Overstepping the garnet isograd: a comparison of QuiG barometry and thermodynamic modeling

The consequences of overstepping the garnet isograd reaction have been investigated by comparing the composition of garnet formed at overstepped P–T conditions (the overstep or “OS” model) with the P–T conditions that would be inferred by assuming garnet nucleated in equilibrium with the matrix assemblage at the isograd (the equilibrium or “EQ” model). The garnet nucleus composition formed at overstepped conditions is calculated as the composition that produces the maximum decrease in Gibbs free energy from the equilibrated, garnet-absent, matrix assemblage for the bulk composition under study. Isopleths were then calculated for this garnet nucleus composition assuming equilibrium with the matrix assemblage (the EQ model). Comparison of the actual P–T conditions of nucleation (the OS model) with those inferred from the EQ model reveals considerable discrepancy between the two. In general, the inferred garnet nucleation P–T conditions (the EQ model) are at a lower temperature and higher or lower pressure (depending on the coexisting calcic phase(s)) than the actual (OS model) nucleation conditions. Moreover, the degree of discrepancy increases with the degree of overstepping. Independent estimates of the pressure of nucleation of garnet were made using the Raman shift of quartz inclusions in garnet (quartz-in-garnet or QuiG barometry). To test the validity of this method, an experimental synthesis of garnet containing quartz inclusions was made at 800 °C, 20 kbar, and the measured Raman shift reproduced the synthesis conditions to within 120 bars. Raman band shifts from three natural samples were then used to calculate an isochore along which garnet was presumed to have nucleated. Model calculations were made at several temperatures along this isochore (the OS model), and these P–T conditions were compared to those computed assuming equilibrium nucleation (the EQ model) to estimate the degree of overstepping displayed by these samples. A sample from the garnet isograd in eastern Vermont is consistent with overstepping of around 10 degrees and 0.6 kbar (affinities of around 2 kJ/mole garnet). A sample from the staurolite–kyanite zone in the same terrane requires overstepping of around 50 °C and 2–5 kbar (affinities of around 10–18 kJ/mole garnet). A similar amount of overstepping was inferred for a blueschist sample from Sifnos, Greece. These results indicate that overstepping of garnet nucleation reactions may be common and pronounced in regionally metamorphosed terranes, and that the P–T conditions and paths inferred from garnet zoning studies may be egregiously in error.     

Thermal and rheological controls on the formation of mafic enclaves or banded pumice

Magma mixing can occur in a fluid manner to produce banded pumice or in a brittle manner to form enclaves. We propose that the critical control on mixing style is a competition between developing networks of crystals in the intruding magma that impart a strength to the magma and melting and disrupting those networks in the host. X-ray computed tomography analysis demonstrates that banded pumice from the 1915 Mt. Lassen eruption lacks crystal networks. In contrast, rhyodacite hosts with mafic enclaves from Chaos Crags contain well-developed networks of large crystals. We present a one-dimensional conductive cooling model that predicts mixing style, either ductile or brittle, as a function of magma compositions, temperatures, and the size of the intruding dike. Our model relies on three assumptions: (1) Mixing is initiated by the injection of a hot dike into a cooler magma body with a yield strength; (2) when magma crystallinity exceeds a critical value, 13 vol% plagioclase, the magma develops a yield strength; and (3) when total crystallinity exceeds 40 vol%, the magma has a penetrative crystal network and is effectively solid. Importantly, because the two magmas are of different compositions, their crystallinities and viscosities do not have the same variations with temperature. As the intruding magma cools, it crystallizes from the outside in, while simultaneously, host magma temperature near the intruder rises. Mixing of the two magmas begins when the host magma is heated sufficiently to (1) disrupt the crystal network and (2) initiate convection. If the shear stress exerted by the convecting host magma on the dike is greater than the yield strength of the dike margin (and dike crystallinity does not exceed 40 %), then fluid mixing occurs, otherwise enclaves form by brittle deformation of the dike. Application of the model to magma compositions representative of Lassen and Chaos Crags shows that emplacement of dikes <1 m thick should produce enclaves, whereas thicker dikes should generate fluid mixing and form banded pumice within days to weeks of emplacement. Similar relationships apply to other modeled magmatic systems, including Pinatubo, Unzen, and Ksudach/Shtuybel’ volcanoes. For all studied systems, the absolute size of the intruding dike, not just its proportion relative to the host, influences mixing style.     

Primary melt from Sannome-gata volcano,NE Japan arc: constraints on generation conditions of rear-arc magmas

The conditions under which rear-arc magmas are generated were estimated using primary basalts from the Sannome-gata volcano, located in the rear of the NE Japan arc. Scoriae from the volcano occur with abundant crustal and mantle xenoliths, suggesting that the magma ascended rapidly from the upper mantle. The scoriae show significant variations in their whole-rock compositions (7.9–11.1 wt% MgO). High-MgO scoriae (MgO > ~9.5 wt%) have mostly homogeneous ⁸⁷Sr/⁸⁶Sr ratios (0.70318–0.70320), whereas low-MgO scoriae (MgO < ~9 wt%) have higher ⁸⁷Sr/⁸⁶Sr ratios (>0.70327); ratios tend to increase with decreasing MgO content. The high-MgO scoriae are aphyric, containing ~5 vol% olivine microphenocrysts with Mg# [100 × Mg/(Mg + Fe²⁺)] of up to 90. In contrast, the low-MgO scoriae have crustal xenocrysts of plagioclase, alkali feldspar, and quartz, and the mineralogic modes correlate negatively with whole-rock MgO content. On the basis of these observations, it is inferred that the high-MgO scoriae represent primary or near-primary melts, while the low-MgO scoriae underwent considerable interaction with the crust. Using thermodynamic analysis of the observed petrological features of the high-MgO scoriae, the eruption temperature of the magmas was constrained to 1,160–1,220 °C. Given that the source mantle was depleted MORB-source mantle, the primary magma was plausibly generated by ~7 % melting of a garnet-bearing spinel peridotite; taking this into consideration, and considering the constraints of multi-component thermodynamics, we estimated that the primary Sannome-gata magma was generated in the source mantle with 0.5–0.6 wt% H₂O at 1,220–1,230 °C and at ~1.8 GPa, and that the H₂O content of the primary magma was 6–7 wt%. The rear-arc Sannome-gata magma was generated by a lower degree of melting of the mantle at greater depths and lower temperatures than the frontal-arc magma from the Iwate volcano, which was also estimated to be generated by ~15 % melting of the source mantle with 0.6–0.7 wt% H₂O at ~1,250 °C and at ~1.3 GPa.     

Settling and compaction of chromite cumulates employing a centrifuging piston cylinder and application to layered mafic intrusions

The time scales and mechanics of gravitationally driven crystal settling and compaction is investigated through high temperature (1,280–1,500 °C) centrifuge-assisted experiments on a chromite-basalt melt system at 100–1,500g (0.5 GPa). Subsequently, the feasibility of this process for the formation of dense chromite cumulate layers in large layered mafic intrusions (LMIs) is assessed. Centrifugation leads to a single cumulate layer formed at the gravitational bottom of the capsule. The experimentally observed mechanical settling velocity of a suspension of ~24 vol% chromite is calculated to be about half (~0.53) of the Stokes settling velocity, with a sedimentation exponent n of 2.35 (3). Gravitational settling leads to an orthocumulate layer with a porosity of 0.52 (all porosities as fraction). Formation times for such a layer from a magma with initial chromite contents of 0.1–1 vol% are 140–3.5 days, equal to a growth rate of 0.007–0.3 m/day for grain sizes of 1–2 mm. More compacted chromite layers form with increasing centrifugation time and acceleration through chemical compaction: An increase of grain contact areas and grain sizes together with a decrease in porosity is best explained by pressure dissolution at grain contacts, reprecipitation and grain growth into the intergranular space and a concomitant expulsion of intergranular melt. The relation between the porosity in the cumulate pile and effective pressure integrated over time (Δρ · h · a · t) is best fit with a logarithmic function, in fact confirming that a (pressure) dissolution–reprecipitation process is the dominant mechanism of compaction. The experimentally derived equation allows calculating compaction times: 70–80 % chromite at the bottom of a 1-m-thick chromite layer are reached after 9–250 years, whereas equivalent compaction times are 0.2–0.9 years for olivine (both for 2 mm grain size). The experiments allow to determine the bulk viscosities of chromite and olivine cumulates to be of magnitude 10⁹ Pa s, much lower than previously reported. As long as melt escape from the compacting cumulate remains homogeneous, fluidization does not play any role; however, channelized melt flow may lead to suspension and upward movement of cumulate crystals. In LMIs, chromitite layers are typically part of a sequence with layers of mafic minerals, compaction occurs under the additional weight of the overlying layers and can be achieved in a few years to decades.     

Zircon evidence for a ~200 k.y. supereruption-related thermal flare-up in the Miocene southern Black Mountains,western Arizona,USA

The Silver Creek caldera (southern Black Mountains, western Arizona) is the source of the 18.8 Ma, >700 km³ Peach Spring Tuff (PST) supereruption, the largest eruption generated in the Colorado River Extensional Corridor (CREC) of the southwestern United States. Within and immediately surrounding the caldera is a sequence of volcanics and intrusions ranging in age from ~19 to 17 Ma. These units offer a record of magmatic processes prior to, during, and immediately following the PST eruption. To investigate the thermal evolution of the magmatic center that produced the PST, we applied a combination of Ti-in-zircon thermometry, zircon saturation thermometry, and high-precision U–Pb CA–TIMS zircon dating to representative pre- and post-supereruption volcanic and intrusive units from the caldera and its environs. Similar to intracaldera PST zircons, zircons from a pre-PST trachytic lava (19 Ma) and a post-PST caldera intrusion (18.8 Ma) yield exceptionally high-Ti concentrations (most >20 ppm, some up to nearly 60 ppm), corresponding to calculated temperatures that exceed 900 °C. In these units, Ti-in-zircon temperatures typically surpass zircon saturation temperatures (ZSTs), suggesting the entrainment of zircon that had grown in hotter environments within the magmatic system. Titanium concentrations in younger volcanic and intrusive units (~18.7–17.5 Ma) decline through time, corresponding to an average cooling rate of 10^?3.5 °C/year. The ~200 k.y. thermal peak evident at Silver Creek caldera is spatially limited: elsewhere in the Miocene record of the northern CREC, Ti-in-zircon concentrations and ZSTs are much lower, suggesting that felsic magmas were generally substantially cooler.     

Pre- and syn-eruptive degassing and crystallisation processes of the 2010 and 2006 eruptions of Merapi volcano,Indonesia

The 2010 eruption of Merapi (VEI 4) was the volcano’s largest since 1872. In contrast to the prolonged and effusive dome-forming eruptions typical of Merapi’s recent activity, the 2010 eruption began explosively, before a new dome was rapidly emplaced. This new dome was subsequently destroyed by explosions, generating pyroclastic density currents (PDCs), predominantly consisting of dark coloured, dense blocks of basaltic andesite dome lava. A shift towards open-vent conditions in the later stages of the eruption culminated in multiple explosions and the generation of PDCs with conspicuous grey scoria and white pumice clasts resulting from sub-plinian convective column collapse. This paper presents geochemical data for melt inclusions and their clinopyroxene hosts extracted from dense dome lava, grey scoria and white pumice generated during the peak of the 2010 eruption. These are compared with clinopyroxene-hosted melt inclusions from scoriaceous dome fragments from the prolonged dome-forming 2006 eruption, to elucidate any relationship between pre-eruptive degassing and crystallisation processes and eruptive style. Secondary ion mass spectrometry analysis of volatiles (H₂O, CO₂) and light lithophile elements (Li, B, Be) is augmented by electron microprobe analysis of major elements and volatiles (Cl, S, F) in melt inclusions and groundmass glass. Geobarometric analysis shows that the clinopyroxene phenocrysts crystallised at depths of up to 20 km, with the greatest calculated depths associated with phenocrysts from the white pumice. Based on their volatile contents, melt inclusions have re-equilibrated during shallower storage and/or ascent, at depths of ~0.6–9.7 km, where the Merapi magma system is interpreted to be highly interconnected and not formed of discrete magma reservoirs. Melt inclusions enriched in Li show uniform “buffered” Cl concentrations, indicating the presence of an exsolved brine phase. Boron-enriched inclusions also support the presence of a brine phase, which helped to stabilise B in the melt. Calculations based on S concentrations in melt inclusions and groundmass glass require a degassing melt volume of 0.36 km³ in order to produce the mass of SO₂ emitted during the 2010 eruption. This volume is approximately an order of magnitude higher than the erupted magma (DRE) volume. The transition between the contrasting eruptive styles in 2010 and 2006 is linked to changes in magmatic flux and changes in degassing style, with the explosive activity in 2010 driven by an influx of deep magma, which overwhelmed the shallower magma system and ascended rapidly, accompanied by closed-system degassing.     

Deciphering petrogenic processes using Pb isotope ratios from time-series samples at Bezymianny and Klyuchevskoy volcanoes,Central Kamchatka Depression

The Klyuchevskoy group of volcanoes in the Kamchatka arc erupts compositionally diverse magmas (high-Mg basalts to dacites) over small spatial scales. New high-precision Pb isotope data from modern juvenile (1956–present) erupted products and hosted enclaves and xenoliths from Bezymianny volcano reveal that Bezymianny and Klyuchevskoy volcanoes, separated by only 9 km, undergo varying degrees of crustal processing through independent crustal columns. Lead isotope compositions of Klyuchevskoy basalts–basaltic andesites are more radiogenic than Bezymianny andesites (²⁰⁸Pb/²⁰⁴Pb = 37.850–37.903, ²⁰⁷Pb/²⁰⁴Pb = 15.468–15.480, and ²⁰⁶Pb/²⁰⁴Pb = 18.249–18.278 at Bezymianny; ²⁰⁸Pb/²⁰⁴Pb = 37.907–37.949, ²⁰⁷Pb/²⁰⁴Pb = 15.478–15.487, and ²⁰⁶Pb/²⁰⁴Pb = 18.289–18.305 at Klyuchevskoy). A mid-crustal xenolith with a crystallization pressure of 5.2 ± 0.6 kbars inferred from two-pyroxene geobarometry and basaltic andesite enclaves from Bezymianny record less radiogenic Pb isotope compositions than their host magmas. Hence, assimilation of such lithologies in the middle or lower crust can explain the Pb isotope data in Bezymianny andesites, although a component of magma mixing with less radiogenic mafic recharge magmas and possible mantle heterogeneity cannot be excluded. Lead isotope compositions for the Klyuchevskoy Group are less radiogenic than other arc segments (Karymsky—Eastern Volcanic Zone; Shiveluch—Northern Central Kamchatka Depression), which indicate increased lower-crustal assimilation beneath the Klyuchevskoy Group. Decadal timescale Pb isotope variations at Klyuchevskoy demonstrate rapid changes in the magnitude of assimilation at a volcanic center. Lead isotope data coupled with trace element data reflect the influence of crustal processes on magma compositions even in thin mafic volcanic arcs.     

Continuous zircon growth during long-lived granulite facies metamorphism: a microtextural,U–Pb,Lu–Hf and trace element study of Caledonian rocks from the Arctic

Microtextural, U–Pb, trace element and Lu–Hf analyses of zircons from gneisses dredged from the Chukchi Borderland indicate a long-lived, Cambrian–Ordovician, granulite facies metamorphism. These results reveal a complete prograde, peak and cooling history of zircon growth during anatexis. Early increasing temperatures caused modification and Pb-loss of Precambrian zircons by recrystallization and dissolution/re-precipitation of existing grains. Small variations in initial ¹⁷⁶Hf/¹⁷⁷Hf results (0.282325–0.282042) and flat HREE patterns of these zircons indicate that they grew by dissolution/re-precipitation in the presence of garnet. Zircons subsequently crystallized from a partial melt during peak to post-peak metamorphism from 530 to 485 Ma. A broad range of initial ¹⁷⁶Hf/¹⁷⁷Hf ratios (0.282693–0.282050) and mineral inclusions within zircons suggest that this phase of growth incorporated Zr and Hf obtained from the breakdown of Zr-enriched phases. Microtextural evidence along with trace element and isotopic data suggests that final growth of metamorphic rims on zircon occurred during slow cooling and crystallization of residual partial melts during the early Ordovician (485–470 Ma). Younger, late Ordovician–Silurian (420–450 Ma) euhedral, oscillatory-zoned, trace element-enriched zircons crystallized within leucocratic veins that intrude the gneisses. Their age corresponds to granitoids dated from this same dredge. The intrusives and veins provide evidence that the Chukchi Borderland rifted from a position near Pearya and northwest Svalbard, which represent the northern continuation of the Caledonian orogen. Evidence for earlier Cambrian metamorphism has not been reported from this region. The age of granulite facies metamorphism reported here represents the earliest phase of deformation in the Arctic Caledonides.     

Dissolution–precipitation processes governing the carbonation and silicification of the serpentinite sole of the New Caledonia ophiolite

The weathering of mantle peridotite tectonically exposed to the atmosphere leads commonly to natural carbonation processes. Extensive cryptocrystalline magnesite veins and stock-work are widespread in the serpentinite sole of the New Caledonia ophiolite. Silica is systematically associated with magnesite. It is commonly admitted that Mg and Si are released during the laterization of overlying peridotites. Thus, the occurrence of these veins is generally attributed to a per descensum mechanism that involves the infiltration of meteoric waters enriched in dissolved atmospheric CO₂. In this study, we investigate serpentinite carbonation processes, and related silicification, based on a detailed petrographic and crystal chemical study of serpentinites. The relationships between serpentine and alteration products are described using an original method for the analysis of micro-X-ray fluorescence images performed at the centimeter scale. Our investigations highlight a carbonation mechanism, together with precipitation of amorphous silica and sepiolite, based on a dissolution–precipitation process. In contrast with the per descensum Mg/Si-enrichment model that is mainly concentrated in rock fractures, dissolution–precipitation process is much more pervasive. Thus, although the texture of rocks remains relatively preserved, this process extends more widely into the rock and may represent a major part of total carbonation of the ophiolite.     

Titanium- and water-rich metamorphic olivine in high-pressure serpentinites from the Voltri Massif (Ligurian Alps,Italy): evidence for deep subduction of high-field strength and fluid-mobile elements

Titanium- and water-rich metamorphic olivine (Fo 86–88) is reported from partially dehydrated serpentinites from the Voltri complex, Ligurian Alps. The rocks are composed of mostly antigorite and olivine in addition to magnetite, chlorite, clinopyroxene and Ti-clinohumite. In situ secondary ion mass spectrometry (SIMS) data show that metamorphic olivine has very high and strongly correlated H₂O (up to 0.7 wt%) and TiO₂ contents (up to 0.85 wt%). Ti-rich olivine shows colourless to yellow pleochroism. Olivine associated with Ti-clinohumite contains low Ti, suggesting that Ti-rich olivine is not the breakdown product of Ti-clinohumite. Fourier transform infrared spectroscopy (FTIR) absorption spectra show peaks of serpentine, Ti-clinohumite and OH-related Si vacancies. Combining FTIR and SIMS data, we suggest the presence of clustered planar defects or nanoscale exsolutions of Ti-clinohumite in olivine. These defects or exsolutions contain more H₂O (x ~ 0.1 in the formula 4Mg₂SiO₄·(1?x)Mg(OH,F)₂·xTiO₂) than Ti-clinohumite in the sample matrix (x = 0.34–0.46). In addition to TiO₂ and H₂O, secondary olivine contains significant Li (2–60 ppm), B (10–20 ppm), F (10–130 ppm) and Zr (0.9–2.1 ppm). It is enriched in ¹¹B (δ¹¹B = +17 to +23 ‰). Our data indicate that secondary olivine may play a significant role in transporting water, high-field strength and fluid-mobile elements into the deeper mantle as well as introduce significant B isotope anomalies. Release of hydrogen from H₂O-rich olivine subducted into the deep mantle may result in strongly reduced mantle domains.