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.     

Enrichments of the mantle sources beneath the Southern Volcanic Zone (Andes) by fluids and melts derived from abraded upper continental crust

Mafic basaltic-andesitic volcanic rocks from the Andean Southern Volcanic Zone (SVZ) exhibit a northward increase in crustal components in primitive arc magmas from the Central through the Transitional and Northern SVZ segments. New elemental and Sr–Nd-high-precision Pb isotope data from the Quaternary arc volcanic centres of Maipo (NSVZ) and Infernillo and Laguna del Maule (TSVZ) are argued to reflect mainly their mantle source and its melting. For the C-T-NSVZ, we identify two types of source enrichment: one, represented by Antuco in CSVZ, but also present northward along the arc, was dominated by fluids which enriched a pre-metasomatic South Atlantic depleted MORB mantle type asthenosphere. The second enrichment was by melts having the characteristics of upper continental crust (UCC), distinctly different from Chile trench sediments. We suggest that granitic rocks entered the source mantle by means of subduction erosion in response to the northward increasingly strong coupling of the converging plates. Both types of enrichment had the same Pb isotope composition in the TSVZ with no significant component derived from the subducting oceanic crust. Pb–Sr–Nd isotopes indicate a major crustal compositional change at the southern end of the NSVZ. Modelling suggests addition of around 2 % UCC for Infernillo and 5 % for Maipo.     

Amphibole as an archivist of magmatic crystallization conditions: problems,potential, and implications for inferring magma storage prior to the paroxysmal 2010 eruption of Mount Merapi,Indonesia

Amphibole is widely employed to calculate crystallization temperature and pressure, although its potential as a geobarometer has always been debated. Recently, Ridolfi et al. (Contrib Mineral Petrol 160:45–66, 2010) and Ridolfi and Renzulli (Contrib Mineral Petrol 163:877–895, 2012) have presented calibrations for calculating temperature, pressure, fO₂, melt H₂O, and melt major and minor oxide composition from amphibole with a large compositional range. Using their calibrations, we have (i) calculated crystallization conditions for amphibole from eleven published experimental studies to examine the problems and the potential of the new calibrations; and (ii) calculated crystallization conditions for amphibole from basaltic–andesitic pyroclasts erupted during the paroxysmal 2010 eruption of Mount Merapi in Java, Indonesia, to infer pre-eruptive conditions. Our comparison of experimental and calculated values shows that calculated crystallization temperatures are reasonable estimates. Calculated fO₂ and melt SiO₂ content yields potentially useful estimates at moderately reduced to moderately oxidized conditions and intermediate to felsic melt compositions. However, calculated crystallization pressure and melt H₂O content are untenable estimates that largely reflect compositional variation in the crystallizing magmas and crystallization temperature and not the calculated parameters. Amphibole from Merapi’s pyroclasts yields calculated conditions of ~200–800 MPa, ~900–1,050 °C, ~NNO + 0.3–NNO + 1.1, ~3.7–7.2 wt% melt H₂O, and ~58–71 wt% melt SiO₂. We interpret the variations in calculated temperature, fO₂, and melt SiO₂ content as reasonable estimates, but conclude that the large calculated pressure variation for amphibole from Merapi and many other arc volcanoes is evidence for thorough mixing of mafic to felsic magmas and not necessarily evidence for crystallization over a large depth range. In contrast, bimodal pressure estimates obtained for other arc magmas reflect amphibole crystallization from mafic and more evolved magmas, respectively, and should not necessarily be taken as evidence for crystallization in two reservoirs at variable depth.     

Temporal evolution and compositional signatures of two supervolcanic systems recorded in zircons from Mangakino volcanic centre,New Zealand

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