Bruno Scaillet

Evidence for mantle metasomatism by hydrous silicic melts derived from subducted oceanic crust.

The low concentrations of niobium, tantalum and titanium observed in island-arc basalts are thought to result from modification of the sub-arc mantle by a metasomatic agent, deficient in these elements, that originates from within the subducted oceanic crust. Whether this agent is an hydrous fluid or a silica-rich melt has been discussed using mainly a trace-element approach and related to variable thermal regimes of subduction zones. Melting of basalt in the absence of fluid both requires high temperatures and yields melt compositions unlike those found in most modern or Mesozoic island arcs. Thus, metasomatism by fluids has been thought to be the most common situation. Here, however, we show that the melting of basalt under both H2O-added and low-temperature conditions can yield extremely alkali-rich silicic liquids, the alkali content of which increases with pressure. These liquids are deficient in titanium and in the elements niobium and tantalum and are virtually identical to glasses preserved in mantle xenoliths found in subduction zones and to veins found in exhumed metamorphic terranes of fossil convergent zones. We also found that the interaction between such liquids and mantle olivine produces modal mineralogies that are identical to those observed in metasomatized Alpine-type peridotites. We therefore suggest that mantle metasomatism by slab-derived melt is a more common process than previously thought.

Carbonatite Melts and Electrical Conductivity in the Asthenosphere

Electrically conductive regions in Earths mantle have been interpreted to reflect the presence of either silicate melt or water dissolved in olivine. On the basis of laboratory measurements, we show that molten carbonates have electrical conductivities that are three orders of magnitude higher than those of molten silicate and five orders of magnitude higher than those of hydrated olivine. High conductivities in the asthenosphere probably indicate the presence of small amounts of carbonate melt in peridotite and can therefore be interpreted in terms of carbon concentration in the upper mantle. We show that the conductivity of the oceanic asthenosphere can be explained by 0.1 volume percent of carbonatite melts on average, which agrees with the carbon dioxide content of mid-ocean ridge basalts.

Decadal to monthly timescales of magma transfer and reservoir growth at a caldera volcano

Caldera-forming volcanic eruptions are low-frequency, high-impact events capable of discharging tens to thousands of cubic kilometres of magma explosively on timescales of hours to days, with devastating effects on local and global scales. Because no such eruption has been monitored during its long build-up phase, the precursor phenomena are not well understood. Geophysical signals obtained during recent episodes of unrest at calderas such as Yellowstone, USA, and Campi Flegrei, Italy, are difficult to interpret, and the conditions necessary for large eruptions are poorly constrained. Here we present a study of pre-eruptive magmatic processes and their timescales using chemically zoned crystals from the ‘Minoan’ caldera-forming eruption of Santorini volcano, Greece, which occurred in the late 1600s bc. The results provide insights into how rapidly large silicic systems may pass from a quiescent state to one on the edge of eruption. Despite the large volume of erupted magma (40–60 cubic kilometres), and the 18,000-year gestation period between the Minoan eruption and the previous major eruption, most crystals in the Minoan magma record processes that occurred less than about 100 years before the eruption. Recharge of the magma reservoir by large volumes of silicic magma (and some mafic magma) occurred during the century before eruption, and mixing between different silicic magma batches was still taking place during the final months. Final assembly of large silicic magma reservoirs may occur on timescales that are geologically very short by comparison with the preceding repose period, with major growth phases immediately before eruption. These observations have implications for the monitoring of long-dormant, but potentially active, caldera systems.

Redox control of sulfur degassing in silicic magmas

Explosive eruptions involve mainly silicic magmas in which sulfur solubility and diffusivity are low. This inhibits sulfur exsolution during magma uprise as compared to more mafic magmas such as basalts. Silicic magmas can nevertheless liberate large quantities of sulfur as shown by the monitoring of SO 2 in recent explosive silicic eruptions in arc settings, which invariably have displayed an excess of sulfur relative to that calculated from melt degassing. If this excess sulfur is stored in a fluid phase, it implies a strong preference of sulfur for the fluid over the melt under oxidized conditions, with fluid/melt partition coefficients varying between 50 and 2612, depending on melt composition. Experimentally determined sulfur partition coefficients for a dacite bulk composition confirm this trend and show that in volcanic eruptions displaying excess gaseous sulfur, the magmas were probably fluid-saturated at depth. The experiments show that in more reduced silicic magmas, those coexisting only with pyrrhotite, the partition coefficient decreases dramatically to values around 1, because pyrrhotite locks up nearly all the sulfur of the magma. Reevaluation of the sulfur yields of some major historical eruptions in the light of these results shows that for oxidized magmas, the presence of 1-5 wt % fluid may indeed account for the differences observed between the petrologic estimate of the sulfur yield and that constrained from ice core data. Explosive eruptions of very large magnitude but involving reduced and cool silicic magmas, such as the Toba or the Bishop events, release only minor amounts of sulfur and could have consequently negligible long-term (years to centuries) atmospherical effects. This redox control on sulfur release diminishes as the melt composition becomes less silicic and as temperature increases, because both factors favor more efficient melt sulfur degassing owing to the increased diffusivity of sulfur in silicate melts under such conditions.

Redox evolution of a degassing magma rising to the surface

Volatiles carried by magmas, either dissolved or exsolved, have a fundamental effect on a variety of geological phenomena, such as magma dynamics and the composition of the Earth’s atmosphere. In particular, the redox state of volcanic gases emanating at the Earth’s surface is widely believed to mirror that of the magma source, and is thought to have exerted a first-order control on the secular evolution of atmospheric oxygen. Oxygen fugacity (fO2) estimated from lava or related gas chemistry, however, may vary by as much as one log unit, and the reason for such differences remains obscure. Here we use a coupled chemical–physical model of conduit flow to show that the redox state evolution of an ascending magma, and thus of its coexisting gas phase, is strongly dependent on both the composition and the amount of gas in the reservoir. Magmas with no sulphur show a systematic fO2 increase during ascent, by as much as 2 log units. Magmas with sulphur show also a change of redox state during ascent, but the direction of change depends on the initial fO2 in the reservoir. Our calculations closely reproduce the H2S/SO2 ratios of volcanic gases observed at convergent settings, yet the difference between fO2 in the reservoir and that at the exit of the volcanic conduit may be as much as 1.5 log units. Thus, the redox state of erupted magmas is not necessarily a good proxy of the redox state of the gases they emit. Our findings may require re-evaluation of models aimed at quantifying the role of magmatic volatiles in geological processes.

Effects of f O2 and H2O on andesite phase relations between 2 and 4 kbar

Experimental phase equilibria have been investigated on three medium-K silicic andesite (60–61 wt % SiO2) samples from Mount Pelee at 2–4 kbar, 850–1040°C, under both vapor-saturated CO2-free and vapor-saturated CO2-bearing conditions. Most experiments were crystallization experiments using dry glasses prepared from the natural rocks. Both normal- and rapid quench experiments were performed. Two ranges of oxygen fugacity (fO2) were investigated: NNO (Ni-NiO buffer) to NNO + 1 and NNO + 2 to NNO + 3. At 2 kbar for moderately oxidizing conditions, plagioclase (pl) and magnetite (mt) are the liquidus phases, followed by low-Ca pyroxene (opx); these three phases coexist over a large temperature (T)-H2O range (875–950°C and 5–7 wt % H2O in melt). Amphibole (am) is stable under near vapor-saturated CO2-free conditions at 876°C. At 900°C, ilmenite (ilm) is found only in experiments less than or equal to NNO. Upon increasing pressure (P) under vapor-saturated CO2-free conditions, pl + mt is replaced by am + mt on the liquidus above 3.5 kbar. For highly oxidizing conditions, mt is the sole liquidus phase at 2 kbar, followed by pl and opx, except in the most H2O-rich part of the diagram at 930°C, where opx is replaced by Ca-rich pyroxene (cpx) and am. Compositions of ferromagnesian phases systematically correlate with changingfO2 Experimental glasses range from andesitic through dacitic to rhyolitic, showing systematic compositional variations with pl + opx + mt fractionation (increase of SiO2 and K2O, decrease of Al2O3, CaO, FeOt, and MgO). FeO*/MgO moderately increases with increasing SiO2. For fO2 conditions typical of calk-alkaline magmatism (approximately NNO + 1), magnetite is either a liquidus or a near-liquidus phase in hydrous silicic andesite magmas, and this should stimulate reexamination for the mechanisms of generation of andesites by fractionation from basaltic parents.

Phase equilibrium constraints on the viscosity of silicic magmas: 1. Volcanic‐plutonic comparison

By using recently determined experimental phase equilibria we show that the viscosity of granitic magmas emplaced at upper crustal levels is approximately constant at ∼104.5 Pa s, irrespective of their temperature and level of emplacement. Magmas crystallizing as granitic plutons are not water-poor and thus not more viscous than their extrusive equivalents. Instead, comparison between pre-eruption magma viscosities of extrusive silicic-intermediate and intrusive granitic magmas shows that the former are on average slightly more viscous. Given the typical strain rates in silicic magma chambers, magma rheological behavior is expected to be dominantly Newtonian, bubbles having a minor rheological influence at depth although exceptions can exist. Thus whether a silicic-intermediate magma is erupted or frozen at depth depends primarily on the rheological properties of surrounding terranes or on external tectonic factors, but not on the rheology of the magma itself. However, preemptive viscosities of extrusive magmas rarely exceed 106 Pa.s, which suggests that crystal-melt mushes with higher viscosities cannot leave the magma storage regions beneath volcanoes. The narrow range of viscosities displayed by silicic-intermediate magmas results from both the strong control that pressure exerts on volatile solubilities in silicate melts and thermal limitations required to produce acid magmas. Considerations of the relationships between magma crystallinities, bulk SiO2, and preemptive melt H2O contents show that the higher the melt H2O content is the higher the maximum crystallinity that a given magma will be while still being potentially erupted. An empirical correlation is proposed that enables us to estimate preemptive melt H2O contents of erupted magmas by knowing their crystallinity and bulk SiO2.

Atmospheric oxygenation caused by a change in volcanic degassing pressure

The Precambrian history of our planet is marked by two major events: a pulse of continental crust formation at the end of the Archaean eon and a weak oxygenation of the atmosphere (the Great Oxidation Event) that followed, at 2.45 billion years ago. This oxygenation has been linked to the emergence of oxygenic cyanobacteria and to changes in the compositions of volcanic gases, but not to the composition of erupting lavas—geochemical constraints indicate that the oxidation state of basalts and their mantle sources has remained constant since 3.5 billion years ago. Here we propose that a decrease in the average pressure of volcanic degassing changed the oxidation state of sulphur in volcanic gases, initiating the modern biogeochemical sulphur cycle and triggering atmospheric oxygenation. Using thermodynamic calculations simulating gas–melt equilibria in erupting magmas, we suggest that mostly submarine Archaean volcanoes produced gases with SO2/H2S < 1 and low sulphur content. Emergence of the continents due to a global decrease in sea level and growth of the continental crust in the late Archaean then led to widespread subaerial volcanism, which in turn yielded gases much richer in sulphur and dominated by SO2. Dissolution of sulphur in sea water and the onset of sulphate reduction processes could then oxidize the atmosphere.

Magma storage conditions and control of eruption regime in silicic volcanoes: experimental evidence from Mt. Pelée

Differences of eruption regimes in silicic volcanoes, e.g. effusive versus explosive, have commonly been ascribed either to stratification of volatiles in the magma storage region or to gas loss through permeable conduit walls. Recent Plinian and Pelean eruptions of silicic andesite magmas from Mt. Pelee (P1: 650 yr B.P., 1902, 1929) show no systematic variations in bulk rock and phenocryst and glass compositions. Rare coexisting Fesingle bondTi oxide pairs in Pelean products yieldT between 840 and 902°C, and ΔNNO between +0.4 and +0.8. Pre-eruptive melt H2O contents, calculated from plagioclase-melt equilibria, span values from 1.9 to 5.5 wt%. Glass inclusions from the P1 Plinian fallout have H2O contents between 4.2 and 7.1 wt%. In contrast, the Pelean inclusions have H2O contents commonly <3 wt%, due to post-entrapment modifications upon eruption. Phase equilibrium studies allow pre-eruptive conditions to be precisely determined and demonstrate that recent eruptions, either Plinian or Pelean, tapped magmas with melt H2O contents of 5.3-6.3 wt%, stored at 2 ± 0.5 kbar, 875-900°C and ΔNNO = +0.4-0.8. Differences in eruptive style at Mt. Pelee are unrelated to systematic variations in pre-eruptive magmatic H2O concentrations, but may be caused by contrasting modes of degassing in the conduit.

Badrinath-Gangotri plutons (Garhwal, India):petrological and geochemical evidence for fractionation processes in a high Himalayan leucogranite.

The Gangotri leucogranite is the western end of the Badrinath granite, one of the largest bodies of the High Himalayan Leucogranite belt (HHL). It is a typical fine grained tourmaline + muscovite ± biotite leucogranite. The petrography shows a lack of restitic phases. The inferred crystallization sequence is characterized by the early appearance of plagioclase, quartz and biotite and by the late crystallization of the K-feldspar. This suggests that, in spite of being of near minimum melt composition, the granite probably had long crystallization or melting interval, in agreement with previous experimental studies. Tourmaline and muscovite have a mainly magmatic origin. Even though the major element composition is homogeneous, there are several geochemical trends (when CaO decreases there is an increase in Na2O, Rb, Sn, U, B, F and a decrease in K2O, Fe2O3, TiO2, Sr, Ba, Zr, REE, Th) which are best explained by a fractionation process with early crystallizing phases. Experimental solubility models for zircon and monazite in felsic melt support a magmatic origin for these two accessory phases as well. Rb/Sr isotope data show this granite to have, like other HHL, heterogeneous isotopic values for Sr (initial 87Sr/86Sr ratios, calculated at 20 Ma, range between 0.765 and 0.785). Therefore no mixing (i.e. no convection) occurred between the different batches of magma. In contrast 18O data show little variation (13.04% ± 0.25), implying a source with homogeneous 18O values. Differences in timing between fluid infiltration and the onset of melting, related to differences in temperature of the source, could explain why source homogenization occurred for the Gangotri and not for the Manaslu granite. The use of experimental results for solubility and the position of the accessory minerals during melting, predict a low viscosity for the melt during its extraction. This in turn explains the lack of restitic phases (major and accessory) in the granite as well as some field features (lensoid shape, pronounced magmatic layering). Based on the petrographic and isotopic studies, it is suggested that the mechanism of ascent was not diapiric but rather that the melt ascended along several fractures and the level of emplacement was partialy controlled by the density contrast between the melt and host rocks.