Multiple timescale constraints for high-flux magma chamber assembly prior to the Late Bronze Age eruption of Santorini (Greece)

The rhyodacitic magma discharged during the 30–80 km³ DRE (dense rock equivalent) Late Bronze Age (LBA; also called ‘Minoan’) eruption of Santorini caldera is known from previous studies to have had a complex history of polybaric ascent and storage prior to eruption. We refine the timescales of these processes by modelling Mg–Fe diffusion profiles in orthopyroxene and clinopyroxene crystals. The data are integrated with previously published information on the LBA eruption (phase equilibria studies, melt inclusion volatile barometry, Mg-in-plagioclase diffusion chronometry), as well as new plagioclase crystal size distributions and the established pre-LBA history of the volcano, to reconstruct the events that led up to the assembly and discharge of the LBA magma chamber. Orthopyroxene, clinopyroxene and plagioclase crystals in the rhyodacite have compositionally distinct rims, overgrowing relict, probably source-derived, more magnesian (or calcic) cores, and record one or more crystallization (plag???opx?>?cpx) events during the few centuries to years prior to eruption. The crystallization event(s) can be explained by the rapid transfer of rhyodacitic melt from a dioritic/gabbroic region of the subcaldera pluton (mostly in the 8–12 km depth range), followed by injection, cooling and mixing in a large melt lens at 4–6 km depth (the pre-eruptive magma chamber). Since crystals from all eruptive phases yield similar timescales, the melt transfer event(s), the last of which took place less than 2 years before the eruption, must have involved most of the magma that subsequently erupted. The data are consistent with a model in which prolonged generation, storage and segregation of silicic melts were followed by gravitational instability in the subcaldera pluton, causing the rapid interconnection and amalgamation of melt-rich domains. The melts then drained to the top of the pluton, at fluxes of up to 0.1–1 km³ year^??1, where steep vertical gradients of density and rheology probably caused them to inject laterally, forming a short-lived holding chamber prior to eruption. This interpretation is consistent with growing evidence that some large silicic magma chambers are transient features on geological timescales. A similar process preceded at least one earlier caldera-forming eruption on Santorini, suggesting that it may be a general feature of this rift-hosted magmatic system.     

Carbon and nitrogen isotope,and mineral inclusion studies on the diamonds from the Pozanti–Karsanti chromitite,Turkey

The Pozanti–Karsanti ophiolite (PKO) is one of the largest oceanic remnants in the Tauride belt, Turkey. Micro-diamonds were recovered from the podiform chromitites, and these diamonds were investigated based on morphology, color, cathodoluminescence, nitrogen content, carbon and nitrogen isotopes, internal structure and inclusions. The diamonds recovered from the PKO are mainly mixed-habit diamonds with sectors of different brightness under the cathodoluminescence images. The total δ¹³C range of the PKO diamonds varies between ??18.8 and ??28.4‰, with a principle δ¹³C mode at ??25‰. Nitrogen contents of the diamonds range from 7 to 541 ppm with a mean value of 171 ppm, and the δ¹⁵N values range from ??19.1 to 16.6‰, with a δ¹⁵N mode of ??9‰. Stacking faults and partial dislocations are commonly observed in the Transmission Electron Microscopy foils whereas inclusions are rather rare. Combinations of (Ca_0.81Mn_0.19)SiO₃, NiMnCo-alloy and nano-sized, quenched fluid phases were observed as inclusions in the PKO diamonds. We believe that the ¹³C-depleted carbon signature of the PKO diamonds derived from previously subducted crustal matter. These diamonds may have crystallized from C-saturated fluids in the asthenospheric mantle at depth below 250 km which were subsequently carried rapidly upward by asthenospheric melts.     

Experimental study of quartz inclusions in garnet at pressures up to 3.0 GPa: evaluating validity of the quartz-in-garnet inclusion elastic thermobarometer

Garnet crystals with quartz inclusions were hydrothermally crystallized from oxide starting materials in piston–cylinder apparatuses at pressures from 0.5 to 3 GPa and temperatures ranging from 700 to 800 °C to study how entrapment conditions affect remnant pressures of quartz inclusions used for quartz-in-garnet (QuiG) elastic thermobarometry. Systematic changes of the 128, 206 and 464 cm^?1 Raman band frequencies of quartz were used to determine pressures of quartz inclusions in garnet using Raman spectroscopy calibrations that describe the P–T dependencies of Raman band shifts for quartz under hydrostatic pressure. Within analytical uncertainties, inclusion pressures calculated for each of the three Raman band frequencies are equivalent, which suggests that non-hydrostatic stress effects caused by elastic anisotropy in quartz are smaller than measurement errors. The experimental quartz inclusions have pressures ranging from ??0.351 to 1.247 GPa that span the range of values observed for quartz inclusions in garnets from natural rocks. Quartz inclusion pressures were used to model P–T conditions at which the inclusions could have been trapped. The accuracy of QuiG thermobarometry was evaluated by considering the differences between pressures measured during experiments and pressures calculated using published equation of state parameters for quartz and garnet. Our experimental results demonstrate that Raman measurements performed at room temperature can be used without corrections to estimate garnet crystallization pressures. Calculated entrapment pressures for quartz inclusions in garnet are less than ~?10% different from pressures measured during the experiments. Because the method is simple to apply with reasonable accuracy, we expect widespread usage of QuiG thermobarometry to estimate crystallization conditions for garnet-bearing silicic rocks.     

Electrical conductivity of the plagioclase–NaCl–water system and its implication for the high conductivity anomalies in the mid-lower crust of Tibet Plateau

In order to investigate the origin of the high conductivity anomalies geophysically observed in the mid-lower crust of Tibet Plateau, the electrical conductivity of plagioclase–NaCl–water system was measured at 1.2 GPa and 400–900 K. The relationship between electrical conductivity and temperature follows the Arrhenius law. The bulk conductivity increases with the fluid fraction and salinity, but is almost independent of temperature (activation enthalpy less than 0.1 eV). The conductivity of plagioclase–NaCl–water system is much lower than that of albite–NaCl–water system with similar fluid fraction and salinity, indicating a strong effect of the major mineral phase on the bulk conductivity of the brine-bearing system. The high conductivity anomalies of 10^?1 and 10⁰ S/m observed in the mid-lower crust of Tibet Plateau can be explained by the aqueous fluid with a volume fraction of 1 and 9%, respectively, if the fluid salinity is 25%. The anomaly value of 10^?1 S/m can be explained by the aqueous fluid with a volume fraction of 6% if the salinity is 10%. In case of Southern Tibet where the heat flow is high, the model of a thin layer of brine-bearing aqueous fluid with a high salinity overlying a thick layer of partial melt is most likely to prevail.     

An experimental study of Fe–Ni exchange between sulfide melt and olivine at upper mantle conditions: implications for mantle sulfide compositions and phase equilibria

The behavior of nickel in the Earth’s mantle is controlled by sulfide melt–olivine reaction. Prior to this study, experiments were carried out at low pressures with narrow range of Ni/Fe in sulfide melt. As the mantle becomes more reduced with depth, experiments at comparable conditions provide an assessment of the effect of pressure at low-oxygen fugacity conditions. In this study, we constrain the Fe–Ni composition of molten sulfide in the Earth’s upper mantle via sulfide melt–olivine reaction experiments at 2 GPa, 1200 and 1400 °C, with sulfide melt \(X_{{{\text{Ni}}}}^{{{\text{Sulfide}}}}=\frac{{{\text{Ni}}}}{{{\text{Ni}}+{\text{Fe}}}}\) (atomic ratio) ranging from 0 to 0.94. To verify the approach to equilibrium and to explore the effect of \({f_{{{\text{O}}_{\text{2}}}}}\) on Fe–Ni exchange between phases, four different suites of experiments were conducted, varying in their experimental geometry and initial composition. Effects of Ni secondary fluorescence on olivine analyses were corrected using the PENELOPE algorithm (Baró et al., Nucl Instrum Methods Phys Res B 100:31–46, 1995), “zero time” experiments, and measurements before and after dissolution of surrounding sulfides. Oxygen fugacities in the experiments, estimated from the measured O contents of sulfide melts and from the compositions of coexisting olivines, were 3.0?±?1.0 log units more reduced than the fayalite–magnetite-quartz (FMQ) buffer (suite 1, 2 and 3), and FMQ ??1 or more oxidized (suite 4). For the reduced (suites 1–3) experiments, Fe–Ni distribution coefficients \(K_{{\text{D}}}^{{}}=\frac{{(X_{{{\text{Ni}}}}^{{{\text{sulfide}}}}/X_{{{\text{Fe}}}}^{{{\text{sulfide}}}})}}{{(X_{{{\text{Ni}}}}^{{{\text{olivine}}}}/X_{{{\text{Fe}}}}^{{{\text{olivine}}}})}}\) are small, averaging 10.0?±?5.7, with little variation as a function of total Ni content. More oxidized experiments (suite 4) give larger values of K_D (21.1–25.2). Compared to previous determinations at 100 kPa, values of K_D from this study are chiefly lower, in large part owing to the more reduced conditions of the experiments. The observed difference does not seem attributable to differences in temperature and pressure between experimental studies. It may be related in part to the effects of metal/sulfur ratio in sulfide melt. Application of these results to the composition of molten sulfide in peridotite indicates that compositions are intermediate in composition (\(X_{{{\text{Ni}}}}^{{{\text{sulfide}}}}\)?~?0.4–0.6) in the shallow mantle at 50 km, becomes more Ni rich with depth as the O content of the melt diminishes, reaching a maximum (0.6–0.7) at depths near 80–120 km, and then becomes more Fe rich in the deeper mantle where conditions are more reduced, approaching (\(X_{{{\text{Ni}}}}^{{{\text{sulfide}}}}\)?~?0.28)?>?140 km depth. Because Ni-rich sulfide in the shallow upper mantle melts at lower temperature than more Fe-rich compositions, mantle sulfide is likely molten in much of the deep continental lithosphere, including regions of diamond formation.     

Experimental calibration of vanadium partitioning and stable isotope fractionation between hydrous granitic melt and magnetite at 800 °C and 0.5 GPa

Vanadium has multiple oxidation states in silicate melts and minerals, a property that also promotes fractionation of its isotopes. As a result, vanadium isotopes vary during magmatic differentiation, and can be powerful indicators of redox processes at high temperatures if their partitioning behaviour can be determined. To quantify the partitioning and isotope fractionation factor of V between magnetite and melt, piston cylinder experiments were performed in which magnetite and a hydrous, haplogranitic melt were equilibrated at 800 °C and 0.5 GPa over a range of oxygen fugacities (\({f_{{{\text{O}}_{\text{2}}}}}\)), bracketing those of terrestrial magmas. Magnetite is isotopically light with respect to the coexisting melt, a tendency ascribed to the VI-fold V³⁺ and V⁴⁺ in magnetite, and a mixture of IV- and VI-fold V⁵⁺ and V⁴⁺ in the melt. The magnitude of the fractionation factor systematically increases with increasing log\({f_{{{\text{O}}_{\text{2}}}}}\) relative to the Fayalite–Magnetite–Quartz buffer (FMQ), from ?⁵¹V_mag-gl = ? 0.63?±?0.09‰ at FMQ ? 1 to ? 0.92?±?0.11‰ (SD) at ≈?FMQ?+?5, reflecting constant V³⁺/V⁴⁺ in magnetite but increasing V⁵⁺/V⁴⁺ in the melt with increasing log\({f_{{{\text{O}}_{\text{2}}}}}\). These first mineral-melt measurements of V isotope fractionation factors underline the importance of both oxidation state and co-ordination environment in controlling isotopic fractionation. The fractionation factors determined experimentally are in excellent agreement with those needed to explain natural isotope variations in magmatic suites. Furthermore, these experiments provide a useful framework in which to interpret vanadium isotope variations in natural rocks and magnetites, and may be used as a potential fingerprint the redox state of the magma from which they crystallise.     

Petrogenesis of low-δ<Superscript>18</Superscript>O quartz porphyry dykes,Koegel Fontein complex,South Africa

This paper investigates the origin of low-δ¹⁸O quartz porphyry dykes associated with the 144–133 Ma Koegel Fontein Igneous Complex, which was intruded during the initial phase of breakup of Africa and South America. The 25-km diameter Rietpoort Granite is the largest and youngest phase of activity, and is roofed by a 10-km diameter pendant of gneiss. Quartz porphyry (QP) dykes, up to 15 m in width, strike NW–SE across the complex. The QP dykes that intruded outside the granite have similar quartz phenocryst δ¹⁸O values (average 8.0‰, ± 0.7, n?=?33) to the granite (average 8.3?±?1.0, n?=?7). The QP dykes that intruded the roof pendant have quartz phenocrysts with more variable δ¹⁸O values (average 1.6‰, ± 2.1, n?=?55). In some cases quartz phenocrysts have δ¹⁸O values as low as ? 2.5‰. The variation in δ¹⁸O value within the quartz crystal population of individual dykes is small relative to the overall range, and core and rim material from individual quartz phenocrysts in three samples are identical within error. There is no evidence that quartz phenocryst δ¹⁸O values have been affected by fluid–rock interaction. Based on a ?_quartz?magma value of 0.6‰, magma δ¹⁸O values must have been as low as ? 3.1‰. Samples collected along the length of the two main QP dykes that traverse the roof pendant have quartz phenocryst δ¹⁸O values that range from +?1.1 to +?4.6‰, and ? 2.3 to +?5.6‰, respectively. These δ¹⁸O values correlate negatively (r = ? 0.96) with initial ⁸⁷Sr/⁸⁶Sr, which can be explained by the event that lowered δ¹⁸O values of the source being older than the dykes. We suggest that the QP dykes were fed by magma produced by partial melting of gneiss, which had been variably altered at high temperature by ¹⁸O-depleted meteoric water during global glaciation at ~?550 Ma. The early melts had variable δ¹⁸O value but as melt pockets interconnected during melting, the δ¹⁸O values approached that of average gneiss. Variable quartz phenocryst δ¹⁸O values in the same dyke can be explained by vertical emplacement, at variable rates of ascent along the dyke. The lateral variation in quartz, and hence magma δ¹⁸O value at a particular point along a single dyke would depend on the rate of ascent of magma at that point along the dyke, and the ‘age’ of the particular magma batch.     

Textural and micro-analytical insights into mafic–felsic interactions during the Oruanui eruption,Taupo

Quenched juvenile mafic inclusions (enclaves) are an occasional but informative component in the deposits of large felsic eruptions. Typically, the groundmasses of these inclusions rapidly crystallize as the mafic magma is chilled against a more voluminous, cooler felsic host, providing a physical and chemical record of the nature and timing of mafic–felsic interactions. We examine mafic inclusions of two compositional lineages (tholeiitic and calc-alkaline) from deposits of the 25.4 ka Oruanui eruption (Taupo, New Zealand). 2-D quantitative textural data from analysis of back-scattered electron images reveal a marked diversity in the groundmass textures of the inclusions, including median crystal sizes (amphibole: 14–45 µm; plagioclase: 21–75 µm) and aspect ratios (amphibole: 1.7–4.2; plagioclase: 2.1–4.0), area number densities (amphibole: 122–2660 mm^?2; plagioclase: 117–2990 mm^?2), area fractions (?) of minerals (?_plag?=?23–45%, ?_amph?=?0–28%, ?_cpx?=?0–6%, ?_oxides?=?0.6–5.5%), and the relative abundance of plagioclase and amphibole (?_plag/?_amph?=?1.0–4.6). Textural parameters vary more significantly within, rather than between, the two compositional lineages, and in some cases show marked variations across individual clasts, implying that each inclusion’s cooling history, rather than bulk composition, was the dominant control on textural development. Groundmass mineral compositions are also diverse both within and between inclusions (e.g. plagioclase from An_34–92, with typical intra-clast variability of ~?20 mol%), and do not correlate with bulk chemistry. Diverse groundmass textures and mineral and glass chemistries are inferred to reflect complex interplay of a range of factors including the degree and rate of undercooling, bulk composition, water content and, possibly, intensive variables. Our data are inconsistent with breakup of a crystallizing ponded mafic layer at the base of the Oruanui melt-dominant body, instead implying that each inclusion partially crystallized as a discrete body with a unique cooling history. Extensive ingestion of mush-derived macro-crystals suggests that mechanical breakup of mafic feeder dikes occurred within a transition zone between the mush and melt-dominant magma body. In this zone, the mush lacked yield strength, as has been inferred from field studies of narrow (meters to few tens of meters) mush-melt transition zones preserved in composite intrusions. Evidence for plastic deformation of inclusions during eruption and the abundance of fresh residual glass in inclusions from all eruptive phases suggest that the inclusions formed syn-eruptively, and must have been formed recurrently at multiple stages throughout the eruption.