Buoyancy-controlled eruption of magmas at Mt Etna

Buoyancy controls the ability of magma to rise, its ascent rate and the style of the eruptions. Geophysical, geological and petrological data have been integrated to evaluate the buoyancy of magmas at Mt Etna. The density difference between host rocks and magmas is mainly related to the amount of H₂O dissolved in the magma and to the bubble‐liquid separation processes. In the depth interval 22–2 km b.s.l. highly hydrated (H₂O ～ 3%) basaltic magmas or mixtures of bubbles + liquid have positive buoyancy and rise rapidly. Conversely, bubble‐depleted liquids, with an intermediate H₂O content (～ 1.5%), having neutral buoyancy, will spread out and form magmatic reservoirs at different depths until cooling/crystallization further modify composition and density. These different processes account for the magma compositions, location of magmatic reservoirs as determined by geophysical methods, and the complex eruptive cycles (slow effusions, fire fountains and Plinian eruptions) that have been observed in the history of the volcano.     

Generation of CO2-rich melts during basalt magma ascent and degassing

To test mechanisms of basaltic magma degassing, continuous decompressions of volatile-bearing (2.7–3.8 wt% H₂O, 600–1,300 ppm CO₂) Stromboli melts were performed from 250–200 to 50–25 MPa at 1,180–1,140 °C. Ascent rates were varied from 0.25 to ~1.5 m/s. Glasses after decompression show a wide range of textures, from totally bubble-free to bubble-rich, the latter with bubble number densities from 10⁴ to 10⁶ cm^?3, similar to Stromboli pumices. Vesicularities range from 0 to ~20 vol%. Final melt H₂O concentrations are homogeneous and always close to solubilities. In contrast, the rate of vesiculation controls the final melt CO₂ concentration. High vesicularity charges have glass CO₂ concentrations that follow theoretical equilibrium degassing paths, whereas glasses from low vesicularity charges show marked deviations from equilibrium, with CO₂ concentrations up to one order of magnitude higher than solubilities. FTIR profiles and maps reveal glass CO₂ concentration gradients near the gas–melt interface. Our results stress the importance of bubble nucleation and growth, and of volatile diffusivities, for basaltic melt degassing. Two characteristic distances, the gas interface distance (distance either between bubbles or to gas–melt interfaces) and the volatile diffusion distance, control the degassing process. Melts containing numerous and large bubbles have gas interface distances shorter than volatile diffusion distances, and degassing proceeds by equilibrium partitioning of CO₂ and H₂O between melt and gas bubbles. For melts where either bubble nucleation is inhibited or bubble growth is limited, gas interface distances are longer than volatile diffusion distances. Degassing proceeds by diffusive volatile transfer at the gas–melt interface and is kinetically limited by the diffusivities of volatiles in the melt. Our experiments show that CO₂-oversaturated melts can be generated as a result of magma decompression. They provide a new explanation for the occurrence of CO₂-rich natural basaltic glasses and open new perspectives for understanding explosive basaltic volcanism.     

Bubble growth in slightly supersaturated albite melt at constant pressure

Bubble growth experiments were performed in a piston-cylinder by hydrating albite melt with ∼11 wt.% H₂O at 550 MPa followed by rapid decompression at 1 MPa s⁻¹ to pressures of 450 or 400 MPa. At these conditions the melt was supersaturated with ∼0.5 or ∼1.5 wt.% H₂O, respectively, which caused rapid exsolution and bubble growth. Results at 1200 °C demonstrate that portions of the initial cumulative bubble-area distributions may be characterized by a power law with an exponent near 1, but they rapidly evolve to exponential distributions and approach a unimodal distribution after 32 h of growth. This evolution occurs by the growth of larger bubbles at the expense of smaller ones. The growth rate of the average bubble radius in these experiments is described by a power law whose exponent is 0.35, close to the theoretical exponent of 1/3 for phase growth in which coalescence is dominated by Ostwald ripening of the bubbles. Over the range of pressures and water contents investigated at 1200 °C, the bubble-size distributions and growth rate are not significantly affected by changes in the amount of exsolved water or by splitting the decompression path into two steps. Similar decompression experiments at 800 °C are dominated by smaller bubbles than in the 1200 °C experiments and also demonstrate exponential cumulative size distributions, but consistently contain a small fraction of larger bubbles. The growth rate of these bubble radii cannot be fit with a power law, but a logarithmic dependence of the bubble radii on time is possible, suggesting a difference in the growth mechanisms at low and high temperatures. This difference is attributed to the orders of magnitude changes in melt viscosity and water diffusion in the melt as the temperature varies from 800 to 1200 °C. At 1200 °C the transport properties of albite melt resemble those of natural basaltic melts whereas at 800 °C the properties are similar to those of andesitic to dacitic melts. The decompression rate used in this study exceeds natural rates by one to two orders of magnitude. Thus, these results indicate that natural mafic-to-intermediate magmas supersaturated with only a small excess of water should easily nucleate bubbles during ascent and that bubble growth in mafic magmas will proceed much more rapidly than in andesitic to dacitic magmas. Intermediate composition magmas also may be capable of forming bimodal bubble-size distributions even in the case when only one nucleation event occurred. The rapid evolution of the bubble-size distribution from a power law to an exponential may be useful in constraining the time duration between bubble nucleation and the quenching of natural samples.     

Volatile loss from melt inclusions in pyroclasts of differing sizes

We have investigated the loss of H₂O from olivine-hosted melt inclusions (MIs) by designing an experiment using tephra samples that cooled at different rates owing to their different sizes: ash, lapilli, and bomb samples that were deposited on the same day (10/17/74) of the sub-Plinian eruption of Volcán de Fuego in Guatemala. Ion microprobe, laser ablation-ICPMS, and electron probe analyses show that MIs from ash and lapilli record the highest H₂O contents, up to 4.4 wt%. On the other hand, MIs from bombs indicate up to 30 % lower H₂O contents (loss of ~1 wt% H₂O) and 10 % post-entrapment crystallization of olivine. This evidence is consistent with the longer cooling time available for a bomb-sized clast, up to 10 min for a 3–4-cm radius bomb, assuming conductive cooling and the fastest H diffusivities measured in olivine (D~10^?9 to 10^?10 m²/s). On the other hand, several lines of evidence point to some water loss prior to eruption, during magma ascent and degassing in the conduit. Thus, results point to both slower post-eruptive cooling and slower magma ascent affecting MIs from bombs, leading to H₂O loss over the timescale of minutes to hours. The important implication of this study is that a significant portion of the published data on H₂O concentrations in olivine-hosted MIs may reflect unrecognized H₂O loss via diffusion. This work highlights the importance of reporting clast and MI sizes in order to assess diffusive effects and the potential benefit of using water loss as a chronometer of magma ascent.     

Heterogeneous bubble nucleation on Fe-Ti oxide crystals in high-silica rhyolitic melts

The nucleation of H₂O bubbles in magmas has been proposed as a trigger for volcanic eruptions. To determine how bubbles nucleate heterogeneously in silicate melts, experiments were carried out in which high-silica rhyolitic melts were hydrated at 740-800°C and 50-175 MPa, decompressed by 20-70 MPa, and held at the lower pressures for ≥10 s before being quenched. The hydration conditions were subliquidus, and all samples contain blocky magnetite + needle-shaped hematite ± plagioclase. Magnetite is abundant at 800°C and high pressures, whereas hematite becomes more abundant at lower temperatures and pressures. Bubbles nucleated in a single event in all samples, with the number density (N_T) of bubbles varying between 2 × 10⁷ and 1 × 10⁹ cm⁻³. At low degrees of supersaturation, one to a few bubbles nucleate on faces of magnetite, but at medium to high degrees of supersaturation, multiple bubbles nucleate on single magnetite grains. On hematite, one to a few bubbles nucleated at the ends of the needle-shaped crystals at medium supersaturations, but formed along their entire lengths at high supersaturations. N_T increases as water diffusivity decreases, indicating that the number of bubbles nucleated is influenced by their growth, which depletes the melt with respect to H₂O and lowers supersaturation. If volcanic eruptions are triggered by bubble formation in magmas stored in shallow-level magma chambers, then the supersaturations needed for heterogeneous nucleation suggest that only small amounts of crystallization are needed, whereas homogeneous nucleation is unlikely to trigger eruptions.     

Volatiles contents, degassing and crystallisation of intermediate magmas at Volcan de Colima, Mexico, inferred from melt inclusions

In volatile-saturated magmas, degassing and crystallisation are interrelated processes which influence the eruption style. Melt inclusions provide critical information on volatile and melt evolution, but this information can be compromised significantly by post-entrapment modification of the inclusions. We assess the reliability and significance of pyroxene-hosted melt inclusion analyses to document the volatile contents (particularly H₂O) and evolution of intermediate arc magmas at Volcán de Colima, Mexico. The melt inclusions have maximal H₂O contents (≤4 wt%) consistent with petrological estimates and the constraint that the magmas crystallised outside the amphibole stability field, demonstrating that pyroxene-hosted melt inclusions can preserve H₂O contents close to their entrapment values even in effusive eruptions with low effusion rates (0.6 m³ s^?1). The absence of noticeable H₂O loss in some of the inclusions requires post-entrapment diffusion coefficients (≤1 × 10^?13 m² s^?1) at least several order of magnitude smaller than experimentally determined H⁺ diffusion coefficient in pyroxenes. The H₂O content distribution is, however, not uniform, and several peaks in the data, interpreted to result from diffusive H₂O reequilibration, are observed around 1 and 0.2 wt%. H₂O diffusive loss is also consistent with the manifest lack of correlations between H₂O and CO₂ or S contents. The absence of textural evidence supporting post-entrapment H₂O loss suggests that diffusion most likely occurred via melt channels prior to sealing of the inclusions, rather than through the host crystals. Good correlation between the melt inclusion sealing and volcano-tectonic seismic swarm depths further indicate that, taken as a whole, the melt inclusion population accurately records the pre-eruptive conditions of the magmatic system. Our data demonstrate that H₂O diffusive loss is a second-order process and that pyroxene-hosted melt inclusions can effectively record the volatile contents and decompression-induced crystallisation paths of vapour-saturated magmas.     

Development and evolution of water vapor vesicles during fast thermal breakdown of muscovite

At 1,175°C-1 bar, muscovite in natural granite powders is completely transformed after 5 min. Due to the overlapping of several processes such as dehydroxylation, mineralogical transformations, collapse and sintering of transformed lamellae, a few parts per thousand of H₂O vapor are trapped, generating bubbles in muscovite pseudomorphs. For short durations (5–40 min), the crystallographic properties of the precursor muscovite control the geometry of the bubbles that may be compared to thick disks with a rounded shape in basal sections and an elongated shape in lateral section, parallel to the former cleavage planes of muscovite. With longer durations the bubbles change from thick disks to spheres, which can be explained by the release of constraints perpendicular to basal planes upon growth of the high temperature Si–Al oxides. With time, the number of bubbles decreases while the bubble size and the porosity of the pseudomorphs increase. Bubble behavior was analyzed in terms of ripening, shape transformations and coalescence.     

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.     

Genesis of fumarolic emissions as inferred by isotope mass balances: CO2 and water at Vulcano Island, Italy

We have developed a quantitative model of CO₂ and H₂O isotopic mixing between magmatic and hydrothermal gases for the fumarolic emissions of the La Fossa crater (Vulcano Island, Italy). On the basis of isotope balance equations, the model takes into account the isotope equilibrium between H₂O and CO₂ and extends the recent model of chemical and energy two-end-member mixing by Nuccio et al. (1999). As a result, the H₂O and CO₂ content and the δD, δ¹⁸O, and δ¹³C isotope compositions for both magmatic and hydrothermal end-members have been assessed. Low contributions of meteoric steam, added at a shallow depth, have been also recognized and quantified in the fumaroles throughout the period from 1988 to 1998. Nonequilibrium oxygen isotope exchange also seems to be occurring between ascending gases and wall rocks along some fumarolic conduits.The δ¹³C_CO2 of the magmatic gases varies around −3 to 1‰ vs. Peedee belemnite (PDB), following a perfect synchronism with the variations of the CO₂ concentration in the magmatic gases. This suggests a process of isotope fractionation because of vapor exsolution caused by magma depressurization. The hydrogen isotopes in the magmatic gases (−1 to −‰ vs. standard mean ocean water [SMOW]), as well as the above δ¹³C_CO2 value, are coherent with a convergent tectonic setting of magma generation, where the local mantle is widely contaminated by fluids released from the subducted slab. Magma contamination in the crust probably amplifies this effect.The computed isotope composition of carbon and hydrogen in the hydrothermal vapors has been used to calculate the δD and δ¹³C of the entire hydrothermal system, including mixed H₂O-CO₂ vapor, liquid water, and dissolved carbon. We have computed values of about 10‰ vs. SMOW for water and −2 to −6.5‰ vs. PDB for CO₂. On these grounds, we think that Mediterranean marine water (δD_H2O ≈ 10‰) feeds the hydrothermal system. It infiltrates at depth throughout the local rocks, reaching oxygen isotope equilibrium at high temperatures. Interaction processes between magmatic gases and the evolving seawater also seem to occur, causing the dissolution of isotopically fractionated aqueous CO₂ and providing the source for hydrothermal carbon. These results have important implications concerning fluid circulation beneath Vulcano and address the more convenient routine of geochemical surveillance.     

Fluid Composition, δD of Channel H2O,and δ18O of Lattice Oxygen in Beryls: Genetic Implications for Brazilian,Colombian, and Afghanistani Emerald Deposits

The fluid composition, δD of channel H₂O, and δ₁₈O of lattice oxygen have been determined in beryl and emerald from a variety of geological environments and used to constrain the origin of the parental fluids from which beryl has grown. Step-heating analyses performed by quadrupolar mass spectrometry were used to quantify the composition of the fluid phases in beryl from granitic pegmatites and greisens and emerald from Brazil, Colombia, and Afghanistan. An important conclusion is that beryl and emerald have a similar fluid composition, with concentrations of H₂O being greater than 90% of the total water in the mineral irrespective of the age of formation (2.0 Ga to 32 Ma) and tectonic settings. However, the Brazilian Santa Terezinha shear-zone emerald deposit contains abundant CO₂, up to 13 wt% of the total fluid. A second conclusion is that the channel H₂O content for some Brazilian emeralds is higher than the range defined for beryl in the literature, especially for those related to the shear-zone type (2.99 lt; H₂O < 3.16 wt%) and the pegmatite type from the Pombos, Pela Ema, and Pirenopolis deposits (2.78 < H₂O < 3.01 wt%). Colombian emeralds have very low H₂O contents (1.30 < H₂O < 1.96 wt%), among the lowest in the world.

Brazilian, Colombian, and Afghanistani emeralds have contrasting and restricted ranges of δ¹⁸O values. In Brazil, emeralds related to pegmatites have a systematic δ¹⁸O inter-deposit variability (+6.3 < δ¹⁸O < +12.4‰). The calculated δ¹⁸O of the fluid was buffered by the host ultrabasic rocks during fluid-rock interaction. Emerald and cogenetic phlogopite related to shear-zone-type deposits have a quite restricted δ¹⁸O range (+12.0 < δ¹⁸O 7lt; +12.4‰); the calculated is interpreted to represent the original isotopic composition of the hydrothermal fluid. Relative to Brazil, the δ¹⁸O of Colombian and Afghanistani emeralds shows strong enrichment in ¹⁸O (+13.4 < δ¹⁸O < +23.6‰), and the high calculated δ¹⁸O of the fluid suggests extensive reaction with 18O-rich sedimentary or metasedimentary rocks.

In Brazil, the δD composition of channels in emerald and the calculated δ¹⁸O^H₂O for phlogopite are compatible with both magmatic and metamorphic origins. A magmatic origin is supported for emeralds associated with the pegmatitic Socotó and Carnaiba deposits (mean δD = ?37.8 ± 8‰) and a metamorphic origin is suggested for the Santa Terezinha shear-zone type (mean δD = ?32.4 ± 3‰). A metamorphic origin is proposed for Colombian emeralds. Afghanistani emeralds have a δD composition of channels (mean δD = ?46.3 ± 1.3‰) that is compatible with both magmatic and metamorphic origins.     

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.     

Fluid inclusion and isotope geochemistry of the Yangla copper deposit,Yunnan, China

The Yangla copper deposit, with Cu reserves of 1.2 Mt, is located between a series of thrust faults in the Jinshajiang–Lancangjiang–Nujiang region, Yunnan, China, and has been mined since 2007. Fluid inclusion trapping conditions ranged from 1.32 to 2.10 kbar at 373–409 °C. Laser Raman spectroscopy confirms that the vapour phase in these inclusions consists of CO₂, CH₄, N₂ and H₂O. The gas phases in the inclusions are H₂O and CO₂, with minor amounts of N₂, O₂, CO, CH₄, C₂H₂, C₂H₄, and C₂H₆. Within the liquid phase, the main cations are Ca²⁺ and Na⁺ while the main anions are SO₄ ^2? and Cl^?. The oxygen and hydrogen isotope compositions of the ore-forming fluids (?3.05‰?≤?δ¹⁸O_H2O?≤?2.5‰; ?100‰?≤?δD?≤??120‰) indicate that they were derived from magma and evolved by mixing with local meteoric water. The δ³⁴S values of sulfides range from ?4.20‰ to 1.85‰(average on ?0.85‰), supporting a magmatic origin. Five molybdenite samples taken from the copper deposit yield a well-constrained ¹⁸⁷Re–¹⁸⁷Os isochron age of 232.8?±?2.4 Ma. Given that the Yangla granodiorite formed between 235.6?±?1.2 Ma and 234.1?±?1.2 Ma, the Cu metallogenesis is slightly younger than the crystallization age of the parent magma. A tectonic model that combines hydrothermal fluid flow and isotope compositions is proposed to explain the formation of the Yangla copper deposit. At first, westward subduction of the Jinshajiang Oceanic Plate in the Early Permian resulted in the development of a series of thrust faults. This was accompanied by fractional melting beneath the overriding plate, triggering magma ascent and extensive volcanism. The thrust faults, which were then placed under tension during a change in tectonic mode from compression to extension in the Late Triassic, formed favorable pathways for the magmatic ore-forming fluids. These fluids precipitated copper-sulfides to form the Yangla deposit.     

Effects of CO<Subscript>2</Subscript> flushing on crystal textures and compositions: experimental evidence from recent K-trachybasalts erupted at Mt. Etna

Changes in magmatic assemblages and crystal stability as a response of CO₂-flushing in basaltic systems have rarely been directly addressed experimentally, making the role of CO₂ in magma dynamics still controversial and object of scientific debate. We conducted a series of experiments to understand the response of magmas from Etna volcano to CO₂ flushing. We performed a first experiment at 300 MPa to synthesize a starting material composed of crystals of some hundreds of µm and melt pools. This material is representative of an initial magmatic assemblage composed of plagioclase, clinopyroxene and a water-undersaturated melt with 1.6 wt% H₂O. In a second step, the initial assemblage was equilibrated at 300 and 100 MPa with fluids having different XCO ₂ ^fl (CO₂/(H₂O + CO₂)). At low XCO ₂ ^fl (< 0.2 to 0.4), plagioclase is completely dissolved and clinopyroxene show dissolution textures. For relatively high XCO ₂ ^fl (0.9 at 300 MPa), the flushing of a CO₂-rich fluid phase leads to an increase of the amount of clinopyroxene and a decrease of the abundance of plagioclase at 300 MPa. This decrease of plagioclase proportion is associated with a change in An content. Our experiments demonstrate that flushing basaltic systems with fluids may drastically affect crystal textures and phase equilibria depending on proportions of H₂O and CO₂ in the fluid phase. Since texture and crystal proportions are among the most important parameters governing the rheology of magmas, fluid flushing will also influence magma ascent to the Earth’s surface. The experimental results open new perspectives to decipher the textural and compositional record of minerals observed in volcanic rocks from Mt. Etna, and at the same time offer the basis for interpreting the information preserved in minerals from other basaltic volcanoes erupting magmas enriched in CO₂.     

Source and H2O content of high-MgO magmas in island arc settings: an experimental study of a primitive calc-alkaline basalt from St. Vincent, lesser antilles arc

Liquidus phase relationships have been determined for a high-MgO basalt (STV301: MgO=12.5 wt%, Ni=250 ppm, Cr=728 ppm) from Black Point, St Vincent (Lesser Antilles arc). Piston-cylinder experiments were conducted between 7.5 and 20 kbar under both hydrous and oxidizing conditions. AuPd capsules were used as containers. Compositions of supraliquidus glasses and mass-balance calculations show that Fe loss is < 10% in the majority of experiments. Two series of water concentrations in melt were investigated: (i) 1.5 wt% and (ii) 4.5 wt% H₂O, as determined by SIMS analyses on quenched glasses and with the by difference technique. The Fe³⁺/Fe²⁺ partitioning between Cr-Al spinel and melt and olivine-spinel equilibria show that oxidizing fO₂ were imposed (NNO + 1.5 for the 1.5 wt% H₂O series, NNO + 2.3 for the 4.5 wt% H₂O series). For both series of water concentrations, the liquid is multiply-saturated with a spinel lherzolite phase assemblage on its liquidus, at 1235°C, 11.5 kbar (1.5 wt% H₂O) and 1185°C, 16 kbar (4.5 wt% H₂O). Liquidus phases are homogeneous and comparable to typical mantle compositions. Mineral-melt partition coefficients are generally identical to values under anhydrous conditions. The modal proportion cpx/opx on the liquidus decreases from the 1.5 wt% to the 4.5 wt% H₂O series. The experimental data are consistent with STV301 being a product of partial melting of lherzolitic mantle. Conditions of multiple saturation progressively evolve toward lower temperatures and higher pressures with increasing melt H₂O concentration. Phase equilibria constraints, i.e., the necessity of preserving the mantle signature seen in high-MgO and picritic arc basalts, and glass inclusion data suggest that STV301 was extracted relatively dry (∼ 2 wt% H₂O) from its mantle source. However, not all primary arc basalts are extracted under similarly dry conditions because more hydrous melts will crystallize during ascent and will not be present unmodified at the surface. From degrees of melting calculated from experiments on KLB-1, extraction of a 12.5 wt% MgO melt with ∼ 2 wt% H₂O would require a H₂O concentration of 0.3 wt% in the sub-arc mantle. For mantle sources fluxed with a slab-derived hydrous component, extracted melts may contain up to ∼ 5.5 wt% H₂O.     

Interdiffusion of Na,K,and Ca Between Granitic Melts and NaCl Liquid

This study is aimed at determining the diffusion coefficient of net-work modifiers (mainly Na, K, and Ca) in a two-phase melt-NaCl system, in which the melts are granitic and the system is NaCl-rich in composition. The diffusion coefficients of Na, K, and Ca were measured at the temperatures of 750 – 1400°C, pressures of 0.001 × 10⁸ – 2 × 10⁸ Pa, and initial H₂O contents of 0 wt% –6.9 wt% in the granitic melts. The diffusion coefficients of Fe and Mg were difficult to resolve. In all experiments a NaCl melt was present as well. In the absence of H₂O, the diffusion of net-work modifiers follows an Arrhanious equation at 1 × 10⁵ Pa: lgD_ca=−3. 88−5140/T, lgD_k =−3. 79−4040/T, and lgD_Na, =−4.99−3350/T, where D is in cm² /s andT is in K. The diffusion coefficients of Ca, Na, K, and Fe increase non-linearly with increasing H₂O content in the melt. The presence of about 2 wt% H₂O m the melt will lead to a dramatical increase in diffusivity, but higher H₂O content has only a minor effect. This change is probably the result of a change in the melt structure when H₂O is present. The diffusion coefficients measured in this study are significantly different from those in previous works. This may be understood in terms of the “transient two-liquid equilibrium” theory. Element interdiffusion depends not only on its concentration, but also on its activity co-efficient gradient, which is reflected by the distribution coefficient, of the two contacting melts.     

Volatile constituents in magmatic inclusions

Laser Raman microprobe has been applied to the analysis of volatile components in shrinkage gas bubbles of individual magmatic inclusions in quartz crystal fragments and phenocrystals from the Mesozoic volcanic complexes of Tonglu and Shouchang, Zhejiang Province. Quantitative analyses are given for CO₂, CH₄, H₂O, CO, H₂, N₂, H₂S, and SO₂. In conjunction with the microthermometry and microbarometry data and the chemical composition of magmatic inclusions, the results permit one to calculate the physico-chemical parametersP _total,fO ₂ ,fCO ₂ ,fCH ₄ ,fH ₂O,fCO, andfH ₂ at the time individual magmatic inclusions were trapped. Based on the data obtained, some physico-chemical conditions for the Mesozoic volcanic magma evolution in the Tonglu and Shouchang areas are discussed. This work shows that this type of studies has become an indispensable new and rising domain in modern magmatic petrology, especially modern volcanic petrology. It can help us to reconstruct the physico-chemistry of the crystallization-evolution of a natural magma. The project was financially supported by the National Science Foundation of China.     

Carbon dioxide in petrogenesis III: role of volatiles in the ascent of alkaline magma with special reference to xenolith-bearing mafic lavas

Kinetic and fluid dynamic constraints on deep-seated magma migration rates suggest ascent velocities in the range 10 to 30 m/s, 10^–1 to 10 m/s and 10^–2 to 5 m/s for kimberlitic, garnet peridotite-bearing and spinel peridotite-bearing alkalic magmas. These rates virtually demand translithospheric magma transport by a fracture as opposed to diapiric mechanism. The hypothesis that volatile exsolution accelerates magma through the deep lithosphere is tested by solution of the appropriate set of conservation, mass balance and volatile component solubility equations governing the steady ascent (decompression) of compressible, two-phase magma (melt+H₂O+CO₂) in which irreversible phenomena (friction, heat transfer) are accounted for. The results of the numerical experiments were designed to test the importance of melt bulk composition (kimberlite, nephelinite, alkali basalt), initial conditions (mass flux (M), heat transfer coefficient (B), lumped friction factor (C _f )), conduit width (D), initial magma volatile content and geothermal gradients. The fractional increase in ascent rate (u/u _i ) is rarely greater than approximately 2 during translithospheric migration. The propellant hypothesis is rejected as a first-order mechanism driving magma acceleration during ascent. The most influential parameters governing ascent dynamics are M, C _f , D, B and the geotherm. Because of the relatively incompressible nature of the magmatic volatile phase at P>100 MPa, the initial magma volatile content plays a secondary (although demonstrable) role. The main role of volatiles is in controlling the initial magma flux (M) and the magma pressure during ascent. In adiabatic (B=0) simulations, magma ascends nearly isothermally. Generally, however, the assumption of adiabaticity is a poor one especially for flow through narrow (0.5 to 2 m) conduits in old (cold) lithosphere at rates 10^–1 m/s. The proposed fluid dynamic model is consistent with and complementary to the magma-driven crack propagation models. The generation of mantle metasomatic fluid is a corollary of the non-adiabatic ascent of volatile-bearing magma through the lithosphere. Magma heat death is an important process for the creation of mantle heterogeneity.     

The origin of the fumaroles of La Solfatara (Campi Flegrei, South Italy)

The analysis of gaseous compositions from Solfatara (Campi Flegrei, South Italy) fumaroles since the early 1980s, clearly reveals a double thermobarometric signature. A first signature at temperatures of about 360 °C was inferred by methane-based chemical-isotopic geoindicators and by the H₂/Ar geothermometer. These high temperatures, close to the critical point of water, are representative of a deep zone where magmatic gases flash the hydrothermal liquid, forming a gas plume. A second signature was found to be at around 200-240 °C. At these temperatures, the kinetically fast reactive species (H₂ and CO) re-equilibrate in a pure vapor phase during the rise of the plume. A combination of these observations with an original interpretation of the oxygen isotopic composition of the two dominant species, i.e. H₂O and CO₂, shed light on the origin of fumarolic fluids by showing that effluents are mixture between fluids degassed from a magma body and the vapor generated at about 360 °C by the vaporization of hydrothermal liquids. A typical ‘andesitic’ water type (δD ∼ −20‰, δ¹⁸O ∼10‰) and a CO₂-rich composition (X_CO2∼0.4) has been inferred for the magmatic fluids, while for the hydrothermal component a meteoric origin and a CO₂ fugacity fixed by fluid-rock reaction at high temperatures have been estimated. In the time the fraction of magmatic fluids in the fumaroles increased (up to ∼0.5) at each seismic and ground uplift crisis (bradyseism) which occurred at Campi Flegrei, suggesting that bradyseismic crises are triggered by periodic injections of CO₂-rich magmatic fluids at the bottom of the hydrothermal system.     

Experimental investigation of H2O and Cl− solubilities in F-enriched silicate liquids; implications for volatile saturation of topaz rhyolite magmas

To interpret the degassing of F-bearing felsic magmas, the solubilities of H₂O, NaCl, and KCl in topaz rhyolite liquids have been investigated experimentally at 2000, 500, and ≈1 bar and 700° to 975 °C. Chloride solubility in these liquids increases with decreasing H₂O activity, increasing pressure, increasing F content of the liquid from 0.2 to 1.2 wt% F, and increasing the molar ratio of ((Al + Na + Ca + Mg)/Si). Small quantities of Cl⁻ exert a strong influence on the exsolution of magmatic volatile phases (MVPs) from F-bearing topaz rhyolite melts at shallow crustal pressures. Water- and chloride-bearing volatile phases, such as vapor, brine, or fluid, exsolve from F-enriched silicate liquids containing as little as 1 wt% H₂O and 0.2 to 0.6 wt% Cl at 2000 bar compared with 5 to 6 wt% H₂O required for volatile phase exsolution in chloride-free liquids. The maximum solubility of Cl⁻ in H₂O-poor silicate liquids at 500 and 2000 bar is not related to the maximum solubility of H₂O in chloride-poor liquids by simple linear and negative relationships; there are strong positive deviations from ideality in the activities of each volatile in both the silicate liquid and the MVP(s). Plots of H₂O versus Cl⁻ in rhyolite liquids, for experiments conducted at 500 bar and 910°–930 °C, show a distinct 90° break-in-slope pattern that is indicative of coexisting vapor and brine under closed-system conditions. The presence of two MVPs buffers the H₂O and Cl⁻ concentrations of the silicate liquids. Comparison of these experimentally-determined volatile solubilities with the pre-eruptive H₂O and Cl⁻ concentrations of five North American topaz and tin rhyolite melts, determined from melt inclusion compositions, provides evidence for the exsolution of MVPs from felsic magmas. One of these, the Cerro el Lobo magma, appears to have exsolved alkali chloride-bearing vapor plus brine or a single supercritical fluid phase prior to entrapment of the melt inclusions and prior to eruption. Received: 6 November 1995 / Accepted: 29 January 1998     

Determination of hydrogen content in geological samples using elastic recoil detection analysis (ERDA)

The present study illustrates the interest of using the elastic recoil detection analysis (ERDA) method to characterize any geological sample matrix with respect to hydrogen. ERDA is combined with Rutherford back scattering (RBS) and particle induced X-ray emission (PIXE), allowing the simultaneous characterization of the matrix with respect to major and trace elements (Z > 15). Analyses are performed by mapping of a 4 × 16 μm² incident beam of ⁴He⁺ on large areas (50 × 200 μm²). The method is almost not destructive and requires no calibration with respect to well known hydrous samples. Hydrous and nominally anhydrous phases in contact with each other in the same sample may both be characterized. The depth of the analyses is limited to several μm beneath the surface, allowing tiny samples to be investigated, provided their sizes are larger than the incident beam. Our setup has been improved in order to allow H determination on a micrometric scale with a 5-15% relative uncertainty and a detection limit of 94 wt ppm H₂O. We present multi-elemental mappings on a large panel of samples: (1) natural and analogue synthetic glasses from Stromboli volcano (0.44-4.59 wt% H₂O), natural rhyolitic glasses (1466-1616 wt ppm H₂O); (2) magmatic rhyolitic melt inclusions from Guadeloupe Island (4.37-5.47 wt% H₂O) and their quartz host crystal (2020 ± 230 wt ppm H₂O); (3) nominally anhydrous natural (82-260 wt ppm H₂O) and experimentally hydrated (240-790 wt ppm H₂O) olivines; natural clinopyroxenes (159-716 wt ppm H₂O); natural orthopyroxenes (201-452 wt ppm H₂O); a natural garnet (90 wt ppm H₂O). Results show that ERDA is a strong and accurate reference method that can be used to characterize geological sample from various matrix compositions from high to low water contents. It can be used to calibrate other methods of microanalysis such as Fourier Transform Infrared Spectroscopy (FTIR) or secondary ion mass spectrometry (SIMS).