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Calcite growth-rate inhibition by fulvic acid and magnesium ion—Possible influence on biogenic calcite formation

Increases in ocean surface water dissolved carbon dioxide (CO2) concentrations retard biocalcification by reducing calcite supersaturation (Ωc). Reduced calcification rates may influence growth-rate dependent magnesium ion (Mg) incorporation into biogenic calcite modifying the use of calcifying organisms as paleoclimate proxies. Fulvic acid (FA) at biocalcification sites may further reduce calcification rates. Calcite growth-rate inhibition by FA and Mg, two common constituents of seawater and soil water involved in the formation of biogenic calcite, was measured separately and in combination under identical, highly reproducible experimental conditions. Calcite growth rates (pH=8.5 and Ωc=4.5) are reduced by FA (0.5 mg/L) to 47% and by Mg (10−4 M) to 38%, compared to control experiments containing no added growth-rate inhibitor. Humic acid (HA) is twice as effective a calcite growth-rate inhibitor as FA. Calcite growth rate in the presence of both FA (0.5 mg/L) and Mg (10−4 M) is reduced to 5% of the control rate. Mg inhibits calcite growth rates by substitution for calcium ion at the growth site. In contrast, FA inhibits calcite growth rates by binding multiple carboxylate groups on the calcite surface. FA and Mg together have an increased affinity for the calcite growth sites reducing calcite growth rates.

Journal of Crystal Growth

Naturally occurring vapor-liquid-solid (VLS) Whisker growth of germanium sulfide

The first naturally occurring terrestrial example of vapor-liquid-solid (VLS) growth has been observed in condensates from gases released by burning coal in culm banks. Scanning electron microscopy, X-ray diffraction, and energy dispersive analysis indicate that the crystals consist of elongated rods (≈ 100 μm) of germanium sulfide capped by bulbs depleted in germanium.

Journal of Crystal Growth

Experimental deformation of topaz crystals: Possible embrittlement by intracrystalline water

Crystallographically oriented single‐crystal prisms of gem quality topaz (composition AlSiO (OH− F) where x = 0.04 ± 0.01) were deformed at a confining pressure of 1.50 GPa, a temperature of 800°C, and a strain rate of 2×10 s. Under nearly identical conditions, all crystals of anhydrous rock‐forming minerals that have been tested to date, such as olivine, quartz, feldspars, pyroxenes, and refractory oxides, deform plastically; in contrast, our topaz crystals failed by brittle fracture regardless of the orientation of the compression direction. No optical evidence for plastic deformation was detected. Another suite of experiments with compression perpendicular to the (001) cleavage at = 100°–950°C and a strain rate of 2×10 s displayed two regimes of behavior: (1) at >400°C, fracture strength was independent of temperature, and fracture occurred on one or two surfaces parallel to {103}; (2) at <400°C, the fracture strength increased rapidly with decreasing temperature, no macroscopic stress drop was observed, and many closely spaced conjugate fractures formed on (103) and (103). The anomalous brittleness of topaz compared to anhydrous silicate and oxide crystals indicates that intracrystalline “water” plays a role in the embrittlement. We suggest that water within the topaz crystals promotes fracture in ways similar to the mechanisms of slow crack growth aided by environmental moisture.

Journal of Geophysical Research B: Solid Earth

Diagenesis of Miocene siliceous shales, Temblor Range, California

Siliceous Monterey Shale and related shales of the Temblor Range, Calif., are subdivided into three depth-controlled zones characterized by different forms of silica. These are, in descending stratigraphic order: (1) Biogenic opal zone, with remains of diatoms and other siliceous organisms, (2) diagenetic cristobalite zone, and (3) diagenetic quartz zone. Using the top of the youngest marine unit, the overlying Etchegoin Formation, as datum, the transition from biogenic opal to disordered cristobalite occurs within the Monterey Shale of Chico Martinez Creek at -730 m, and the ordered cristobalite-to-microquartz transition at about -2,030 m. Temperatures that prevailed at these transition depths while the sedimentary pile lay at the bottom of the sea are estimated at about 50&deg; and 110&deg;C, respectively. Diagenetic cristobalite manifests, downward through a 1,300-m interval of section, a progressive decrease in its d (101) spacing because of a gradual ordering of its internal structure through adjustments in the solid state. Diagenetic microquartz forms only from well-ordered cristobalite that provides the most appropriate concentration of dissolved silica for precipitation of microquartz. Scanning electron micrographs of the silica mineral in pores of rocks made up of disordered cristobalite show aggregates of well-formed bladed crystals, like those described from deep-sea cherts. The pore silica minerals in rocks made up of ordered cristobalite occur as dendritic growths of poorly formed stubby crystals, and the change in crystal habit could be an external expression of the internal ordering process.

California

The Fish Canyon magma body, San Juan volcanic field, Colorado: Rejuvenation and eruption of an upper-crustal batholith

More than 5000 km 3 of nearly compositionally homogeneous crystal-rich dacite (∼68 wt % SiO 2 : ∼45% Pl + Kfs + Qtz + Hbl + Bt + Spn + Mag + Ilm + Ap + Zrn + Po) erupted from the Fish Canyon magma body during three phases: (1) the pre-caldera Pagosa Peak Dacite (an unusual poorly fragmented pyroclastic deposit, ∼200 km 3 ); (2) the syn-collapse Fish Canyon Tuff (one of the largest known ignimbrites, ∼5000 km 3 ); (3) the post-collapse Nutras Creek Dacite (a volumetrically minor lava). The late evolution of the Fish Canyon magma is characterized by rejuvenation of a near-solidus upper-crustal intrusive body (mainly crystal mush) of batholithic dimensions. The necessary thermal input was supplied by a shallow intrusion of more mafic magma represented at the surface by sparse andesitic enclaves in late-erupted Fish Canyon Tuff and by the post-caldera Huerto Andesite. The solidified margins of this intrusion are represented by holocrystalline xenoliths with Fish Canyon mineralogy and mineral chemistry and widely dispersed partially remelted polymineralic aggregates, but dehydration melting was not an important mechanism in the rejuvenation of the Fish Canyon magma. Underlying mafic magma may have evolved H 2 O–F–S–Cl-rich fluids that fluxed melting in the overlying crystal mush. Manifestations of the late up-temperature magma evolution are: (1) resorbed quartz, as well as feldspars displaying a wide spectrum of textures indicative of both resorption and growth, including Rapakivi textures and reverse growth zoning (An 27–28 to An 32–33 ) at the margins of many plagioclase phenocrysts; (2) high Sr, Ba, and Eu contents in the high-SiO 2 rhyolite matrix glass, which are inconsistent with extreme fractional crystallization of feldspar; (3) oscillatory and reverse growth zoning toward the margins of many euhedral hornblende phenocrysts (rimward increases from ∼5·5–6 to 7·7–8·5 wt % Al 2 O 3 ). Homogeneity in magma composition at the chamber-wide scale, contrasting with extreme textural and chemical complexities at the centimeter–millimeter scale, is consistent with a dynamic environment, wherein crystals with a variety of growth and resorption histories were juxtaposed shortly before eruption by convective currents.

Colorado

Pre-eruptive magmatic conditions at Augustine Volcano, Alaska, 2006: Evidence from amphibole geochemistry and textures

Variations in the geochemistry and texture of amphibole phenocrysts erupted from Augustine Volcano in 2006 provide new insights into pre- and syn-eruptive magma storage and mixing. Amphiboles are rare but present in all magma compositions (low- to high-silica andesites) from the 3 month long eruption. Unzoned magnesiohornblende in the high- and low-silica andesites exhibit limited compositional variability, relatively high SiO 2 (up to 49·7 wt %), and relatively low Al 2 O 3 (< 11·1 wt %). Intermediate-silica andesites and quenched mafic enclaves contain amphiboles that vary in composition (e.g. SiO 2 40·8–48·9 wt %, Al 2 O 3 6·52–15·2 wt %) and classification (magnesiohornblende–magnesiohastingsite–tschermakite). Compositional variation in amphibole is primarily controlled by temperature-dependent substitutions. Both high- and low-silica andesites represent remnant magmas that were stored in the shallow crust at 4–8 km depth, remaining distinct owing to a complex subsurface plumbing system. Intermediate-silica andesites and quenched mafic inclusions represent pre-eruptive hybrids of resident high- and low-silica andesite magmas and an intruding basalt. Amphiboles in explosive phase high-silica andesites are largely euhedral and unreacted, consistent with the high magma flux rates from depth during this phase (up to 13 800 m 3 s –1 ). Phenocrysts from the other lithologies have reaction rims that range from 1 to >1000 μm in thickness. Reaction rim microlite sizes correlate with reaction rim thicknesses. Reaction rims <50 μm thick contain microlites 1–10 μm in length whereas reaction rims >80 μm thick contain microlites 10–100 μm in length. Differentiating between heating- and decompression-induced amphibole reaction rim formation is problematic because of a lack of experimental constraints. We attempt a new approach to assessing reaction rim formation, based on a kinetic theory of crystal nucleation and growth, in which the differences in reaction rim textures represent different degrees of amphibole disequilibrium. Large crystals and low number densities suggest relatively lower levels of disequilibrium resulting in growth-dominated crystallization. Smaller crystals and larger number densities are indicative of higher nucleation rates and a high driving force.

Alaska

Deducing growth mechanisms for minerals from the shapes of crystal size distributions

Crystal size distributions (CSDs) of natural and synthetic samples are observed to have several distinct and different shapes. We have simulated these CSDs using three simple equations: the Law of Proportionate Effect (LPE), a mass balance equation, and equations for Ostwald ripening. The following crystal growth mechanisms are simulated using these equations and their modifications: (1) continuous nucleation and growth in an open system, during which crystals nucleate at either a constant, decaying, or accelerating nucleation rate, and then grow according to the LPE; (2) surface-controlled growth in an open system, during which crystals grow with an essentially unlimited supply of nutrients according to the LPE; (3) supply-controlled growth in an open system, during which crystals grow with a specified, limited supply of nutrients according to the LPE; (4) supply- or surface-controlled Ostwald ripening in a closed system, during which the relative rate of crystal dissolution and growth is controlled by differences in specific surface area and by diffusion rate; and (5) supply-controlled random ripening in a closed system, during which the rate of crystal dissolution and growth is random with respect to specific surface area. Each of these mechanisms affects the shapes of CSDs. For example, mechanism (1) above with a constant nucleation rate yields asymptotically-shaped CSDs for which the variance of the natural logarithms of the crystal sizes (??2) increases exponentially with the mean of the natural logarithms of the sizes (??). Mechanism (2) yields lognormally-shaped CSDs, for which ??2 increases linearly with ??, whereas mechanisms (3) and (5) do not change the shapes of CSDs, with ??2 remaining constant with increasing ??. During supply-controlled Ostwald ripening (4), initial lognormally-shaped CSDs become more symmetric, with ??2 decreasing with increasing ??. Thus, crystal growth mechanisms often can be deduced by noting trends in ?? versus ??2 of CSDs for a series of related samples.

American Journal of Science

Lunar ferroan anorthosites: mineralogy, compositional variations, and petrogenesis

Detailed petrologic study of a suite of lunar ferroan anorthosites indicates that their mineral compositional variations are generally consistent with derivation of these anorthosites from a common parent magma. There are continuous compositional variations in major elements and smooth trends in minor elements (Mg, Fe in plagioclase; Al, Ti, Cr in pyroxene). Relict textures, zoning, and possible primary trends of mineral compositional variations are preserved in many of the anorthosites. The presence of heterogeneous, bimodal, and/or trimodal pyroxene compositions suggests that some of the anorthosites are polymict rocks; however, they are composed entirely of ferroan-anorthosite-suite lithologies. Some aspects of the mineral composition data suggest that complex processes operated during formation of the ferroan anorthosites. The lack of a well-defined, positive or negative trend of pyroxene Mg/(Mg + Fe) versus plagioclase anorthite content, the homogenization of mineral compositions in some anorthosites, and the varied and apparently enriched Mn contents of pyroxenes in some anorthosites suggest that original igneous compositional characteristics have been altered during and/or after crystallization. Processes operative during anorthosite formation may have included some mixing of different melts, trapping of variable amounts of intercumulus liquid, postcrystallization redistribution of elements, or perturbations both during adcumulus growth and subsequent to crystallization by impact events. FeO and MgO contents of the highly calcic plagioclase typical of these anorthosites suggest that the plagioclase-melt distribution coefficients for these elements need to be reassessed.

Journal of Geophysical Research

Effects of a low-lipid diet on the gut microbiome and head kidney transcriptome of juvenile Chinook Salmon

Objective Pacific salmon Oncorhynchus spp. reared in production hatcheries are typically fed high-lipid, energy-dense diets to achieve large size and high body condition prior to release. In contrast, juveniles in natural environments tend to consume low-lipid, high-protein diets, and fish reared for research or conservation purposes are sometimes fed diets that are formulated to mimic natural diets and promote wild-like phenotypes. Understanding how these alternative diets affect fish health beyond growth and body condition could ultimately contribute to improving hatchery fish fitness. Methods In this work, we evaluated changes in the fecal microbiome and gene expression of juvenile Chinook Salmon O. tshawytscha on a standard high-lipid hatchery diet versus a low-lipid diet formulated to mimic the nutrition profile of natural-origin fish. To evaluate the time scale at which diet alters the fecal microbiome, we collected longitudinal samples over a 12-week period and switched the diets of a subset of fish twice during the experiment. We used 16S ribosomal RNA gene amplicon sequencing to characterize fecal microbiome differences between fish on the two diets as well as hatchery-reared fish at a production hatchery, hatchery fish that had been captured after release into a stream, and natural-origin, stream-reared fish of similar ages. Additionally, we conducted RNA sequencing on head kidney samples from laboratory-reared fish to evaluate changes in gene expression in this important immune organ. Results We found that the low-lipid diet and the hatchery diet resulted in microbiomes that differed from the microbiome of natural-origin fish and from each other and that diet-driven changes to the microbiome could occur in under 14 d. The low-lipid diet did not result in a microbiome that resembled the microbiome of naturally produced fish. Instead, the low-lipid diet resulted in a microbiome community that was distinct from those of fish reared on the hatchery diet and fish sampled from the wild. The RNA sequencing results indicated differential enrichment of pathways related to immunity, metabolism, and hormone synthesis between fish that were fed the two experimental diets. Conclusions The results suggest that additional environmental factors influence the microbiome more strongly than diet formulation or that the low-lipid diet has a smaller effect on the microbiome than a natural, ­invertebrate-based diet. Given that the gut microbiome and systemic immune function contribute significantly to disease resistance, our findings highlight the importance of understanding how diets fed to fish in captivity may affect fish health beyond growth and body condition metrics.

Journal of Aquatic Animal Health

Experimental and textural constraints on mafic enclave formation in volcanic rocks

We have used experiments and textural analysis to investigate the process of enclave formation during magma mixing at Southwest Trident volcano, Alaska. Andesite enclaves are present throughout the four dacite lava flows produced by the eruption, and resemble mafic enclaves commonly found in other volcanic rocks. Our experiments replicate the pressure–temperature–time path taken by enclave-forming andesite magma as it is engulfed in dacite during magma mixing. Pressure and temperature information for the andesite and dacite are from [Coombs et al., Contrib. Mineral. Petrol. 140 (2000) 99–118]. The andesite was annealed at 1000°C, and then cooled to 890°C at rates of 110°C h −1 , 10°C h −1 , and 2°C h −1 . Once cooled to 890°C, andesite was held at this lower temperature from times ranging from 1 to 40 h. The andesite that was cooled at the slower rates of 2°C h −1 and 10°C h −1 most resembles enclave groundmass texturally and compositionally. Based on simple thermal calculations, these rates are more consistent with cooling of the andesite groundmass below an andesite–dacite interface than with cooling of enclave-sized spheres. If enclaves do crystallize as spheres, post-crystallization disaggregation must occur. Calculations using the MELTS algorithm [Ghiorso and Sack, Contrib. Mineral. Petrol. 119 (1995) 197–212] show that for incoming andesite to become less dense than the dacite ∼34 volume % of its groundmass must crystallize to undergo ∼18 volume % vesiculation; these values are similar to those determined for Southwest Trident enclaves. Thus such crystallization may lead to ‘flotation’ of enclaves and be a viable mechanism for enclave formation and dispersal. The residual melt in the cooling experiments did not evolve to rhyolitic compositions such as seen in natural enclaves due to a lack of a decompression step in the experiments. Decompression experiments on Southwest Trident dacite suggest an average ascent rate for the eruption of ∼2–3 MPa h −1 . An andesite experiment that was cooled and then decompressed at this rate contains melt that matches that of the natural enclaves. It is apparent that decompression (ascent)-induced crystallization occurs in enclaves, but not in the form of microlites as happens in the dacite host, due either to insufficient residence time at chamber temperatures or to the pre-existing microphenocrysts which act as sites for new growth.

Alaska

Thermal conductivity of hydrate-bearing sediments

A thorough understanding of the thermal conductivity of hydrate-bearing sediments is necessary for evaluating phase transformation processes that would accompany energy production from gas hydrate deposits and for estimating regional heat flow based on the observed depth to the base of the gas hydrate stability zone. The coexistence of multiple phases (gas hydrate, liquid and gas pore fill, and solid sediment grains) and their complex spatial arrangement hinder the a priori prediction of the thermal conductivity of hydrate-bearing sediments. Previous studies have been unable to capture the full parameter space covered by variations in grain size, specific surface, degree of saturation, nature of pore filling material, and effective stress for hydrate-bearing samples. Here we report on systematic measurements of the thermal conductivity of air dry, water- and tetrohydrofuran (THF)-saturated, and THF hydrate–saturated sand and clay samples at vertical effective stress of 0.05 to 1 MPa (corresponding to depths as great as 100 m below seafloor). Results reveal that the bulk thermal conductivity of the samples in every case reflects a complex interplay among particle size, effective stress, porosity, and fluid-versus-hydrate filled pore spaces. The thermal conductivity of THF hydrate–bearing soils increases upon hydrate formation although the thermal conductivities of THF solution and THF hydrate are almost the same. Several mechanisms can contribute to this effect including cryogenic suction during hydrate crystal growth and the ensuing porosity reduction in the surrounding sediment, increased mean effective stress due to hydrate formation under zero lateral strain conditions, and decreased interface thermal impedance as grain-liquid interfaces are transformed into grain-hydrate interfaces.

Journal of Geophysical Research B: Solid Earth

Comparative rhyolite systems: Inferences from vent patterns and eruptive episodicities: Eastern California and Laguna del Maule

Distilling my experience in having field mapped in detail the volcanic fields at Laguna del Maule and Long Valley and having worked out their time-volume-composition magmatic histories, I compare and contrast the postglacial rhyolites of the former with six multi-vent eruptive sequences of rhyolite in California. Compilations and discussions are made of volcanic-field areas and longevities, their compositions, vent distributions, individual batch and total volumes, eruptive episodicities, and tectonic influences. Growth of long-lived pluton-scale reservoirs of granitic crystal mush, from which the rhyolite melts separated, are interpreted in terms of conceptual models I published previously—(1) fundamentally basaltic transcrustal magmatism, 1981; (2) the deep-crustal MASH zone model, 1988; and (3) the rhyolite-melt crystal-mush model, 2001. Inferences and speculations are advanced concerning processes and timescales of rhyolite-melt separation from granitic mush and of prompt or long-delayed subsequent eruption.

California

High-pressure deformation of calcite marble and its transformation to aragonite under non-hydrostatic conditions

We conducted deformation experiments on Carrara marble in the aragonite and calcite stability fields to observe the synkinematic transformation of calcite to aragonite, and to identify any relationships between transformation and deformation or sample strength. Deformation-induced microstructures in calcite crystals varied most significantly with temperature, ranging from limited slip and twinning at 400°C, limited recrystallization at 500°C, widespread recrystallization at 600 and 700°C, to grain growth at 800–900°C. Variations in confining pressure from 0.3 to 2.0 GPa have no apparent effect on calcite deformation microstructures. Aragonite grew in 10 −6 -10 −7 s −1 strain rate tests conducted for 18–524 h at confining pressures of 1.7–2.0 GPa and temperatures of 500–600°C. As in our previously reported hydrostatic experiments on this same transformation, the aragonite nucleated on calcite grain boundaries. The extent of transformation varied from a few percent conversion near pistons at 400°C, 2.0 GPa and 10 −4 s −1 strain rate in a 0.8 h long experiment, to 98% transformation in a 21-day test at a strain rate of 10 −7 s −7 , a temperature of 600°C and a pressure of 2.0 GPa. At 500°C, porphyroblastic 100–200 μm aragonite crystals grew at a rate faster than 8 × 10 −1 m s −1 . At 600°C, the growth of aragonite neoblasts was slower, ≈6 × 10 −1 m s −1 , and formed ‘glove-and-finger’ cellularprecipitation-like textures identical to those observed in hydrostatic experiments. The transformation to aragonite is not accompanied by a shear instability or anisotropic aragonite growth, consistent with its relatively small volume change and latent heat in comparison with compounds that do display those features.

Journal of Structural Geology

Degassing and differentiation in subglacial volcanoes, Iceland

Within the neovolcanic zones of Iceland many volcanoes grew upward through icecaps that have subsequently melted. These steep-walled and flat-topped basaltic subglacial volcanoes, called tuyas, are composed of a lower sequence of subaqueously erupted, pillowed lavas overlain by breccias and hyaloclastites produced by phreatomagmatic explosions in shallow water, capped by a subaerially erupted lava plateau. Glass and whole-rock analyses of samples collected from six tuyas indicate systematic variations in major elements showing that the individual volcanoes are monogenetic, and that commonly the tholeiitic magmas differentiated and became more evolved through the course of the eruption that built the tuya. At Herdubreid, the most extensively studies tuya, the upward change in composition indicates that more than 50 wt.% of the first erupted lavas need crystallize over a range of 60°C to produce the last erupted lavas. The S content of glass commonly decreases upward in the tuyas from an average of about 0.08 wt.% at the base to < 0.02 wt.% in the subaerially erupted lava at the top, and is a measure of the depth of water (or ice) above the eruptive vent. The extensive subsurface crystallization that generates the more evolved, lower-temperature melts during the growth of the tuyas, apparently results from cooling and degassing of magma contained in shallow magma chambers and feeders beneath the volcanoes. Cooling may result from percolation of meltwater down cracks, vaporization, and cycling in a hydrothermal circulation. Degassing occurs when progressively lower pressure eruption (as the volcanic vent grows above the ice/water surface) lowers the volatile vapour pressure of subsurface melt, thus elevating the temperature of the liquidus and hastening liquid-crystal differentiation.

Journal of Volcanology and Geothermal Research

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

The geochemical and textural transition between the Reef Package and its hanging wall, Stillwater Complex, Montana, USA

The highest grade Pd-Pt deposit on Earth, the J-M Reef, is hosted in coarse-grained to pegmatoidal cumulates called the Reef Package. Decades of mine development of the J-M Reef have revealed that a distinct discontinuity in rock fabric marks the top of the rock unit that hosts economic-grade sulfide mineralization. Mine geologists refer to this discontinuity as the hanging wall contact. This contact is the top of the Reef Package and is always locatable—either by the change in rock fabric or by distinctive hanging wall textures of silicate minerals—even when the reef sulfide mineralization is absent. This rather subtle textural feature is used reliably by mine geologists to follow the Reef during exploration and mine development. Although some high tenor sulfides (>1000 ppm Pd in 100% sulfide) are found sporadically in the hanging wall cumulates, these accumulations are too small to be economically viable. We present quantitative rock fabric data for four Reef Package and hanging wall intersections collected by electron back-scattered diffraction (EBSD). Plagioclase fabrics in the hanging wall are characterized by low variance in grain sizes and a strong point maximum concentration of (010) and a perpendicular girdle distribution of [100] consistent with an axial B-type fabric. These fabrics are indicative of either compaction of the crystal mush or crystal settling of nucleated crystals, the bulk magma in a chamber. Conversely, the fabrics of the Reef Package show higher variance grain in size distributions and weak to undeveloped preferred orientation of plagioclase crystals that did not undergo significant alignment or textural equilibration of plagioclase grains. The absence of foliation in the Reef Package stands in contrast both to hanging wall fabrics and to other reported EBSD datasets of plagioclase crystals orientations from the Bushveld Complex, the Skaergaard Intrusion, and the Rum Intrusion. Furthermore, plagioclase crystal size distributions for the Reef Package show flatter slopes and convex profiles with fewer crystals at small size fractions indicating the dissolution of small crystals during partial melting and textural coarsening (i.e . Ostwald ripening) and crystal growth. Crystal growth was favored over the nucleation of new crystals during prolonged interaction with a hot infiltrating melt into the resident mush resulting in the coarse-grained textures of the Reef Package cumulates. The hanging wall contact represents a boundary between partially remelted crystal mush of the Reef Package, where sulfide mineralization formed and accumulated, and an overlying essentially barren cumulate pile. The hanging wall cumulates formed following the cessation of footwall erosion and the resumption of crystal accumulation by normal magma chamber processes.

Montana

Dating individual zones in phenocrysts from the 2016–2017 eruption of Bogoslof volcano provides constraints on timescales of magmatic processes

We investigate the rates of magmatic processes using clinopyroxene diffusion chronometry on volcanic products erupted in August 2017 at the end of the 9-month eruption of Bogoslof volcano. The eruptive products contain plagioclase, clinopyroxene, and amphibole, all of which exhibit sharp chemical boundaries and are occasionally observed in multi-phase crystal clots with shared zoning boundaries across different mineral phases. At the shared boundaries in crystal clots, clinopyroxene and plagioclase continued to grow but abruptly changed composition from Mg# 81.7 ± 5.8 to 72.9 ± 3.0 and An 82.5±1.4 to An 61.3±5.7 , respectively. Additionally, the sharp boundary marks where amphibole became unstable and began forming a reaction rim. Synthesizing these observations, we were able to determine that the shared boundaries formed as a result of rapid decompression during magma ascent, followed by storage in a shallow cryptodome, where magma accumulated prior to erupting. In order to determine the timescales of magma ascent and subsequent crystal residence times, we applied diffusion chronometry on zoned clinopyroxene phenocrysts using Mg# concentrations at 1056 °C determined from Fe Ti oxide pairs. Our diffusion modeling results show that diffusion began at the stepwise boundaries in clinopyroxenes no more than180 days before the final explosive event. These results were then used to calculate crystal growth rates for shared plagioclase and amphibole rims, as shared zones in crystal clots indicate that the boundaries in all three phases formed contemporaneously. We calculate growth rates of plagioclase crystals (1.7 ± 0.99 × 10 −6 um/s) and amphibole reaction rims (2.8 ± 0.47 × 10 −6 um/s). The calculated natural growth rate of plagioclase was then used to constrain additional magmatic timescales from growth rate chronometry, results of which support our diffusion timescales. Our results indicate that the distinct boundaries in all three mineral phases formed due to ascent-driven decompression followed by shallow emplacement of mafic magma that occurred continually throughout the course of the eruption. By subtracting diffusion timescales from the date that the samples were erupted, the oldest crystal boundaries correspond to March 2017, seemingly correlating with increases in both seismicity and SO 2 emissions. These observations may suggest that our petrochronometric results are supported by interdisciplinary observations.

Alaska

Scanning electron microscope observations of sublimates from Merapi Volcano, Indonesia

Sublimates were sampled from high-temperature (up to 800°C) fumaroles at Merapi volcano, Indonesia in January 1984. Sampling is accomplished by inserting silica tubes into high-temperature vents. Volcanic gas flows through the tubes and sublimates precipitate on the inner walls in response to the temperature gradient. With decreasing temperature (800–500°C) in the tubes, there are five sublimate zones: 1) cristobalite, magnetite, and halite; 2) halite, sylvite, K-Ca sulfate (K 2 Ca[SO 4 ] 2 ), acmite, wollastonite, and pyrite; 3) halite, sylvite, galena, Pb-Bi sulfide, aphthitalite, sphalerite, and Cs-K sulfate; 4) halite, sylvite, galena, PbKCl 3 , aphthitalite, and Na-K-Fe sulfate ([Na, K] 2 Fe[SO 4 ]Cl 2 ); and 5) halite, sylvite, galena, PbKCl 3 , and various sulfates of Pb, Cu, and Zn. Texturally, the sublimate phases grade from large, well-formed crystals at their highest-temperature occurrence to more numerous, smaller crystals that are less perfect at lower temperatures. These changes imply that the crystal nucleation and growth rates increase and decrease, respectively, as temperature decreases. Several of the sublimate phases also exhibit highly anisotropic morphologies (whiskers, platelets, spheres), especially below their highest temperature of deposition. Overall, the textural data suggest that the gas is saturated or slightly supersaturated with the phases at their hottest occurrence, but that the gas becomes increasingly supersaturated with the phases at lower temperatures. The anisotropic morphologies probably form because the crystals grow toward more supersaturated conditions in the center of the tube. The gas fails to maintain equilibrium with the precipitating sublimates because the high velocity of the carrier gas prevents complete mass transfer from the gas stream to the tube walls.

Merapi Volcano