low-δ 18 O alteration may be related to: (1) deeply buried and unexposed older deposits of Picabo-age or Twin Falls-age low-δ 18 O volcanics; and/or (2) regionally-abundant late Eocene Challis volcanics, which were hydrothermally altered near the surface prior to or during peak Picabo magmatism. Basin and Range extension, specifically the formation of metamorphic core complexes exposed in the region, could have facilitated the generation of low-δ 18 O magmas by exhuming heated rocks and creating the large water-rock ratios necessary for shallow hydrothermal alteration of tectonically (rift zones) and volcanically (calderas) buried volcanic rocks. These interpretations highlight the major processes by which supereruptive volumes of magma are generated in the SRP, mechanisms applicable to producing rhyolites worldwide that are facilitated by plume driven volcanism and extensional tectonics.

Idaho