Plume chemistry provides insights into mechanisms of sulfur and halogen degassing in basaltic volcanoes

This paper deals with sulfur, chlorine and fluorine abundances in the eruptive volcanic plume of the huge October 2002-January 2003 eruption of Mount Etna, aiming at relating the relevant compositional variations observed throughout with changes in eruption dynamics and degassing mechanisms. The recurrent sampling of plume acidic volatiles by filter-pack methodology revealed that, during the study period, S/Cl and Cl/F ratios ranged from 0.1-6.8 and 0.9-5.6, respectively. Plume S/Cl ratios increased by a factor of ∼10 as volcanic activity drifted from paroxysmal lava fountaining (mid- and late November) to passive degassing and minor effusion (early January), and then decreased to the low values (S/Cl=0.1) typical of the final stages of the eruption. Parallel variations in chlorine to fluorine ratios were also observed. A theoretical model is proposed for quantitative interpretation of these changes in plume composition. The model calculates the composition of a volatile phase exsolving from an ascending Etna magma, based on knowledge of solubilities and abundances in the undegassed melt of sulfur and halogens [T.M. Gerlach, EOS 72 (1991), 249, 254-255]. According to this model, degassing of Etnean basaltic melt at high pressures and depths (>100 MPa, 3 km) is likely to release a CO₂+H₂O-rich vapor phase with S/Cl molar ratios ∼1. Extensive sulfur and chlorine degassing from the melt would take place at shallower depth (P<20 MPa, 0.6 km), with S/Cl ratios in the vapor phase increasing as pressure drops to 0.1 MPa. Comparisons between model compositions and volcanic plume data demonstrate that the chemical trends observed during the eruption may be explained by increased degassing due to depressurization of a basaltic magma batch ascending toward the surface.     

Sulfur and chlorine degassing from primitive arc magmas: temporal changes during the 1982–1983 eruptions of Galunggung (West Java, Indonesia)

The 1982–1983 eruptions of Galunggung represent a nine-month period of intermittent volcanic activity with significant changes in explosivity and emission of volatiles. Eruptions started with Vulcanian explosions but changed gradually to Strombolian activity. Compositions of juvenile material changed from basaltic andesite to high-Mg basalt, which are among the most primitive rock types known in the Indonesian arc system. Although bulk compositions suggest a single evolution trend, we infer from the compositions of melt inclusions in olivine phenocrysts that the magmas represent derivatives of a complex spectrum of primary melts. Primitive inclusions in olivine phenocrysts from magma erupted during the Strombolian phase contain up to 2000 ppm sulfur, but concentrations decrease rapidly with increasing SiO₂ down to matrix glass values (50–100 ppm). ‘Vulcanian’ inclusions appear to be degassed before eruption (200 ppm S). Chlorine concentrations increase from 750 to 2200 ppm in Strombolian, and from 800 to 1500 in Vulcanian magmas, whereas matrix glass contains about 1000 ppm in both cases. Ash leachates show two cycles of decreasing S/Cl ratios: from 9.7 to 5.6 at the start of the activity, and from 12.2 to 2.0 after four months. As the second cycle follows upon increased seismic activity at shallow depth, it probably reflects degassing of fresh sulfur-rich magma arriving in the shallow Galunggung reservoir. In contrast to the degassed state of Vulcanian magma, the significant amounts of adsorbed sulfur on the ashes point to an excess source of sulfur, which was most likely derived from intruding Strombolian magma. Hence, the observed sulfur flux of 2 Mt is not in accordance with a petrologic estimate of 0.09 Mt. Using a published value of 550 Mt of erupted material about 0.34 km³ fresh undegassed magma is needed to account for the observed sulfur flux. This is close to the erupted volume of Vulcanian magma (0.26 km³), which presumably was replaced completely by Strombolian magma during the eruption. Using the petrologic method, we calculate a total release of 0.3 Mt chlorine, which agrees well with an output of 0.47 Mt estimated independently from S/Cl ratios of the ash leachates and TOMS sulfur yields. Ash leachates show that about 35% of the sulfur and 30% of the chlorine was scavenged from the eruption plumes. Our results suggest that sulfur and chlorine were largely decoupled during degassing, which resulted in considerable variations in S/Cl ratios during the Galunggung eruptions. We infer that sulfur degassing reflects the arrival of fresh magma at shallow depth, whereas chlorine is largely derived from simultaneously erupted material. As a consequence, the petrologic estimates are more consistent with observed emissions for chlorine than for sulfur.     

Petrology and sulfur and chlorine emissions of the 1963 eruption of Gunung Agung,Bali, Indonesia

 The 1963 eruption of Gunung Agung produced 0.95 km³ dense rock equivalent (DRE) of olivine±hornblende-bearing, weakly phyric, basaltic andesite tephra and lava. Evidence for magma mixing in the eruptive products includes whole-rock compatible and incompatible trace element trends, reverse and complex compositional zoning of mineral phases, disequilibrium mineral assemblages, sieve-textured plagioclase phenocrysts, and augite rims on reversely zoned orthopyroxene. Basalt magma mixed with pre-existing andesite magma shortly before eruption to yield basaltic andesite with a temperature of 1040–1100  °C at an assumed pressure of 2 kb, f O₂>NNO, and an average melt volatile content (H₂O±CO₂) of 4.3 wt.%. Magma-mixing end members may have provided some of the S and Cl emitted in the eruption. Glass inclusions in phenocrysts contain an average of 650 ppm S and 3130 ppm Cl as compared with 70 ppm and 2220 ppm, respectively, in the matrix glass. Maximum S and Cl contents of glass inclusions approach 1800 and 5000 ppm, respectively. Application of the petrologic method to products of the 1963 eruption for estimating volatile release yields of 2.5×10¹²g (Mt) of SO₂ and 3.4 Mt of Cl released from the 0.65 km³ of juvenile tephra which contributed to stratospheric injection of H₂SO₄ aerosols on 17 March and 16 May, when eruption column heights exceeded 20 km above sea level. An independent estimate of SO₂ release from atmospheric aerosol loading (11–12 Mt) suggests that approximately 7 Mt of SO₂ was injected into the stratosphere. The difference between the two estimates can be most readily accounted for by the partitioning of S, as well as some Cl, from the magma into a water-rich vapor phase which was released upon eruption. For other recent high-S-release eruptions of more evolved and oxidized magmas (El Chichón, Pinatubo), the petrologic method gives values two orders of magnitude less than independent estimates of SO₂ emissions. Results from this study of the Agung 1963 magma and its volatile emissions, and from related studies on eruptions of more mafic magmas, suggest that SO₂ emissions from eruptions of higher-S-solubility magma may be more reliably estimated by the petrologic method than may those from more-evolved magma eruptions. Received: 29 June 1994 / Accepted: 25 April 1996     

Variation of volatile concentration in a magma system of Satsuma-Iwojima volcano deduced from melt inclusion analyses

Chemical analyses of 30 melt inclusions from Satsuma-Iwojima volcano, Japan, were carried out to investigate volatile evolution in a magma chamber beneath the volcano from about 6300 yr BP to the present. Large variations in volatile concentrations of melts were observed. (1) Water concentration of rhyolitic melts decreases with time; 3–4.6 wt.% at the time of latest caldera-forming eruption of Takeshima pyroclastic flow deposit (ca. 6300 yr BP), 3 wt.% for small pyroclastic flow (ca. 1300 yr BP) of Iwodake, post-caldera rhyolitic dome, and 0.7–1.4 wt.% for submarine lava eruption (Showa-Iwojima) in 1934. (2) Rhyolitic melts of the Takeshima and Iwodake eruptions contained CO₂ of less than 40 ppm, while the Showa-Iwojima melt has higher CO₂ concentration of up to 140 ppm. (3) Water and CO₂ concentrations of basaltic to andesitic melt of Inamuradake, a post-caldera basaltic scoria cone, are 1.2–2.8 wt.% and ≤290 ppm, respectively.Volatile evolution in the magma chamber is interpreted as follows: (1) the rhyolitic magma at the time of the latest caldera-forming eruption (ca. 6300 yr BP) was gas-saturated due to pressure variation in the magma chamber because the large variation in water concentration of the melt was attributed to exsolution of volatile in the magma prior to the eruption. Iwodake eruption (ca. 1300 yr BP) was caused by a remnant of the caldera-forming rhyolitic magma, suggested from the similarity of major element composition between these magmas. (2) Volatile composition of the Showa-Iwojima rhyolitic melt agrees with that of magmatic gases presently discharging from a summit of Iwodake, indicating the low pressure degassing condition. (3) The degassing of the magma chamber by magma convection in a conduit of Iwodake during non-eruptive but active degassing period for longer than 800 years decreased water concentration of the rhyolitic magma. (4) Geological and petrological observations indicate that a stratified magma chamber, which consists of a lower basaltic layer and an upper rhyolitic layer, might have existed during the post-caldera stage. Addition of CO₂ from the underlying basaltic magma to the upper gas-undersaturated (degassed) rhyolitic magma increased CO₂ concentration of the rhyolitic magma.     

Magma degassing and basaltic eruption styles: a case study of 2000 year BP Xitle volcano in central Mexico

To investigate the relationship between volatile abundances and eruption style, we have analyzed major element and volatile (H₂O, CO₂, S) concentrations in olivine-hosted melt inclusions in tephra from the 2000 yr BP eruption of Xitle volcano in the central Trans-Mexican Volcanic Belt. The Xitle eruption was dominantly effusive, with fluid lava flows accounting for 95% of the total dense rock erupted material (1.1 km³). However, in addition to the initial, Strombolian, cinder cone-building phase, there was a later explosive phase that interrupted effusive activity and deposited three widespread ash fall layers. Major element compositions of olivine-hosted melt inclusions from these ash layers range from 52 to 58 wt.% SiO₂, and olivine host compositions are Fo_84–86. Water concentrations in the melt inclusions are variable (0.2–1.3 wt.% H₂O), with an average of 0.45±0.3 (1σ) wt.% H₂O. Sulfur concentrations vary from below detection (50 ppm) to 1000 ppm but are mostly ≤200 ppm and show little correlation with H₂O. Only the two inclusions with the highest H₂O have detectable CO₂ (310–340 ppm), indicating inclusion entrapment at higher pressures (700–900 bars) than for the other inclusions (≤80 bars). The low and variable H₂O and S contents of melt inclusions combined with the absence of less soluble CO₂ indicates shallow-level degassing before olivine crystallization and melt inclusion formation. Olivine morphologies are consistent with the interpretation that most crystallization occurred rapidly during near-surface H₂O loss. During cinder cone eruptions, the switch from initial explosive activity to effusive eruption probably occurs when the ascent velocity of magma becomes slow enough to allow near-complete degassing of magma at shallow depths within the cone as a result of buoyantly rising gas bubbles. This allows degassed lavas to flow laterally and exit near the base of the cone while gas escapes through bubbly magma in the uppermost part of the conduit just below the crater. The major element compositions of melt inclusions at Xitle show that the short-lived phase of renewed explosive activity was triggered by a magma recharge event, which could have increased overpressure in the storage reservoir beneath Xitle, leading to increased ascent velocities and decreased time available for degassing during ascent.     

Petrological characteristics and volatile content of magma from the 2000 eruption of Miyakejima Volcano, Japan

Among the series of eruptions at Miyakejima volcano in 2000, the largest summit explosion occurred on 18 August 2000. During this explosion, vesiculated bombs and lapilli having cauliflower-like shapes were ejected as essential products. Petrological observation and chemical analyses of the essential ejecta and melt inclusions were carried out in order to investigate magma ascent and eruption processes. SEM images indicate that the essential bombs and lapilli have similar textures, which have many tiny bubbles, crystal-rich and glass-poor groundmass and microphenocrysts of plagioclase, augite and olivine. Black ash particles, which compose 40% of the air-fall ash from the explosion, also have similar textures to the essential bombs. Whole-rock analyses show that the chemical composition of all essential ejecta is basaltic (SiO₂=51–52 wt%). Chemical analyses of melt inclusions in plagioclase and olivine phenocrysts indicate that melt in the magma had 0.9–1.9 wt% H₂O, <0.011 wt% CO₂, 0.04–0.17 wt% S and 0.06–0.1 wt% Cl. The variation in volatile content suggests degassing of the magma during ascent up to a depth of about 1 km. The ratio of H₂O and S content of melt inclusions is similar to that of volcanic gas, which has been intensely and continuously emitted from the summit since the end of August 2000, indicating that the 18 August magma is the source of the gas emission. Based on the volatile content of the melt inclusions and the volcanic gas composition, the initial bulk volatile content of the magma was estimated to be 1.6–1.9 wt% H₂O, 0.08–0.1 wt% CO₂, 0.11–0.17 wt% S and 0.06–0.07 wt% Cl. The basaltic magma ascended from a deeper chamber (10 km) due to decrease in magma density caused by volatile exsolution with pressure decrease. The highly vesiculated magma, which had at least 30 vol% bubbles, may have come into contact with ground water at sea level causing the large explosion of 18 August 2000.Editorial responsibility: S. Nakada, T. DuittAn erratum to this article can be found at     

Chlorine and fluorine in tholeiitic and alkaline lavas of Etna (Sicily)

Chlorine and fluorine were measured from whole-rock samples from tholeiites (150,000 years old) to present-day hawaiites. The overall range of F content is from 240 to 985 ppm, with a slight decrease of F/Th and F/Cl ratios, from tholeiites to hawaiites. Chlorine is positively correlated with Th (Cl/Th=100) as well as K₂O and P₂O₅, as the differentiation progresses, and, increases from 220 ppm in tholeiites to 2410 ppm in mugearites. Data obtained from present-day hawaiites indicate that Cl lost by degassing during eruption is limited. However, Cl contents of some whole-rock samples are inconsistent with previous results published for melt inclusions of phenocrysts from the same historic hawaiite samples and suggesting outgassing of Cl prior to the eruption. This implies that apparent correlation between Cl and Th can be considered as the result of superimposition of several petrogenetic processes. Results point out the richness of Etnean tholeiites in chlorine compared to M.A.R. basalts. Such a character could have been inherited from the mantle source or during the mantle source melting.     

The November 2002 eruption of Piton de la Fournaise,Réunion: tracking the pre-eruptive thermal evolution of magma using melt inclusions

The November 2002 eruption of Piton de la Fournaise in the Indian Ocean was typical of the activity of the volcano from 1999 to 2006 in terms of duration and volume of magma ejected. The first magma erupted was a basaltic liquid with a small proportion of olivine phenocrysts (Fo₈₁) that contain small numbers of melt inclusions. In subsequent flows, olivine crystals were more abundant and richer in Mg (Fo_83–84). These crystals contain numerous melt and fluid inclusions, healed fractures, and dislocation features such as kink bands. The major element composition of melt inclusions in this later olivine (Fo_83–84) is out of equilibrium with that of its host as a result of extensive post-entrapment crystallization and Fe²⁺ loss by diffusion during cooling. Melt inclusions in Fo₈₁ olivine are also chemically out of equilibrium with their hosts but to a lesser degree. Using olivine–melt geothermometry, we determined that melt inclusions in Fo₈₁ olivine were trapped at lower temperature (1,182 ± 1°C) than inclusions in Fo_83–84 olivine (1,199–1,227°C). This methodology was also used to estimate eruption temperatures. The November 2002 melt inclusion compositions suggest that they were at temperatures between 1,070°C and 1,133°C immediately before eruption and quenching. This relatively wide temperature range may reflect the fact that most of the melt inclusions were from olivine in lava samples and therefore likely underwent minor but variable amounts of post-eruptive crystallization and Fe²⁺ loss by diffusion due to their relatively slow cooling on the surface. In contrast, melt inclusions in tephra samples from past major eruptions yielded a narrower range of higher eruption temperatures (1,163–1,181°C). The melt inclusion data presented here and in earlier publications are consistent with a model of magma recharge from depth during major eruptions, followed by storage, cooling, and crystallization at shallow levels prior to expulsion during events similar in magnitude to the relatively small November 2002 eruption.     

Compositionally zoned crystals and real-time degassing data reveal changes in magma transfer dynamics during the 2006 summit eruptive episodes of Mt. Etna

One of the major objectives of volcanology remains relating variations in surface monitoring signals to the magmatic processes at depth that cause these variations. We present a method that enables compositional and temporal information stored in zoning of minerals (olivine in this case) to be linked to observations of real-time degassing data. The integrated record may reveal details of the dynamics of gradual evolution of a plumbing system during eruption. We illustrate our approach using the 2006 summit eruptive episodes of Mt. Etna. We find that the history tracked by olivine crystals, and hence, most likely the magma pathways within the shallow plumbing system of Mt. Etna, differed considerably between the July and October eruptions. The compositional and temporal record preserved in the olivine zoning patterns reveal two mafic recharge events within months of each other (June and September 2006), and each of these magma supplies may have triggered the initiation of different eruptive cycles (July 14–24 and August 31–December 14). Correlation of these observations with gas monitoring data shows that the systematic rise of the CO₂/SO₂ gas values is associated with the gradual (pre- and syn-eruptive) supply of batches of gas-rich mafic magma into segments of Etna’s shallow plumbing system, where mixing with pre-existing and more evolved magma occurred.     

Gas emissions from failed and actual eruptions from Cook Inlet Volcanoes,Alaska, 1989–2006

Cook Inlet volcanoes that experienced an eruption between 1989 and 2006 had mean gas emission rates that were roughly an order of magnitude higher than at volcanoes where unrest stalled. For the six events studied, mean emission rates for eruptions were ∼13,000 t/d CO₂ and 5200 t/d SO₂, but only ∼1200 t/d CO₂ and 500 t/d SO₂ for non-eruptive events (‘failed eruptions’). Statistical analysis suggests degassing thresholds for eruption on the order of 1500 and 1000 t/d for CO₂ and SO₂, respectively. Emission rates greater than 4000 and 2000 t/d for CO₂ and SO₂, respectively, almost exclusively resulted during eruptive events (the only exception being two measurements at Fourpeaked). While this analysis could suggest that unerupted magmas have lower pre-eruptive volatile contents, we favor the explanations that either the amount of magma feeding actual eruptions is larger than that driving failed eruptions, or that magmas from failed eruptions experience less decompression such that the majority of H₂O remains dissolved and thus insufficient permeability is produced to release the trapped volatile phase (or both). In the majority of unrest and eruption sequences, increases in CO₂ emission relative to SO₂ emission were observed early in the sequence. With time, all events converged to a common molar value of C/S between 0.5 and 2. These geochemical trends argue for roughly similar decompression histories until shallow levels are reached beneath the edifice (i.e., from 20–35 to ∼4–6 km) and perhaps roughly similar initial volatile contents in all cases. Early elevated CO₂ levels that we find at these high-latitude, andesitic arc volcanoes have also been observed at mid-latitude, relatively snow-free, basaltic volcanoes such as Stromboli and Etna. Typically such patterns are attributed to injection and decompression of deep (CO₂-rich) magma into a shallower chamber and open system degassing prior to eruption. Here we argue that the C/S trends probably represent tapping of vapor-saturated regions with high C/S, and then gradual degassing of remaining dissolved volatiles as the magma progresses toward the surface. At these volcanoes, however, C/S is often accentuated due to early preferential scrubbing of sulfur gases. The range of equilibrium degassing is consistent with the bulk degassing of a magma with initial CO₂ and S of 0.6 and 0.2 wt.%, respectively, similar to what has been suggested for primitive Redoubt magmas.     

The pre-eruptive volatile contents of recent basaltic and pantelleritic magmas at Pantelleria (Italy)

Pantelleria Island, located in the Sicily Channel Rift Zone (Italy), is the type locality for the peralkaline rhyolitic rocks called pantellerites. In the last 50 ka, after the large Green Tuff caldera-forming eruption, volcanic activity at Pantelleria has consisted of effusive and explosive eruptions mostly vented inside and along the rim of the caldera and producing silicic lava flows, lava domes and poorly dispersed pantelleritic pumice fall deposits. Basaltic cinder cones and lava flows are only present outside the caldera in the NW sector of the island. The most recent basaltic (Cuddie Rosse, ～ 20 ka) and pantelleritic (Cuddia Randazzo and Cuddia del Gallo, ～ 6 ka) pyroclastic products were sampled to investigate magmatic volatile contents through the study of melt inclusions.The melt inclusions in pyroxene and olivine phenocrysts of Cuddie Rosse scoriae have an alkali basalt composition. The dissolved volatiles comprise 0.9–1.6 wt.% H₂O, several hundred ppm of CO₂, 1600–2000 ppm of sulphur and 500–900 ppm of chlorine. The water–carbon dioxide couple gives a confining pressure ～ 2 kbar prior to the eruption. This result indicates that episodes of magma ponding and crystallization occurred in the upper crust prior to eruption. The melt inclusions in feldspar, fayalite and aenigmatite phenocrysts of Cuddia del Gallo and Cuddia Randazzo pumice have a pantelleritic composition (Agpaitic Indices 1.3–2.1), up to 4.4 wt.% H₂O, 8700 ppm Cl, 6000 ppm F, and CO₂ below the detection limit. Sulphur averaging 420 ppm has been measured in Cuddia Randazzo melt inclusions. These data indicate relatively high volatile contents for these low-energy Strombolian-type eruptions. Melt inclusions in Cuddia del Gallo pumice show the most evolved composition (Agpaitic Indices 2–2.1) and the highest volatile content, in agreement with fluid saturation conditions in the magma chamber prior to the eruption. This implies a confining pressure of ～ 1 kbar for the top of the pantelleritic reservoir. The composition of melt inclusions and mineralogical assemblage of Cuddia Randazzo pumice indicate that it has a lower evolutionary degree (Agpaitic Indices 1.3–1.8) and lower pre-eruptive Cl and H₂O contents than Cuddia del Gallo pumice. An increase in pressure due to the exsolution of volatiles in the upper part of the pantelleritic reservoir may have triggered the Cuddia del Gallo explosive eruption. Evidence of widespread pre-eruptive mingling between trachytes and pantellerites suggests that the intrusion of trachytic magma into the pantelleritic reservoir likely played a major role in destabilizing the magma system just prior to the Cuddia Randazzo event.     

Temporal variation in the lavas of Mayon volcano, Philippines

Chemical and petrographic analyses of 51 sequential lava flows from the central vent of Mayon volcano show cyclical variation. In the two most recent cycles, from 1800 to 1876 and from 1881 to the present, one to three basaltic flows are followed by six to ten andesitic flows. Modal and whole-rock chemical parameters show the most regular cyclical variation; calculated groundmass chemical parameters vary less regularly. There is also a long-term trend, over approximately 1700 years of exposed section, toward more basic compositions.The cyclical variation in modes and the chemical composition of the lavas apparently results from periodic influxes of basaltic magma from depth into a shallow magma system. Fractional crystallization of olivine, augite, hypersthene, calcic plagioclase, magnetite and pargasitic hornblende produces successively more andesitic lavas until the next influx of basaltic magma. Differentiation in a deep zone of magma generation is not excluded by the data, but is more likely responsible for the overall change toward more basic compositions than for the cyclical variation.Three points in a cycle — the beginning of basaltic lavas, the beginning of andesitic lavas and a leveling-off of SiO₂, K₂ O and K₂O/Na₂O values — correspond roughly to the beginning of frequent effusive eruptions (with or without an early Plinian eruption), frequent weak to moderately explosive (Strombolian) eruptions, and less frequent explosive (Vulcanian) eruptions, respectively. Recognition of the current stage in a cycle can give a qualitative indication of the nature of forthcoming eruptions. Changes in several specific parameters may precede basaltic lavas and allow early detection of basaltic influxes. These include minima in the glass inclusion/plagioclase phenocryst and phenocryst/groundmass ratios, vesicularity and groundmass TiO₂, a decrease in hypersthene phenocrysts, and constant values for the whole-rock K₂O/Na₂O ratio. The Mayon area is densely populated, making prediction of eruption type important for safety and land-use planning.     

Témoignages de la contamination dans les produits des éruptions explosives des M. Silvestri (1892) et M. Rossi (1669) (M. Etna)

Resume Les différentes étapes de la cristallisation des pyroclastes des Monti Rossi et Silvestri ont été reconstituées par l'étude des inclusions vitreuses intraminérales.L'olivine magnésienne (Fo 82) et le diopside cristallisent à partir d'un liquide basaltique de nature alcaline au cours de l'ascension, sous une forte pression de fluides liée à la quantité importante de gaz dissous (4 à 5% dont 2800–3500 ppm de S).L'« ouverture » du système s'accompagne de la démixtion d'environ 50% de la phase volatile dissoute.Les oxydes Fe-Ti, les olivines (Fo 74-75) et les salites cristallisent alors, à partir d'un liquide partiellement dégazé (2 à 2,5% d'éléments volatils, dont 1200 ppm de S), de composition hawaïtique, dans un domaine de température compris entre 1160 et 1140°C.Le plagioclase (An 82) se sépare tardivement dans un liquide dont la composition se rapproche de celle du liquide résiduel. Ce stade d'évolution qui s'accompagne d'une accumulation de gaz démixé, témoigne de conditions pré-éruptives de subsurface.Les teneurs anormalement élevées en fluides des basaltes alcalins etnéens comparées à celles de basaltes de même composition (par exemple dans les inclusions des Fo 82 du Piton de la Fournaise, des volatils 2%, S=1200 ppm et Cl=200 à 400 ppm) nous ont conduit à envisager la contribution de l'encaissant sédimentaire.La présence dans les produits des Silvestri de nombreuses enclaves carbonatées (fassaïte, wollastonite, anorthite), argilo-schisteuses (plagioclase, hercynite, sulfures) et gréseuses (quartz, verres rhyolitiques), l'abondance des inclusions fluides (CO₂, SO₂) dans les minéraux néoformés, les témoignages de phénomènes locaux d'assimilation (verres riches en Ca, Si...) viennent renforcer l'idée du rôle de la contamination (au moins en ce qui concerne les fluides) par l'encaissant sédimentaire, négligée jusqu'ici dans le cas des laves de l'Etna.

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The melt inclusions trapped inside crystals have allowed the determination of the different crystallization steps, for the M. Rossi and M. Silvestri pyroclastic products.Magnesian olivine (Fo 82) and diopside crystallize from an alkali basaltic liquid, during ascent. The high concentration (4–5% with S=2800–3500 ppm) of volatiles in glass inclusions involves a strong fluid pressure.The release of about 50% of dissolved gases reflects the « opening » of the magmatic system. Therefore, olivine (Fo 74-70), salite and Fe-Ti oxydes, crystallize from an hawaiitic melt, with lower volatile content (2 to 2,5% with S=1200 ppm). The temperatures range from 1160°C to 1140°C.Plagioclase phenocrysts (An 82) grow later from a more evolved liquid. Equivalences of gas accumulation infer a pre-eruption crystallization.The unusual content of volatiles in the alkali basalts compared to equivalent oceanic basalts (2% with S=1200 ppm and Cl= 200 to 400 ppm in olivine melt inclusions from Piton de la Fournaise volcano) suggests a wall rock contribution.Numerous xenoliths of carbonates (with fassaite, wollastonite, anorthite assemblages), shale (with plagioclase, hercynite and sulfide) or sandstone (with quartz and rhyolitic glasses) have been found among the M. Silvestri products.Fluid inclusions in the minerals as well as local SiO₂, CaO, FeO enrichments of the magmatic liquid infer partial assimilation of sedimentary rocks.All these observations support a contamination hypothesis, at least for the volatile phase.

     

Effect of Miocene basaltic volcanism in Shanwang (Shandong Province, China) on environmental changes

Miocene(16―10 Ma) basalts,together with significantly well-preserved fossils(including animal and plant fossils) in the contemporaneously tephra-rich Maar sediments,are located in Shanwang volcanic region,Shandong Province,China.Distribution area of the basaltic eruption products is about 240 km2.Detailed field observations indicate that most of basaltic rocks are fissure eruptive products and some are central eruptives constrained by linear faults.The well-preserved fossils in the lacustrine deposits have been considered to be a result of mass mortalities.Based on physically volcanologic modeling results,eruption column of the basaltic fissure activities in the Shanwang volcanic region is estimated to have entered the stratosphere.Petrographic observations indicate that the basalts have porphyritic textures with phenocrysts of olivine,pyroxene,plagioclase feldspar and alkali feldspar setting in groundmass of plagioclase feldspar,alkali feldspar,quartz,apatite and glass.Based on observations of tephra,tuff and tuffites collected in the Maar sediments of the Shanwang area,we determined major element oxide concentrations and volatile composition of melt inclusions in phenocrysts and matrix glasses by electron microprobe analysis.Volatile(including S,Cl,F and H2O) concentrations erupted into the stratosphere were estimated by comparing pre-and post-eruptive volatile concentrations.Our determination results show that contents of S,Cl,F and H2O emitted into the stratosphere were 0.18%― 0.24%,0.03%―0.05%,0.03%―0.05% and 0.4%―0.6%,respectively,which was characterized by high-S contents erupted.Amounts of volatiles emitted in the Shanwang volcanic region are much higher than those in eruptions which had a substantial effect on climate and environment.According to the com-positions and amounts of the volatiles erupted from the Miocene basaltic volcanism in Shanwang,we propose a hypothesis that volatile-rich basaltic volcanism could result in the mass mortalities by in-jecting volatiles(e.g.,SO2,H2S,HCl,HF and H2O) into the stratosphere that would have triggered abrupt environmental changes(including formation of acid rain,temperature decline,ozone depletion,etc.) and altered lake chemistry,and subsequently volcanic ash fall buried and covered the dead animals and plants,forming well-preserved fossils in Shanwang Maar sediments.     

Non-volatile vs volatile behaviours of halogens during the AD 79 plinian eruption of Mt. Vesuvius, Italy

Pre-eruptive conditions and degassing processes of the AD 79 plinian eruption of Mt. Vesuvius are constrained by systematic F and Cl measurements in melt inclusions and matrix glass of pumice clasts from a complete sequence of the pumice-fallout deposits. The entire ‘white pumice’ (WP) magma and the upper part of the ‘grey pumice’ (GP) magma were saturated relative to sub-critical fluids (a Cl-rich H₂O vapour phase and a brine), with a Cl melt content buffered at ~ 5300 ppm, and a mean H₂O content of ~ 5%. The majority of the GP magma was not fluid-saturated. From these results it can be estimated that the WP magma chamber had a low vertical extent (< 500 m) and was located at a depth of ~ 7.5 km while the GP magma reservoir was located just beneath the WP one, but its vertical extent cannot be constrained. This is approximately two times deeper than previous estimates. H₂O degassing during the WP eruption followed a typical closed-system evolution, whereas GP clasts followed a more complex degassing path. Contrary to H₂O, Cl was not efficiently degassed during the plinian phase of the eruption.

This study shows that F and Cl behave as incompatible elements in fluid-undersaturated phonolitic melts. H₂O saturation is necessary for a significant partitioning of Cl into the fluid phase. However, Cl cannot be extracted in significant quantity from phonolitic melts during rapid H₂O degassing, e.g. during plinian eruptions, due to kinetics effects. Halogen contents are better preserved in volcanic glass (melt inclusions or matrix glass) than H₂O, therefore the combined analysis of both volatile species is required for reliable determination of pre-eruptive conditions and syn-eruptive degassing processes in magmas stored at shallow depths.     

A tale of two magmas,Fuego, Guatemala

Fuego volcano in Guatemala erupted in 1974 in a basaltic sub-Plinian event, which has been well documented and studied. In 1999, after a period of quiescence lasting 20 years, Fuego erupted again, this time less violently, but with persistent low-level activity. This study investigates the link between these episodes. Previous melt inclusion studies have shown magma erupted in 1974 to have been a volatile-rich hybrid tapped from a vertically extensive system. By contrast, magma erupted in 1999 and 2003 is similar in composition to that erupted in 1974, but melt inclusions are more evolved. Although melt inclusions from the later period are CO₂ rich (up to ∼1,500 ppm), they have low H₂O concentration (max 1.5 wt.%, compared to ∼6 wt.% in 1974). These melt inclusions have a modified H₂O concentration due to diffusive re-equilibration at shallow pressures. Despite this diffusive exchange, both eruptions show evidence of recent mingling of the same low and higher K melts, one of which was slightly cooler than the other and as a result traversed the amphibole stability field. (²¹⁰Pb/²²⁶Ra) data on selected bulk rock samples from 1974 suggest that whereas the cooler, more evolved end-member may have been degassing since the last major eruption in the 1930s, the warmer end-member intruded at most a decade prior to the 1974 eruption. The two end-members are thus batches of the same magma emplaced shallowly ∼30 years apart during which time the older batch was cooled and differentiated before mixing with the younger influx. The presence of the same two melts in the later eruptions suggests that magma in 1999 and 2003 is partly residual from 1974. The current eruptive activity is clearing the system of this residual magma prior to an expected new magma batch.     

Phenocryst-hosted melt inclusions record stalling of magma during ascent in the conduit and upper magma reservoir prior to vulcanian explosions, Soufrière Hills volcano, Montserrat, West Indies

The mechanics of explosive eruptions influence magma ascent pathways. Vulcanian explosions involve a stop–start mechanism that recurs on various timescales, evacuating the uppermost portions of the conduit. During the repose time between explosions, magma rises from depth and refills the conduit and stalls until the overpressure is sufficient to generate another explosion. We have analyzed major elements, Cl, S, H₂O, and CO₂ in plagioclase-hosted melt inclusions, sampled from pumice erupted during four vulcanian events at Soufrière Hills volcano, Montserrat, to determine melt compositions prior to eruption. Using Fourier transform infrared spectroscopy, we measured values up to 6.7 wt.% H₂O and 80 ppm CO₂. Of 42 melt inclusions, 81 % cluster between 2.8 and 5.4 wt.% H₂O (57 to 173 MPa or 2–7 km), suggesting lower conduit to upper magma reservoir conditions. We propose two models to explain the magmatic conditions prior to eruption. In Model 1, melt inclusions were trapped during crystal growth in magma that was stalled in the lower conduit to upper magma reservoir, and during trapping, the magma was undergoing closed-system degassing with up to 1 wt.% free vapor. This model can explain the melt inclusions with higher H₂O contents since these have sampled the upper parts of the magma reservoir. However, the model cannot explain the melt inclusions with lower H₂O because the timescale for plagioclase crystallization and melt inclusion entrapment is longer than the magma residence time in the conduit. In Model 2, melt inclusions were originally trapped at deeper levels of the magma chamber, but then lost hydrogen by diffusion through the plagioclase host during periodic stalling of the magma in the lower conduit system. In this second scenario, which we favor, the melt inclusions record re-equilibration depths within the lower conduit to upper magma reservoir.     

Viscosity of hydrous Etna basalt: implications for Plinian-style basaltic eruptions

Water dissolved in a silicate melt can strongly influence its physical properties and thus magma behavior during crystallization, degassing, foaming and fragmentation. Etna is a basaltic volcano whose activity is dominated by effusive eruptions which have long represented a threat to the densely populated, surrounding area. Recently, recognition of the products of a Plinian eruption (122 B.C.) has raised further issues for hazard assessment at Etna and other basaltic volcanoes. Constraining the behavior of Etna magma under conditions relevant to both effusive and explosive hazards requires viscosity data under conditions near the glass transition. Here we have investigated the viscosity of hydrous Etna lava in order to better understand eruptive processes which characterize this volcano. The experimental methods which have been used include piston cylinder synthesis of the hydrated melts, micropenetration viscometry for low-temperature viscosity measurements, and near-infrared spectroscopy for the evaluation of sample homogeneity and measurements of water content. Additionally, scanning calorimetric determinations were performed to check whether incipient crystallization had occurred. Sample compositions were determined using electron microprobe analysis and ⁵⁷Fe Mössbauer spectroscopy. Results from this study are compared with previous reports of trachytic, phonolitic and model calc-alkaline rhyolite (HPG8) compositions. The viscosity of the basaltic melt (dry and wet) has been parameterized in terms of temperature and water content via the non-Arrhenian equation: log₁₀-=-4.643+(5,812.44-427.042H₂O)/(T(K)-499.31+28.742ln(H₂O)) where - is the viscosity in Pa s, H₂O is the water content in wt%, and T is the temperature in Kelvin. We observe that the viscosity of alkali basalt (at more than 0.5 wt% H₂O) is similar to that of an alkaline trachyte (Agnano-Monte Spina eruption, Phlegrean Fields) and much higher than that of a peralkaline phonolite (Teide, Tenerife) at similar silica contents and NBO/T. For water contents above 1.5 wt%, the viscosity of the basalt is similar to that of rhyolitic melts with similar water contents. At temperatures ranging from 1,050 to 1,150 °C and with water contents between 0.5 and 2.3 wt% (eruptive conditions), the viscosities calculated using the equation defined in this study are (1) in reasonable agreement with those calculated using Shaw's model, and (2) much lower than those experimentally determined in a previous study. However, outside these temperature and water content ranges, the agreement with Shaw's model (1972) breaks down.     

Magma–conduit interaction at Piton de la Fournaise volcano (Réunion Island): a melt and fluid inclusion study

Major-element, Cl, S, F analyses have been performed on a wide selection of melt inclusions trapped in olivine (Fo_81–87) from scoria and crystal-rich lapilli samples of Piton de la Fournaise volcano. As a whole, they display a transitional basaltic composition. The melt inclusions (8–9 wt.% MgO, 0.62–0.73 wt.% K₂O) are in equilibrium with olivines (Fo_81–85) in the samples from the Central Feeding Zone and the South-East Feeding Zone and show a slight alkaline affinity. The melt inclusions in olivines (Fo_85–87) from the North-West Rift (NWR) contain 9.3–9.7 wt.% MgO and 0.54–0.58 wt.% K₂O, with a more tholeiitic tendency. In oceanitic lavas and crystal-rich lapilli, the olivine xenocrysts are recognisable by the presence of one or more secondary shear plane fracture(s) filled up with CO₂ and alkali-rich basaltic melt inclusions. In dunite nodules, olivines present also contain several secondary shear plane fracture(s) filled up with CO₂ and high-SiO₂ melt inclusions. Secondary CO₂-rich fluid inclusions in olivine (Fo_85–87) from the NWR samples indicate PCO₂ up to 500 MPa whereas, PCO₂ ranges from 95 MPa to few tenths of bars in the other samples. Both the primary melt inclusions and the secondary fluid inclusions strongly suggest that the olivine crystallises and accumulates over a wide depth range (15 km). It is envisioned that cumulative pockets with low residual porosity are repeatedly percolated with a CO₂-rich fluid phase, possibly associated with basaltic to SiO₂-rich melts, and are finally disrupted and entrained to the surface when vigorous magma transfer occurs. The SiO₂-rich residual melts in early-formed dunitic or gabbroic bodies may have acted as contaminant agents for the more alkali character of magmas vented through the central feeding system, where a well-developed cumulative system is thought to exist. Finally, the existence of secondary fluid and melt inclusions in olivines implies that the dunitic bodies are weakened on the micrometric scale.     

Influence of pre-eruptive storage conditions and volatile contents on explosive Plinian style eruptions of basic magma

Sub-Plinian to Plinian eruptions of basic magma present a challenge to modeling volcanic behavior because many models rely on magma becoming viscous enough during ascent to behave brittlely and cause fragmentation. Such models are unable, however, to strain low viscosity magma fast enough for it to behave brittlely. That assumes that such magmas actually have low viscosities, but the rare Plinian eruptions of basic magma may in fact result from them being anomalously viscous. Here, we examine two such eruptions, the 122 B.C. eruption of hawaiitic basalt from Mt. Etna and the late Pleistocene eruption of basaltic andesite from Masaya Caldera, to test whether they were anomalously viscous. We carried out hydrothermal experiments on both magmas and analyzed glass inclusions in plagioclase phenocrysts from each to determine their most likely pre-eruptive temperatures and water contents. We find that the hawaiite was last stored at 1,000–1,020°C, whereas the basaltic andesite was last stored at 1,010–1,060°C, and that both were water saturated with ∼3.0 wt.% water dissolved in them. Such water contents are not high enough to trigger Plinian explosive behavior, as much more hydrous basic magmas erupt less violently. In addition, despite being relatively cool, the viscosities of both magmas would range from ∼10^2.2–2.5 Pa s before erupting to ∼10⁴ Pa s when essentially degassed, all of which are too fluid to cause brittle disruption. Without invoking special external forces to explain all such eruptions, one of the more plausible explanations is that when the bubble content reaches some critical value the fragile foam-like magma disrupts. The rarity of Plinian eruptions of basic magma may be because such magmas must ascend fast enough to retain their bubbles.