Heterogeneously entrapped,vapor-rich melt inclusions record pre-eruptive magmatic volatile contents

Silicate melt inclusions (MI) commonly provide the best record of pre-eruptive H₂O and CO₂ contents of subvolcanic melts, but the concentrations of CO₂ and H₂O in the melt (glass) phase within MI can be modified by partitioning into a vapor bubble after trapping. Melt inclusions may also enclose vapor bubbles together with the melt (i.e., heterogeneous entrapment), affecting the bulk volatile composition of the MI, and its post-entrapment evolution. In this study, we use numerical modeling to examine the systematics of post-entrapment volatile evolution within MI containing various proportions of trapped vapor from zero to 95 volume percent. Modeling indicates that inclusions that trap only a vapor-saturated melt exhibit significant decrease in CO₂ and moderate increase in H₂O concentrations in the melt upon nucleation and growth of a vapor bubble. In contrast, inclusions that trap melt plus vapor exhibit subdued CO₂ depletion at equivalent conditions. In the extreme case of inclusions that trap mostly the vapor phase (i.e., CO₂–H₂O fluid inclusions containing trapped melt), degassing of CO₂ from the melt is negligible. In the latter scenario, the large fraction of vapor enclosed in the MI during trapping essentially serves as a buffer, preventing post-entrapment modification of volatile concentrations in the melt. Hence, the glass phase within such heterogeneously entrapped, vapor-rich MI records the volatile concentrations of the melt at the time of trapping. These numerical modeling results suggest that heterogeneously entrapped MI containing large vapor bubbles represent amenable samples for constraining pre-eruptive volatile concentrations of subvolcanic melts.     

In situ observations of bubble growth in basaltic,andesitic and rhyodacitic melts

Bubble growth strongly affects the physical properties of degassing magmas and their eruption dynamics. Natural samples and products from quench experiments provide only a snapshot of the final state of volatile exsolution, leaving the processes occurring during its early stages unconstrained. In order to fill this gap, we present in situ high-temperature observations of bubble growth in magmas of different compositions (basalt, andesite and rhyodacite) at 1,100 to 1,240 °C and 0.1 MPa (1 bar), obtained using a moissanite cell apparatus. The data show that nucleation occurs at very small degrees of supersaturaturation (<60 MPa in basalt and andesite, 200 MPa in rhyodacite), probably due to heterogeneous nucleation of bubbles occurring simultaneously with the nucleation of crystals. During the early stages of exsolution, melt degassing is the driving mechanism of bubble growth, with coalescence becoming increasingly important as exsolution progresses. Ostwald ripening occurs only at the end of the process and only in basaltic melt. The average bubble growth rate (G _R) ranges from 3.4 × 10^?6 to 5.2 × 10^?7 mm/s, with basalt and andesite showing faster growth rates than rhyodacite. The bubble number density (N _B) at nucleation ranges from 7.9 × 10⁴ mm^?3 to 1.8 × 10⁵ mm^?3 and decreases exponentially over time. While the rhyodacite melt maintained a well-sorted bubble size distribution (BSD) through time, the BSDs of basalt and andesite are much more inhomogeneous. Our experimental observations demonstrate that bubble growth cannot be ascribed to a single mechanism but is rather a combination of many processes, which depend on the physical properties of the melt. Depending on coalescence rate, annealing of bubbles following a single nucleation event can produce complex bubble size distributions. In natural samples, such BSDs may be misinterpreted as resulting from several separate nucleation events. Incipient crystallization upon cooling of a magma may allow bubble nucleation already at very small degrees of supersaturation and could therefore be an important trigger for volatile release and explosive eruptions.     

Basaltic explosive volcanism: Constraints from deposits and models

Basaltic pyroclastic volcanism takes place over a range of scales and styles, from weak discrete Strombolian explosions (～10²–10³ kg s^?1) to Plinian eruptions of moderate intensity (10⁷–10⁸ kg s^?1). Recent well-documented historical eruptions from Etna, Kīlauea and Stromboli typify this diversity. Etna is Europe's largest and most voluminously productive volcano with an extraordinary level and diversity of Strombolian to subplinian activity since 1990. Kīlauea, the reference volcano for Hawaiian fountaining, has four recent eruptions with high fountaining (>400 m) activity in 1959, 1960, 1969 (–1974) and 1983–1986 (–2008); other summit (1971, 1974, 1982) and flank eruptions have been characterized by low fountaining activity. Stromboli is the type location for mildly explosive Strombolian eruptions, and from 1999 to 2008 these persisted at a rate of ca. 9 per hour, briefly interrupted in 2003 and 2007 by vigorous paroxysmal eruptions. Several properties of basaltic pyroclastic deposits described here, such as bed geometry, grain size, clast morphology and vesicularity, and crystal content are keys to understand the dynamics of the parent eruptions.The lack of clear correlations between eruption rate and style, as well as observed rapid fluctuations in eruptive behavior, point to the likelihood of eruption style being moderated by differences in the fluid dynamics of magma and gas ascent and the mechanism by which the erupting magma fragments. In all cases, the erupting magma consists of a mixture of melt and gaseous bubbles. The depth and rate of degassing, melt rheology, bubble rise and coalescence rates, and extent of syn-eruptive microlite growth define complex feedbacks that permit reversible shifts between fragmentation mechanisms and in eruption style and intensity. However, many basaltic explosive eruptions end after an irreversible shift to open-system outgassing and microlite crystallization in melt within the conduit.Clearer understanding of the factors promoting this diversity of basaltic pyroclastic eruptions is of fundamental importance in order to improve understanding of the range of behaviors of these volcanoes and assess hazards of future explosive events at basaltic volcanoes. The three volcanoes used for this review are the sites of large and growing volcano-tourism operations and there is a public need both for better knowledge of the volcanoes’ behavior and improved forecasting of the likely course of future eruptions.     

Melt inclusion constraints on volatile systematics and degassing history of the 2014–2015 Holuhraun eruption,Iceland

The mass of volatiles emitted during volcanic eruptions is often estimated by comparing the volatile contents of undegassed melt inclusions, trapped in crystals at an early stage of magmatic evolution, with that of the degassed matrix glass. Here we present detailed characterisation of magmatic volatiles (H₂O, CO₂, S, Fl and Cl) of crystal-hosted melt and fluid inclusions from the 2014–2015 Holuhraun eruption of the Bárðarbunga volcanic system, Iceland. Based on the ratios of magmatic volatiles to similarly incompatible trace elements, the undegassed primary volatile contents of the Holuhraun parental melt are estimated at 1500–1700 ppm CO₂, 0.13–0.16 wt% H₂O, 60–80 ppm Cl, 130–240 ppm F and 500–800 ppm S. High-density fluid inclusions indicate onset of crystallisation at pressures?≥?0.4 GPa (~?12 km depth) promoting deep degassing of CO₂. Prior to the onset of degassing, the melt CO₂ content may have reached 3000–4000 ppm, with the total magmatic CO₂ budget estimated at  23–55 Mt. SO₂ release commenced at 0.12 GPa (~?3.6 km depth), eventually leading to entrapment of SO₂ vapour in low-density fluid inclusions. We calculate the syn-eruptive volatile release as 22.2 Mt of magmatic H₂O, 5.9–7.7 Mt CO₂, and 11.3 Mt of SO₂ over the course of the eruption; F and Cl release were insignificant. Melt inclusion constraints on syn-eruptive volatile release are similar to estimates made during in situ field monitoring, with the exception of H₂O, where field measurements may be heavily biased by the incorporation of meteoric water.     

The 1783 Lakagigar eruption in Iceland: geochemistry,CO2 and sulfur degassing

About 12.3 km³ of basaltic magma were erupted from the Lakagigar fissure in Iceland in 1783, which may have been derived from the high-level reservoir of Grimsvotn central volcano, by lateral flow within the rifted crust. We have studied the petrology of quenched, glassy tephra from sections through pyroclastic cones along the fissure. The chemical composition of matrix glass of the 1783 tephra is heterogeneous and ranges from olivine tholeiite to Fe–Ti rich basalt, but the most common magma erupted is quartz tholeiite (Mg#43.6 to 37.2). The tephra are characterized by low crystal content (5 to 9 vol%). Glass inclusions trapped in plagioclase and Fo₈₆ to Fo₇₅ olivine phenocrysts show a large range of compositions, from primitive olivine tholeiite (Mg#64.3), quartz tholeiite (Mg#43–37), to Fe–Ti basalts (Mg#33.5) which represent the most differentiated liquids and are trapped as rare melt inclusions in clinopyroxene. Both matrix glass and melt inclusion data indicate a chemically heterogeneous magma reservoir, with quartz tholeiite dominant. LREE-depleted olivine-tholeiite melt-inclusions in Mg-rich olivine and anorthitic-plagioclase phenocrysts may represent primitive magma batches ascending into the reservoir at the time of the eruption. Vesicularity of matrix glasses correlates with differentiation, ranging from 10 to 60 vol.% in evolved quartz-tholeiite glasses, whereas olivine-tholeiite glasses contain less than 10 vol.% vesicles. FTIR analyses of olivine-tholeiite melt-inclusions indicate concentrations of 0.47 wt% H₂O and 430 to 510 ppm for CO₂. Chlorine in glass inclusions and matrix glasses increases from 50 ppm in primitive tholeiite to 230 ppm in Fe–Ti basalts, without clear evidence of degassing. Melt inclusion analyses show that sulfur varies from 915 ppm to 1970 ppm, as total FeO^* increases from 9 to 13.5 wt%. Sulfur degassing correlates both with vesicularity and magma composition. Thus sulfur in matrix glasses decreases from 1490 ppm to 500 ppm, as Mg # decreases from 47 to 37 and vesicularity of the magma strongly increases. These results indicate loss of at least 75% of sulfur during the eruption. The correlation of low sulfur content in matrix glasses with high vesicularity is regarded as evidence of the control of a major exsolving volatile phase on the degassing efficiency of the magma. Our model is consistent a quasi-permanent CO₂ flux through the shallow-level magmatic reservoir of Grimsvotn. Following magma withdrawal from the reservoir and during eruption from the Lakagigar fissure, sulfur degassing was controlled by inherent CO₂-induced vesicularity of the magma.     

H2O–CO2 solubility in mafic alkaline magma: applications to volatile sources and degassing behavior at Erebus volcano, Antarctica

We present new equilibrium mixed-volatile (H₂O–CO₂) solubility data for a phonotephrite from Erebus volcano, Antarctica. H₂O–CO₂-saturated experiments were conducted at 400–700 MPa, 1,190 °C, and ~NNO + 1 in non-end-loaded piston cylinders. Equilibrium H₂O–CO₂ fluid compositions were determined using low-temperature vacuum manometry, and the volatile and major element compositions of the glassy run products were determined by Fourier transform infrared spectroscopy and electron microprobe. Results show that the phonotephrite used in this study will dissolve ~0.8 wt% CO₂ at 700 MPa and a fluid composition of $ X_{{{\text{H}}_{ 2} {\text{O}}}} $ ~0.4, in agreement with previous experimental studies on mafic alkaline rocks. Furthermore, the dissolution of CO₂ at moderate to high $ X_{{{\text{H}}_{ 2} {\text{O}}}}^{\text{fluid}} $ in our experiments exceeds that predicted using lower-pressure experiments on similar melts from the literature, suggesting a departure from Henrian behavior of volatiles in the melt at pressures above 400 MPa. With these data, we place new constraints on the modeling of Erebus melt inclusion and gas emission data and thus the interpretation of its magma plumbing system and the contributions of primitive magmas to passive and explosive degassing from the Erebus phonolite lava lake.     

Segregating gas from melt: an experimental study of the Ostwald ripening of vapor bubbles in magmas

Diffusive coarsening (Ostwald ripening) of H₂O and H₂O-CO₂ bubbles in rhyolite and basaltic andesite melts was studied with elevated temperature–pressure experiments to investigate the rates and time spans over which vapor bubbles may enlarge and attain sufficient buoyancy to segregate in magmatic systems. Bubble growth and segregation are also considered in terms of classical steady-state and transient (non-steady-state) ripening theory. Experimental results are consistent with diffusive coarsening as the dominant mechanism of bubble growth. Ripening is faster in experiments saturated with pure H₂O than in those with a CO₂-rich mixed vapor probably due to faster diffusion of H₂O than CO₂ through the melt. None of the experimental series followed the time^1/3 increase in mean bubble radius and time⁻¹ decrease in bubble number density predicted by classical steady-state ripening theory. Instead, products are interpreted as resulting from transient regime ripening. Application of transient regime theory suggests that bubbly magmas may require from days to 100 years to reach steady-state ripening conditions. Experimental results, as well as theory for steady-state ripening of bubbles that are immobile or undergoing buoyant ascent, indicate that diffusive coarsening efficiently eliminates micron-sized bubbles and would produce mm-sized bubbles in 10²–10⁴ years in crustal magma bodies. Once bubbles attain mm-sizes, their calculated ascent rates are sufficient that they could transit multiple kilometers over hundreds to thousands of years through mafic and silicic melt, respectively. These results show that diffusive coarsening can facilitate transfer of volatiles through, and from, magmatic systems by creating bubbles sufficiently large for rapid ascent.     

Volatiles in pillows of the Mid-Ocean-Ridge-Basalt (MORB) and vitreous basaltic rims

Temperature-resolved analyses of volatiles from Mid-Ocean-Ridge-Basalt (MORB) and vitreous basaltic rims were carried out to investigate the total volatile contents of basaltic melts and the influence of magma contamination on the degassing behaviour of volcanic rocks.With respect to the sources of methane evolution from the MORB the investigations are taken into consideration, the hydrocarbon (HC) release especially from the melt.The current paper presents data for H₂O, CO₂, SO₂, He, H₂, HF, HCl, CO, N₂, O₂, and HC degassing profiles of samples from the MORB sampling cruise 02.10.1983-11.11.1983 with FS Sonne 28 during the GEMINO-1 project near the Carlsberg Ridge (CR) and the Mid-Indian-Ocean-Ridge (MIOR).It aims to estimate the magnitude and nature of source magma volatiles and contamination (crustal material, seawater, atmospheric gases).The degassing of H₂O, CO₂, HCs as well as sulphur and chlorine species, or O₂ from vitreous specimens shows characteristic differences associated with sample position with respect to the lava surface.From the water release by bubbling and diffusion above 700 °C it must be concluded that any assimilation of sea water in vitreous rim is very low. The water content in the vitreous rim is about 0.1-0.2 wt%. The low interaction of melt with sea water is supported by the missing of a significant release of chlorine species during the heat treatment of the sample up to 1450 °C.Mixed H₂O/CO₂ bubbles escape between 700 and 800 °C from the vitreous rim. The CO₂ release in the temperature range of 1060-1170 °C from the basalt and the vitreous rim is interpreted as an indication for the primary carbon-dioxide content in the melt.Above 1100 °C CO₂ and SO₂ are evolved by both diffusion and small bubbles. The quantities of CO₂ in the vitreous rim and the basalt are similar (between 0.05 and 0.15 wt%), whereas the quantities of SO₂ escaping both from the vitreous rim and the crystalline basalt are between 0.013 and 0.024 wt%.Simultaneous with the CO₂ release by bubbling, HC species, especially CH fragments, were observed. The fact that the temperature of release maxima are above 1050 °C in both the vitreous rim and in the basalt is an indication for a geogenetic origin of HCs, e.g. methane.A low temperature of release for methane, which is consistent with biogenetic HC, was observed from the gas-release profiles of the basalts only. The maxima of the low-temperature gas releases are between 80 and 200 °C with a high correlation between the fragments m/z 13 and m/z 15. This correlation is a significant indication for a methane release.The oxygen release profiles of vitreous and crystalline basalts give significant indications for oxygen fugacity below the (QMF) of basaltic magma.Secondary minerals, generated by alteration of basaltic rocks, can be characterized by gas release profiles (GRPs) due to their decomposition in the temperature range below 800 °C. Only in the basalt were there observed indications of alteration processes. Small traces of carbonates (<0.0001 wt%) were detected by the gas release during the decomposition.Processes of degassing at temperatures higher than 800 °C are correlated to volatiles in the melt and to fluid inclusions of the minerals. There are no obvious correlations in the degassing characteristics between H₂O, CO₂ and SO₂. The different maxima of the degassing velocity, especially of CO₂, and SO₂, are indications of the different bonding forces of the site occupancy of the volatiles in the melt and in the glass. A micelle model for bonding sites in the basaltic glass for dissolved volatiles is discussed.     

An Experimental Study of Water and Carbon Dioxide Solubilities in Mid-Ocean Ridge Basaltic Liquids. Part II: Applications to Degassing

Degassing processes in basaltic magmas rich in both water andcarbon dioxide can be modeled using the solubilities of theendmember systems and the assumption of Henry's law. Suitesof vapor-saturated basaltic melts having a range of initialCO₂/H₂O ratios and erupted over a narrow depth interval willdefine negatively sloped arrays on an H₂O vs CO₂ plot. It isimportant that all of the major volatile species be consideredsimultaneously when interpreting trends in dissolved volatilespecies concentrations in magmas. Based on measured concentrations of water and carbon dioxidein basaltic glasses, the composition of the vapor phase at 1200°Cthat could coexist with a basaltic melt and the pressure atwhich it would be vapor saturated can be calculated. The rangein vapor compositions in equilibrium with submarine basaltsreflects the range in water contents in the melts characteristicof each environment. The ranges in the molar proportion of CO₂in vapor phases (X_CO2) calculated to be in equilibrium withsubmarine tholeiitic glasses are 0•93–1•00 formid-ocean ridge basalts (MORB), 0•60–0•99 forglasses from Kilauea [representative of ocean island basalts(OIB)] and 0–0•94 for glasses from back-arc basins(BABB). MORB glasses from spreading centers ranging from slow(e.g. the Mid-Atlantic Ridge) to fast (e.g. East Pacific Rise,9–13°N) are commonly supersaturated with respect toCO₂-rich vapor, resulting from magma ascent rates so rapid thatmagmas erupt on the sea-floor without having been fully degassedby bubble nucleation and growth during ascent. In contrast tothe MORB glasses, volatile contents in submarine glasses fromKilauea are consistent with having been in equilibrium witha vapor phase containing 60–100 mol% CO₂ at the pressureof eruption, reflecting differences in average magma transportrates during eruptions at mid-ocean ridges and hotspot volcanoes. Degassing during decompression of tholeiitic basaltic magmais characterized by strong partitioning of CO₂ into the vaporphase. During open system degassing, CO₂ is rapidly removedfrom the melt with negligible loss of water, until a pressureis reached at which the melt is in equilibrium with nearly purewater vapor. From this pressure downward, the water contentof the melt follows the water solubility curve. During closedsystem degassing, water and CO₂ contents in vapor-saturatedbasaltic magmas will depend strongly on the vapor compositionas determined by the initial volatile concentrations. Deviationfrom open system behavior, toward lower dissolved H₂O and CO₂saturation concentrations at a given pressure, will be greatestin melts having high total volatile concentrations and highCO₂:H₂O ratios. Closed system degassing of basaltic melts havingthe low initial H₂O and CO₂ contents typical of MORB and OIB,however, are similar to the open system case. KEY WORDS: mid-ocean ridge basalts; water and carbon dioxide solubility; degassing     

In situ observation of crystal growth in a basalt melt and the development of crystal size distribution in igneous rocks

The speciation of CO₂ in dacite, phonolite, basaltic andesite, and alkali silicate melt was studied by synchrotron infrared spectroscopy in diamond anvil cells to 1,000 °C and more than 200 kbar. Upon compression to 110 kbar at room temperature, a conversion of molecular CO₂ into a metastable carbonate species was observed for dacite and phonolite glass. Upon heating under high pressure, molecular CO₂ re-appeared. Infrared extinction coefficients of both carbonate and molecular CO₂ decrease with temperature. This effect can be quantitatively modeled as the result of a reduced occupancy of the vibrational ground state. In alkali silicate (NBO/t = 0.98) and basaltic andesite (NBO/t = 0.42) melt, only carbonate was detected up to the highest temperatures studied. For dacite (NBO/t = 0.09) and phonolite melts (NBO/t = 0.14), the equilibrium CO₂ + O^2? = CO₃ ^2? in the melt shifts toward CO₂ with increasing temperature, with ln K = ?4.57 (±1.68) + 5.05 (±1.44) 10³ T ^?1 for dacite melt (ΔH = ?42 kJ mol^?1) and ln K = ?6.13 (±2.41) + 7.82 (±2.41) 10³ T ^?1 for phonolite melt (ΔH = ?65 kJ mol^?1), where K is the molar ratio of carbonate over molecular CO₂ and T is temperature in Kelvin. Together with published data from annealing experiments, these results suggest that ΔS and ΔH are linear functions of NBO/t. Based on this relationship, a general model for CO₂ speciation in silicate melts is developed, with ln K = a + b/T, where T is temperature in Kelvin and a = ?2.69 ? 21.38 (NBO/t), b = 1,480 + 38,810 (NBO/t). The model shows that at temperatures around 1,500 °C, even depolymerized melts such as basalt contain appreciable amounts of molecular CO₂, and therefore, the diffusion coefficient of CO₂ is only slightly dependent on composition at such high temperatures. However, at temperatures close to 1,000 °C, the model predicts a much stronger dependence of CO₂ solubility and speciation on melt composition, in accordance with available solubility data.     

Contrasting compositional trends of rocks and olivine-hosted melt inclusions from Cerro Negro volcano (Central America): implications for decompression-driven fractionation of hydrous magmas

Melt inclusions in olivine Fo_83–72 from tephras of 1867, 1971 and 1992 eruptions of Cerro Negro volcano represent a series of basaltic to andesitic melts of narrow range of MgO (5.6–8 wt %) formed by ~46 wt % fractional crystallization of olivine (~6 wt %), plagioclase (~27 wt %), pyroxene (~13 wt %) and magnetite (<1 wt %) from primitive basaltic melt (average SiO₂ = 49 wt %, MgO = 7.6 wt %, H₂O = 6 wt %) as it ascended to the surface from the depth of about 14 km. The crystallization occurred at increasing liquidus temperature from 1,050 to 1,090 °C in the pressure range from 400 to 50 MPa and was induced by release of mixed H₂O–CO₂ fluid from the melt at decreasing pressure. Matrix glass compositions fall at the high-Si end of the melt inclusion trend and represent the final stage of melt crystallization during and after eruption. The bulk compositions of erupted Cerro Negro magmas (tephras and lavas) range from high- to low-MgO (3–10 wt %) basalts, which form a compositional array crossing the trend of melt inclusions so that virtually no rock from Cerro Negro has composition akin to true melt represented by the inclusions. The variations of the bulk magma (rocks) and melt (melt inclusions) compositions can be generated in a dyke connecting a deep primitive magma reservoir with the Cerro Negro edifice. While the melt inclusions represent the compositional trend of instantaneous melts along the magma pathway at decreasing pressure and H₂O content, occurrence of low-Mg to high-Mg basalts reflects the process of phenocryst re-distribution in progressively evolving melt. The crystallization scenario is anticipated to operate everywhere in dykes feeding basaltic volcanoes and can explain the predominance of plagioclase-rich high-Al basalts in island arc as well as typical compositional variations of magmas during single eruptions.     

Experimental constraints on permeable gas transport in crystalline silicic magmas

The gas and fluid transport in magmas via permeable flow through interconnected bubble networks controls the rate of outgassing from magmas ascending in volcanic conduits and the fluid transport in the mushy boundary layer of magma reservoirs. Hence, clarifying its mechanism and rate is crucial to understanding the explosivity of volcanic eruptions and the evolution and dynamics of a magma reservoir. Recent experimental studies have determined the gas permeabilities in crystal-free rhyolite and basalt. However, no experimental study has investigated the effect of the crystal contents on the permeable gas transport in magmas. In this study, we performed decompression experiments for hydrous rhyolitic melts having crystallinities of 30 and 50 vol% to examine the effect of crystals on the bubble microstructure and gas permeability during magma vesiculation. Size-controlled (100-meshed) corundum crystals were used as an analog of the phenocrysts in silicic magmas. Microstructural analyses using X-ray CT showed that bubbles coalesce and their connectivity increases with a decrease in the final pressure after the decompression, that is, an increase in the vesicularity. As long as the vesicularities of melt part in the crystal-free basis (melt vesicularity) were similar, no clear effect of the crystallinity on the degree of bubble coalescence and connectivity was observed at melt vesicularities <68 vol%. The corundum showed a large contact angle with aqueous fluid as well as plagioclase and alkaline feldspar; this failed to induce the efficient heterogeneous nucleation and coalescence of bubbles on its surface. The gas permeabilities of all the run products were lower than the detection limits of the present analysis (the order of 10⁻¹⁶ m²) at melt vesicularities <68 vol%. These results show that silicic magmas containing 30 and 50 vol% phenocrysts with a large contact angle have low gas permeabilities until the vesicularity becomes large (at least >68 vol%). This result indicates that the permeable fluid transport through a deep volcanic conduit, which has been proposed on the basis of the observations of volcanic gases and natural products, is so slow that other processes, like shear deformation or magma convection, may be needed to explain the observations.     

Carbonatite and highly peralkaline nephelinite melts from Oldoinyo Lengai Volcano,Tanzania: The role of natrite-normative fluid degassing

Oldoinyo Lengai, located in the Gregory Rift in Tanzania, is a world-famous volcano owing to its uniqueness in producing natrocarbonatite melts and because of its extremely high CO₂ flux. The volcano is constructed of highly peralkaline [PI = molar (Na₂O + K₂O)/Al₂O₃ > 2–3] nephelinite and phonolites, both of which likely coexisted with carbonate melt and a CO₂-rich fluid before eruption. Results of a detailed melt inclusion study of the Oldoinyo Lengai nephelinite provide insights into the important role of degassing of CO₂-rich vapor in the formation of natrocarbonatite and highly peralkaline nephelinites. Nepheline phenocrysts trapped primary melt inclusions at 750–800 °C, representing an evolved state of the magmas beneath Oldoinyo Lengai. Raman spectroscopy, heating-quenching experiments, low current EDS and EPMA analyses of quenched melt inclusions suggest that at this temperature, a dominantly natrite_ss-normative, F-rich (7–14 wt%) carbonate melt and an extremely peralkaline (PI = 3.2–7.9), iron-rich nephelinite melt coexisted following degassing of a CO₂ + H₂O-vapor. We furthermore hypothesize that the degassing led to re-equilibration between the melt and liquid phases that remained and involved 1/ mixing between the residual (after degassing) alkali carbonate liquid and an F-rich carbonate melt and 2/ enrichment of the coexisting nephelinite melt in alkalis. We suggest that in the geological past similar processes were responsible for generating highly peralkaline silicate melts in continental rift tectonic settings worldwide.     

Sources, degassing, and contamination of CO2, H2O, He, Ne, and Ar in basaltic glasses from Kolbeinsey Ridge, North Atlantic

New volatile data (CO₂, H₂O, He, Ne, and Ar) are presented for 24 submarine basaltic glasses from the Kolbeinsey Ridge, Tjörnes Fracture Zone and Mohns Ridge, North Atlantic. Low CO₂ and He contents indicate that magmas were strongly outgassed with the extent of degassing increasing toward the south, as expected from shallower ridge depths. Ne and Ar are significantly more abundant in the southernmost glasses than predicted for degassed melt. The strong atmospheric isotopic signal associated with this excess Ne and Ar suggests syn- or posteruptive contamination by air. Degassing, by itself, cannot generate the large variations in δ¹³C values of dissolved CO₂ or coupled CO₂-Ar variations. This suggests that δ¹³C values were also affected by some other processes, most probably melt-crust interaction. Modelling indicates that degassing had a negligible influence on water owing to its higher solubility in basaltic melt than the other volatiles. Low H₂O contents in the glasses reflect melting of a mantle source that is not water-rich relative to the source of N-MORB.Before eruption, Kolbeinsey Ridge melts contained ∼400 ppm CO₂ with δ¹³C of −6‰, 0.1 to 0.35 wt.% H₂O, ³He/⁴He ∼11 R_A, and CO₂/³He of ∼2 × 10⁹. We model restored volatile characteristics and find homogeneous compositions in the source of Kolbeinsey Ridge magmas. Relative to the MORB-source, He and Ne are mildly fractionated while the ⁴⁰Ar/³⁶Ar may be low. The ³He/⁴He ratios in Tjörnes Fracture Zone glasses are slightly higher (13.6 R_A) than on Kolbeinsey Ridge, suggesting a greater contribution of Icelandic mantle from the south, but the lack of ³He/⁴He variation along the Kolbeinsey Ridge is inconsistent with active dispersal of Icelandic mantle beyond the Tjörnes Fracture Zone.     

Experimental study into the petrogenesis of crystal-rich basaltic to andesitic magmas at Arenal volcano

Arenal volcano is nearly unique among arc volcanoes with its 42 year long (1968–2010) continuous, small-scale activity erupting compositionally monotonous basaltic andesites that also dominate the entire, ~7000 year long, eruptive history. Only mineral zoning records reveal that basaltic andesites are the result of complex, open-system processes deriving minerals from a variety of crystallization environments and including the episodic injections of basalt. The condition of the mafic input as well as the generation of crystal-rich basaltic andesites of the recent, 1968–2010, and earlier eruptions were addressed by an experimental study at 200 MPa, 900–1,050 °C, oxidizing and fluid-saturated conditions with various fluid compositions [H₂O/(H₂O + CO₂) = 0.3–1]. Phase equilibria were determined using a phenocryst-poor (~3 vol%) Arenal-like basalt (50.5?wt% SiO₂) from a nearby scoria cone containing olivine (Fo₉₂), plagioclase (An₈₆), clinopyroxene (Mg# = 82) and magnetite (X_ulvö = 0.13). Experimental melts generally reproduce observed compositional trends among Arenal samples. Small differences between experimental melts and natural rocks can be explained by open-system processes. At low pressure (200 MPa), the mineral assemblage as well as the mineral compositions of the natural basalt were reproduced at 1,000 °C and high water activity. The residual melt at these conditions is basaltic andesitic (55 wt% SiO₂) with 5 wt% H₂O. The evolution to more evolved magmas observed at Arenal occurred under fluid-saturated conditions but variable fluid compositions. At 1,000 °C and 200 MPa, a decrease of water content by approximately 1 wt% induces significant changes of the mineral assemblage from olivine + clinopyroxene + plagioclase (5 wt% H₂O in the melt) to clinopyroxene + plagioclase + orthopyroxene (4 wt% H₂O in the melt). Both assemblages are observed in crystal-rich basalt (15 vol%) and basaltic andesites. Experimental data indicate that the lack of orthopyroxene and the presence of amphibole, also observed in basaltic andesitic tephra units, is due to crystallization at nearly water-saturated conditions and temperatures lower than 950 °C. The enigmatic two compositional groups previously known as low- and high-Al₂O₃ samples at Arenal volcano may be explained by low- and high-pressure crystallization, respectively. Using high-Al as signal of deeper crystallization, first magmas of the 1968–2010 eruption evolved deep in the crust and ascent was relatively fast leaving little time for significant compositional overprint by shallower level crystallization.     

Diffusive fractionation of volatiles and their isotopes during bubble growth in magmas

Bubbles grow in decompressing magmas by simple expansion and by diffusive supply of volatiles to the bubble/melt interface. The latter phenomenon is of significant geochemical interest because diffusion can fractionate elements and isotopes (or isotopologues) of dissolved components. This raises the possibility that the character of volatile components in bubbles may not reflect that of volatiles dissolved in the host melt over the lifetime of a bubble—even in the absence of equilibrium vapor/melt isotopic fractionation. Recent experiments have confirmed the existence of an isotope mass effect on diffusion of the volatile element Cl in silicate melt [Fortin et al. (Isotopic fractionation of chlorine during chemical diffusion in a dacitic melt and its implications for isotope behavior during bubble growth (abstract), 2016 Fall AGU Meeting, 2016)], so there is a clear need to understand the efficacy of diffusive fractionation during bubble growth. In this study, numerical models of diffusion and mass redistribution during bubble growth were implemented for both “passive” volatiles—those whose concentrations are generally well below saturation levels—and “active” volatiles such as CO₂ and H₂O, whose elevated concentrations and limited solubilities are the cause of bubble nucleation and growth. Both diffusive and convective bubble-growth scenarios were explored. The magnitude of the isotope mass effect on passive volatiles partitioned into bubbles growing at a constant rate R in a static system depends upon R/D _L, K _d and D _H/D _L (K _d = bubble/melt partition coefficient; D _H/D _L = diffusivity ratio of the heavy and light isotopes). During convective bubble growth, the presence of a discrete (physical) melt boundary layer against the growing bubble (of width x _BL) simplifies outcomes because it leads to the quick onset of steady-state fractionation during growth, the magnitude of which depends mainly upon R?x _BL/D _L and D _H/D _L (bubble/melt fractionation is maximized at R?x _BL/D _L ≈0.1). Constant R is unrealistic for most real systems, so other scenarios were explored by including the solubility and EOS of an “active” volatile (e.g., CO₂) in the numerical simulations. For plausible decompression paths, R increases exponentially with time—leading, potentially, to larger isotopic fractionation of species partitioned into the growing bubble. For volatile species whose isotope mass effects on diffusion have been measured (Cl, Li), predicted isotope fractionation in the exsolved vapor can be as large as ?4‰ for Cl and ?25‰ for Li.     

Phase relations and melting of carbonated peridotite between 10 and 20 GPa: a proxy for alkali- and CO<Subscript>2</Subscript>-rich silicate melts in the deep mantle

We determined the melting phase relations, melt compositions, and melting reactions of carbonated peridotite on two carbonate-bearing peridotite compositions (ACP: alkali-rich peridotite + 5.0 wt % CO₂ and PERC: fertile peridotite + 2.5 wt % CO₂) at 10–20 GPa and 1,500–2,100 °C and constrain isopleths of the CO₂ contents in the silicate melts in the deep mantle. At 10–20 GPa, near-solidus (ACP: 1,400–1,630 °C) carbonatitic melts with < 10 wt % SiO₂ and > 40 wt % CO₂ gradually change to carbonated silicate melts with > 25 wt % SiO₂ and < 25 wt % CO₂ between 1,480 and 1,670 °C in the presence of residual majorite garnet, olivine/wadsleyite, and clinoenstatite/clinopyroxene. With increasing degrees of melting, the melt composition changes to an alkali- and CO₂-rich silicate melt (Mg# = 83.7–91.6; ~ 26–36 wt % MgO; ~ 24–43 wt % SiO₂; ~ 4–13 wt % CaO; ~ 0.6–3.1 wt % Na₂O; and ~ 0.5–3.2 wt % K₂O; ~ 6.4–38.4 wt % CO₂). The temperature of the first appearance of CO₂-rich silicate melt at 10–20 GPa is ~ 440–470 °C lower than the solidus of volatile-free peridotite. Garnet + wadsleyite + clinoenstatite + carbonatitic melt controls initial carbonated silicate melting at a pressure < 15 GPa, whereas garnet + wadsleyite/ringwoodite + carbonatitic melt dominates at pressure > 15 GPa. Similar to hydrous peridotite, majorite garnet is a liquidus phase in carbonated peridotites (ACP and PERC) at 10–20 GPa. The liquidus is likely to be at ~ 2,050 °C or higher at pressures of the present study, which gives a melting interval of more than 670 °C in carbonated peridotite systems. Alkali-rich carbonated silicate melts may thus be produced through partial melting of carbonated peridotite to 20 GPa at near mantle adiabat or even at plume temperature. These alkali- and CO₂-rich silicate melts can percolate upward and may react with volatile-rich materials accumulate at the top of transition zone near 410-km depth. If these refertilized domains migrate upward and convect out of the zone of metal saturation, CO₂ and H₂O flux melting can take place and kimberlite parental magmas can be generated. These mechanisms might be important for mantle dynamics and are potentially effective metasomatic processes in the deep mantle.     

Felsic magmas of the caldera-forming eruptions on the Iturup Island: the first results of studies of melt inclusions in phenocrysts from pumices of the Lvinaya Past and Vetrovoy Isthmus calderas

The paper reports the first results of the petrological studies of magmatic melts that formed siliceous pyroclastic deposits related to voluminous eruptions on Iturup Island. The caldera-forming eruptions of the Lvinaya Past and the Vetrovoy Isthmus, having similar features, resulted from the evolution of silicic melts that originated from partial melting of metabasalts. According to the mineral thermometry results, the melt was crystallized at ~800°C. The phenocrysts from the Vetrovoy Isthmus pumices were crystallized at <1 kbar, while those from the Lvinaya Past were formed at higher pressures. The pyroclastic rock compositions in both calderas correspond to moderately aluminous dacite and rhyolitic dacite of the normal series, whose melts likely did not undergo significant crystallization differentiation before the eruptions. The main volatile components of the magma include H₂O, CO₂, S, F, and Cl. Degassing with emission of water–carbon-dioxide fluid accompanied the early crystallization of plagioclase in the Vetrovoy Isthmus pumice. Evidence of pre-eruption melt degassing in the Lvinaya Past were not found. Water release from the melts may be related to both the early magma degassing and the eruptions. The lack of data evidencing the deep differentiation and mixing of contrasting melts implies a relatively small time period between the acid melt appearance and eruptions.     

Experimental phase relations of a low MgO Aleutian basaltic andesite at XH2O = 0.7–1

We conducted melting experiments on a low MgO (3.29 wt.%) basaltic andesite (54.63 wt.% SiO₂) from Westdahl volcano, Alaska, at XH₂O = 0.7–1 and fO₂ ~ Ni–NiO, at pressures = 0.1–180 MPa and temperatures = 900–1,200 °C. We examine the evolution of the melt along a liquid line of descent during equilibrium crystallization at high H₂O and fO₂ conditions, starting from a high FeOt/MgO, low MgO basaltic andesite. Ti-magnetite formed on the liquidus regardless of XH₂O, followed by clinopyroxene, plagioclase, amphibole, and orthopyroxene. We observe slight but significant differences in the phase stability curves between the XH₂O = 1 and 0.7 experiments. Early crystallization of Ti-magnetite and suppression of plagioclase at higher pressures and temperatures resulted in strongly decreasing melt FeOt/MgO with increasing SiO₂, consistent with a “calc-alkaline” compositional trend, in agreement with prior phase equilibria studies on basalt at similar H₂O and fO₂. Our study helps quantify the impact of small amounts of CO₂ and high fO₂ on the evolution of melts formed during crystallization of a low MgO basaltic andesite magma stored at mid- to shallow crustal conditions. Like the prior studies, we conclude that H₂O strongly influences melt evolution trends, through stabilization of Ti-magnetite on the liquidus and suppression of plagioclase at high P–T conditions.     

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.