Dacitic Melts Research Articles

Sulfide breakdown controls metal signature in volcanic gas at Kawah Ijen volcano, Indonesia

Immiscible sulfide liquid is thought to be an important intermediary in volcanic degassing of sulfur and chalcophile elements by concentrating and transferring metals from magma to hydrous fluid. Here, we track the interaction of sulfide liquid with a fluid exsolving from basalt at Kawah Ijen volcano in Indonesia. As in many other volcanic systems, neither sulfide nor fluid is preserved. Instead, the reaction is recorded in changes in metal and sulfur concentrations in the melt during magma ascent, and shows a two-stage evolution; deep-seated progressive breakdown of sulfide during which metal concentrations in the melt are largely controlled by the sulfide, followed by fluid–melt partitioning controlling metal concentrations at shallow depth once this sulfide has been exhausted. Present-day fumarole gases have similar Zn/Cu, Pb/Cu and Mo/Cu ratios to the reconstructed sulfide, but are enriched in Tl, As and Sb. These enrichments are also observed in melt inclusions in the most recent dacitic deposits at Kawah Ijen. This suggests that the fumarole gases are sourced from a deep, degassing sulfide-saturated basalt, preserved in Zn/Cu, Pb/Cu and Mo/Cu ratios, which subsequently interact with a shallow dacitic melt that enhances Tl, As and Sb emissions.

Globule-rich lavas in the Razjerd district, Qazvin, Iran: a unique volcanic fabric

A hypocrystalline silica-rich (63–67 wt.% SiO2, dacitic composition) lava flow (called G-lava) in the subaerial eruptive sequence of the Alborz Mountains (Razjerd district, Qazvin Province) of northern Iran, contains abundant (40–50 vol.%) 0.1- to 5.0-cm globules set in a matrix of rather similar composition and microtexture. Numerous globules have coalesced, showing triple-point junctions with 120° angles. Both phases in the G-lava (globules and matrix) contain similar microphenocrysts (plagioclase, ortho- and clinopyroxene and magnetite) in a trachytic groundmass. However, their mesostasis differ in colour, in composition, in the amount of glass and their amount of volatiles and silica: in the globules the mesostasis is darker and richer in SiO2 but is volatile poor. Other volcanic materials in the same unit are very similar in composition to the G-lava. The globular fabric was formed with two phases: one poor in volatiles (the globules), the other rich in volatiles (the matrix). The globules are slightly more silicic (66.9 against 64.6 wt.% SiO2), more potassic (3.7 againt 2.8 wt.% K2O) and more viscous (of the order of 103 to 104) than the matrix outside the globules. It seems that the two phases (globules and matrix) with different silica and volatiles contents and thus different vesicularities, viscosities and densities, were produced in the dacitic melt due to temperature and pressure drop and magmatic degassing in the volcanic conduit involved fluid-melt exsolution processes. Some of the volatile-rich melt was probably frothy during eruption, producing volcanic bombs and scoria.

Crustal growth at active continental margins: Numerical modeling

The dynamics and melt sources for crustal growth at active continental margins are analyzed by using a 2D coupled petrological–thermomechanical numerical model of an oceanic-continental subduction zone. This model includes spontaneous slab retreat and bending, dehydration of subducted crust, aqueous fluid transport, partial melting, melt extraction and melt emplacement in form of extrusive volcanics and intrusive plutons. We could identify the following three geodynamic regimes of crustal growth: (i) stable arcs, (ii) compressional arcs with plume development, and (iii) extensional arcs. Crustal growth in a stable subduction setting results in the emplacement of flattened intrusions in the lower crust. At first dacitic melts, extracted from partially molten rocks located atop the slab (gabbros and basalts), intrude into the lower crust followed by mantle-derived (wet peridotite) basaltic melts from the mantle wedge. Thus extending plutons form in the lower crust, characterized by a successively increasing mantle component and low magmatic addition rates (10km3/km/Myrs). Compressional arcs are accomplished by the formation and emplacement of hybrid plumes. In the course of subduction localization and partial melting of basalts and sediments along the slab induces Rayleigh Taylor instabilities. Hence, buoyant plumes are formed, composed of partially molten sediments and basalts of the oceanic crust. Subsequently, these plumes ascend, crosscutting the lithosphere before they finally crystallize within the upper crust in form of silicic intrusions. Additionally, intrusions are formed in the lower crust derived by partial melting of rocks located atop the slab (basalts, gabbros, wet peridotite) and inside the plume (basalts, sediments). Magmatic addition rates are somewhat higher compared to stable arcs (40–70km3/km/Myrs). Subduction in an extensional arc setting results in decompression melting of dry peridotite. The backward motion of the subduction zone relative to the motion of the plate leads to thinning of the overriding plate. Thus, hot and dry asthenosphere rises into the neck as the slab retreats, triggering decompression melting of dry peridotite. Consequently large volumes of mafic (oceanic) crust are formed in the backarc region with total magmatic addition rates being as high as 90–170km3/km/Myrs.

Rift-Related Transition from Andesite to Rhyolite Volcanism in the Taupo Volcanic Zone (New Zealand) Controlled by Crystal–melt Dynamics in Mush Zones with Variable Mineral Assemblages

The Taupo Volcanic Zone (TVZ), located in the North Island of New Zealand, represents part of a magmatic arc that is at present undergoing active extension. Around 0·9 Myr ago, an acceleration in rifting was followed by a progressive transition in the composition of volcanic products (until 0·7 Ma) from typical arc-type andesite into overwhelmingly large, caldera-forming rhyolitic eruptions with subordinate basalt and dacite in the Central TVZ. Despite an obvious compositional gap in the erupted products in the Central TVZ within the last 0·7 Myr (little to no erupted products with SiO2 contents between 55 and 65 wt %), phenocryst minerals (plagioclase, amphibole, pyroxene) show an uninterrupted compositional record that suggests crystallization from a continuum of melt compositions. Coupled with radiogenic isotope evidence, the whole-rock and mineral chemistry data are consistent with magmatic differentiation controlled by crystal fractionation of primary mantle-derived magmas accompanied by some assimilation of local wall-rocks. In the Southern TVZ and in the early part of the Central TVZ, magmatic differentiation was dominated by the lower crustal evolution of relatively dry ( 1wt % H2O) arc basalts, crystallizing a pyroxene^plagioclase-dominated assemblage. However, the conditions of crystallization in the lower crust appear to have changed within the last million years in the Central TVZ, with amphibole and oxides appearing earlier in the crystallization sequence. In this framework and using numerical simulations coupling crystallization kinetics and multiphase fluid dynamics of magma reservoirs, we show that melts extracted from crystal mushes within an optimal ‘extraction window’ ( 50 and 80 vol. % crystals) match those erupted at the surface. Lower crustal mushes fed by basalt with 1wt % H2O (dominated by a pyroxene^plagioclase assemblage) release andesitic melts at the extraction window. These melts then erupt at the surface to form the observed andesitic part of the arc.With a slightly higher water content ( 2 wt %) in the basalt, the melt composition at the extraction window from lower crustal mushes is dacitic rather than andesitic. Although some dacitic melts will reach the surface, most will be trapped in the upper crust and crystallize to form a silicic mush. Extraction of the interstitial liquid after450% crystallization from this upper crustal reservoir produces the large volumes of rhyolitic magma erupted over the past 0·7 Myr (44000 km from ignimbrite-forming eruptions).

Petrology, age, and polychronous sources of the initial magmatism of the Imandra-Varzuga paleorift, Fennoscandian shield

This paper reports new geochemical and isotope data on the volcanogenic complexes of the Arvarench sequence of the Imandra-Varzuga paleorift structure of the Fennoscandian shield. It was established that these complexes are made up of komatiites, basalts, high-Mg andesites, and dacites and occupy a Sumian chronostratigraphic position with U-Pb (SHRIMP) age of 2429 ± 6.6 Ma in the regional Early Precambrian stratigraphic scale of the Kola-Norwegian province of the Fennoscandian shield, thus constraining the Sumian Subhorizon of the Lower Karelian Complex of the Northeastern Fennoscandian shield within 2450–2430 Ma. The high negative eNd, LREE enrichment, and the presence of different-age Archean zircons with REE patterns indicative of disequilibrium crystallization suggest that the parental dacitic melts were derived by anatectic melting of polychronous (3.2, 2.9, 2.8, 2.7 Ga) lithological complexes of the Archean continental crust of the Kola-Norwegian province of the Fennoscandian shield. Numerical petrological-geochemical modeling of generation and evolution of primary melts of the metavolcanic rocks made it possible to establish that the isotope-geochemical peculiarities of the komatiites, basalts, and basaltic andesites can be best described by fractional crystallization of primary komatiite melt contaminated by ∼ 2% of the Archean crustal material of tonalitic composition. The mantle protolith of primary melt in terms of its isotope-geochemical parameters was similar to the “enriched” mantle source of the Paleoproterozoic (2430–2450 Ma) mafic-ultramafic layered intrusions of the Kola-Norwegian province and Sumian metavolcanic rocks of the Fennoscandian shield. The high-Mg andesites of the Arvarench sequence were derived by fractionation of crustally contaminated (∼ 2%) magnesian basalts with elevated Al content (Al2O3 ∼ 15.6 wt %) in equilibrium with 40–50% Cpx40-Ol20-Opx10-Pl10-Mag20 assemblage at P < 1 GPa. Obtained isotope-geochemical data and modeling results could be interpreted by off-subduction geodynamic model of the evolution of mantle plume and its interaction with the Archean continental lithosphere at the early stage of intracratonic rifting.

Bubble nucleation in rhyolite and dacite melts: temperature dependence of surface tension

Surface tension (σ) profoundly influences the ability of gas bubbles to nucleate in silicate melts. To determine how temperature impacts σ, experiments were carried out in which high-silica rhyolite melts with 5 wt% dissolved water were decompressed at temperatures that ranged from 775 to 1,085°C. Decompressions were also carried out using dacite melts with 4.3 wt% dissolved water at 1,150°C. Water bubbles nucleated in rhyolite only when decompressions exceeded 95 MPa at all temperatures. Bubbles nucleated in number densities that increased as decompression increased and at hotter temperatures at a given amount of decompression. After correcting decompression amounts for temperature differences, values for σ were estimated from nucleation rates and found to vary between 0.081 and 0.093 N m−1. Surface tension decreases as temperature increases from 775 to 875°C, but then increases as temperature increases to 1,085°C. Those values overlap previous results, but only when melt viscosity is less than 104 Pa s. For low-viscosity rhyolite, there is a strong correlation of σ with temperature, in which σ increases by 6.9 × 10−5 N m−1 C−1. That variation is robust for 5–9 wt% dissolved water, as long as melt viscosity is ≤104 Pa s. More viscous rhyolite deviates from that correlation probably because nucleation is retarded in stiffer melts. Bubbles nucleated in dacite when decompressions exceeded 87 MPa, and occured in one or more events as decompression increased. Surface tension is estimated to be 0.083 (±0.001) N m−1 and when adjusted for temperature agrees well with previous results for colder and wetter dacite melts. At a given water content, dacite melts have lower surface tensions than rhyolite melts, when corrected to a fixed temperature.

Petrogenesis of high-temperature siliceous melts in volcanic structures of the Altai collisional system of Hercynides ( Eastern Kazakhstan)

We consider the geologic occurrence and PT-conditions of the generation and crystallization of siliceous melts that formed volcanic structures within the Altai collisional system of Hercynides. The data on the geologic occurrence, internal structure, and petrogeochemical age of rocks are presented, as well as results of the thermobarogeochemical studies of inclusions in minerals. The performed investigations showed the presence of siliceous dacitic melts in the studied volcanic structures. These melts were generated in the lower crust (~10 kbar, 1000–1200 ºC) as a result of the partial melting of crustal substrates under the influence of high-temperature mantle melts.

Eruptive history and magmatic evolution of the 1.9 kyr Plinian dacitic Chiltepe Tephra from Apoyeque volcano in west-central Nicaragua

The youngest dacitic Plinian eruption in west-central Nicaragua, forming the 18 km3 Chiltepe Tephra (CT), occurred about nineteen hundred years ago at Apoyeque stratovolcano, which dominates the Chiltepe volcanic complex 15 km north of the capital Managua, where the CT is 2 m thick. We have traced the CT from its proximal facies at the crater rim, through the medial facies in the lowlands around Apoyeque, and to the distal facies up to 550 km offshore in the Pacific. While medial and distal facies consist of widespread Plinian fall deposits, the proximal facies reveals the complexity of this eruption, which we divide into four phases (I–IV). Interaction of rising magma with a pre-existing crater lake generated the phreatomagmatic opening phase I of the eruption, which produced ash fall with accretionary lapilli. Phase II marked a rapid change to persistent magmatic activity that yielded several large Plinian eruptions, declining through a period of unstable eruption conditions, followed by a short hiatus. Phase III began with unstable conditions, probably as a result of eastward migration and widening of the vent, leading to a second period of Plinian eruptions with three major events reaching magma discharge rates five times larger than those of phase II. Phase III again declined through unstable eruption conditions before magmatic activity terminated. Numerous explosions in the shallow hydrothermal system during the final phase IV resulted in the formation of a phreatic tuff ring on the rim of Apoyeque crater. The white, highly-vesicular, dacitic CT pumice contains plagioclase (An45–68), orthopyroxene, clinopyroxene, and minor hornblende, apatite and titanomagnetite phenocrysts. A very subordinate fraction of gray pumice has the highest crystal content, the least evolved bulk-rock, but the most evolved matrix-glass composition. The CT dacite has two unusual compositional features: (1) all white dacite has the same melt (matrix-glass) composition such that variations in bulk-rock compositions (64–68 wt% SiO2) simply reflect different phenocryst contents of 10–35%, interpreted as the result of gradual phenocryst settling in the magma chamber. (2) Abundant olivine crystals with a bimodal distribution in Mg# (modes at Mg# = 0.75 and Mg# = 0.8) are dispersed throughout the erupted dacite. These are clearly out of equilibrium with the dacitic melt and are interpreted as xenocrysts derived from the basaltic Nejapa-Miraflores volcanic lineament that intersects the Chiltepe volcanic complex and was contemporaneously active. Thermobarometric estimates place the dacitic CT magma reservoir in the upper crust (<250 MPa), with a temperature of about 890°C and about 5 wt% water dissolved in the melt. Comparing water and chlorine contents with respective solubility models suggests that volatile degassing began in the magma reservoir and triggered the CT eruption. From the vertical compositional variation pattern of the CT we deduce that the conduit tapped the magma chamber not at the top but from the side, at some deeper level, and that subsequent magma withdrawal was governed by both variations in discharge rate and possible upward migration and/or widening of the conduit entrance.

Timescales of magma differentiation from basalt to andesite beneath Hekla Volcano, Iceland: Constraints from U-series disequilibria in lavas from the last quarter-millennium flows

Measurements of 238U– 230Th– 226Ra disequilibria, Sr–Nd–Pb–Hf isotopes and major-trace elements have been conducted for lavas erupted in the last quarter-millennium at Hekla volcano, Iceland. The volcanic rocks range from basalt to dacite. Most of the lavas (excluding dacitic samples) display limited compositional variations in radiogenic Sr–Nd–Pb–Hf isotopes ( 87Sr/ 86Sr = 0.70319–0.70322; 143Nd/ 144Nd = 0.51302–0.51305; 206Pb/ 204Pb = 19.04–19.06; 207Pb/ 204Pb = 15.53–15.54; 208Pb/ 204Pb = 38.61–38.65; 176Hf/ 177Hf = 0.28311–0.28312). All the samples possess ( 230Th/ 238U) disequilibrium with 230Th excesses, and they show systematic variations in ( 230Th/ 232Th) and ( 238U/ 232Th) ratios. The highest 226Ra excesses occur in the basalt and most differentiated andesite lavas, while some basaltic-andesite lavas have ( 226Ra/ 230Th) ratio that are close to equilibrium. The 238U– 230Th– 226Ra disequilibria variations cannot be produced by simple closed-system fractional crystallization with radioactive decay of 230Th and 226Ra in a magma chamber. A closed-system fractional crystallization model and assimilation and fractional crystallization (AFC) model indicate that the least differentiated basaltic andesites were derived from basalt by fractional crystallization with a differentiation age of ∼24 ± 11 kyr, whereas the andesites were formed by assimilation of crustal material and fractionation of the basaltic-andesites within 2 kyr. Apatite is inferred to play a key role in fractionating the parent–daughter nuclides in 230Th– 238U and 226Ra– 230Th to make the observed variations. Our proposed model is that several batches of basaltic-andesite magmas that formed by fractional crystallization of a basaltic melt from a deeper reservoir, were periodically injected into the shallow crust to form individual magma pockets, and subsequently modifying the original magma compositions via simultaneous assimilation and fractional crystallization. The assimilant is the dacitic melt, which formed by partial melting of the crust.

Partial melting of the dry mafic continental crust: Implications for petrogenesis of C-type adakites

C-type adakites have been commonly considered as a result of partial melting of the mafic lower continental crust (LCC) at high pressure, as supported by high P-T experiments on hydrous basalts. However, because the mafic eclogitic LCC is generally dry, experiments on water-bearing materials cannot be used to constrain the melting processes of the dry mafic LCC. Due to the lack of systematic melting experimental studies on dry mafic rocks at crustal pressures, MELTs software was applied to simulating melting of the dry mafic LCC at 1–2 GPa. Comparison of model results with experimental data indicates that, when melting degree is greater than 20%, melts from the dry mafic LCC at 1–3 GPa cannot produce the C-type adakitic melt with high SiO2 content (∼70%). Although the limited experimental results about dry mafic rock melting at 1–2 GPa in the literature suggest that low degree melting ( 1.8 GPa, low-degree melting can produce dacitic melt with high K2O/Na2O (∼1) if SiO2 content of the melt is controlled by residual garnet. Furthermore, the simulation also suggests that, if pressure is <1.8 GPa, abundant plagioclase (plg) in the residual phase may decrease SiO2 content in the melt to below 62%, much lower than that of the C-type adakites observed in eastern China. Given the high P-T conditions required to produce melts with high SiO2 and extremely low HREE contents, such melts could easily be contaminated by other crustal-derived melts, implying that the C-type adakites from eclogite melting could be less commonly observed in the outcrops than previously believed. Besides the interpretation that garnet fractionates Sr, Y, and REE, high Sr/Y and La/Yb could be also produced by multiple ways such as inheriting the source features and fractional crystallizing clinopyroxene (cpx). Therefore, it may be problematic using high Sr/Y and La/Yb as criteria to identify adakites. Instead, REE patterns with strong depletion of HREE relative to MREE (e.g. high Gd/Yb) could be a better parameter to identify the role of garnet and thus adakites. Finally, geochemical models based on MELTs simulation indicate that Eu anomaly cannot be simply used to constrain the role of plg in magmatism because Eu anomaly in the melt is a function of source characteristics, oxygen fugacity (fO2) of magmatic systems, and plg/mafic minerals mode ratio.

Experimental phase and melting relations of metapelite in the upper mantle: implications for the petrogenesis of intraplate magmas

We performed a series of piston-cylinder experiments on a synthetic pelite starting material over a pressure and temperature range of 3.0–5.0 GPa and 1,100–1,600°C, respectively, to examine the melting behaviour and phase relations of sedimentary rocks at upper mantle conditions. The anhydrous pelite solidus is between 1,150 and 1,200°C at 3.0 GPa and close to 1,250°C at 5.0 GPa, whereas the liquidus is likely to be at 1,600°C or higher at all investigated pressures, giving a large melting interval of over 400°C. The subsolidus paragenesis consists of quartz/coesite, feldspar, garnet, kyanite, rutile, ±clinopyroxene ±apatite. Feldspar, rutile and apatite are rapidly melted out above the solidus, whereas garnet and kyanite are stable to high melt fractions (>70%). Clinopyroxene stability increases with increasing pressure, and quartz/coesite is the sole liquidus phase at all pressures. Feldspars are relatively Na-rich [K/(K + Na) = 0.4–0.5] at 3.0 GPa, but are nearly pure K-feldspar at 5.0 GPa. Clinopyroxenes are jadeite and Ca-eskolaite rich, with jadeite contents increasing with pressure. All supersolidus experiments produced alkaline dacitic melts with relatively constant SiO2 and Al2O3 contents. At 3.0 GPa, initial melting is controlled almost exclusively by feldspar and quartz, giving melts with K2O/Na2O ~1. At 4.0 and 5.0 GPa, low-fraction melting is controlled by jadeite-rich clinopyroxene and K-rich feldspar, which leads to compatible behaviour of Na and melts with K2O/Na2O ≫ 1. Our results indicate that sedimentary protoliths entrained in upwelling heterogeneous mantle domains may undergo melting at greater depths than mafic lithologies to produce ultrapotassic dacitic melts. Such melts are expected to react with and metasomatise the surrounding peridotite, which may subsequently undergo melting at shallower levels to produce compositionally distinct magma types. This scenario may account for many of the distinctive geochemical characteristics of EM-type ocean island magma suites. Moreover, unmelted or partially melted sedimentary rocks in the mantle may contribute to some seismic discontinuities that have been observed beneath intraplate and island-arc volcanic regions.

Erratum to: Chemical interdiffusion of dacite and rhyolite: anhydrous measurements at 1 atm and 10 kbar, application of transition state theory, and diffusion in zoned magma chambers

Chemical diffusivity measurements have been made on anhydrous metaluminous diffusion couples of dacite and rhyolite at 1 atm, 1200°–1400° C, and 10 kbar, 1300°–1600° C, and on anhydrous peraluminous and peralkaline dacite-rhyolite diffusion couples at 10 kbar, 1300°–1600° C. Chemical diffusivities for Si, Al, Fe, Mg, and Ca were measured in all experiments on the metaluminous diffusion couples using Boltzmann-Matano analysis, and Si diffusivities were measured on the other diffusion couples. Two 10 kbar metaluminous experiments were analyzed with the X-ray microprobe and diffusivities of Sr, Y, Zr and Nb were measured. Si diffusivity displays a weak negative correlation with SiO2 content over the range of 65%–75% SiO2. At a given SiO2 content chemical diffusivities of all non-alkali elements are usually within less than an order of magnitude of Si chemical diffusivity and are controlled by partitioning along the diffusion profile so as to maintain local equilibrium at each point along the profile. Alkali chemical diffusivities were not measured but can be estimated from the experiments to be orders of magnitude higher than non-alkali chemical diffusivities. Data were fit to Arrhenius equations for diffusivities measured at 65, 70 and 75% SiO2. At 1 atm the Arrhenius equation for non-alkalies at 70% SiO2 in the metaluminous system is: $$D_T = 72.5\exp \left( { - 82.5 kcal/RT} \right)$$ an at 10 kbar: $$D_T = 0.0673\exp \left( { - 56.5 kcal/RT} \right)$$ whereDT is the diffusivity in cm2/s,R is in calories, andT is in Kelvin. At 65 and 75% SiO2 the pre-exponential factors and activation energies are similar to the values determined at 70% SiO2. Results on the metaluminous system demonstrate that the effect of increasing pressure is to increase the diffusivity at constant temperature, by about a factor of 4 at 1300° C, less at higher temperatures. Ten kbar activation energies and pre-exponential factors for peraluminous and peralkaline systems are slightly smaller than for the metaluminous system and reflect the slightly higher diffusivities in the peraluminous and peralkaline systems consistent with their lower calculated viscosities when compared to the metaluminous system. 1-atm diffusivities can be calculated from melt viscosities using the Eyring equation to within a factor of 5, except for 75% SiO2 diffusivities which consistently display calculated diffusivities approximately an order of magnitude below measured diffusivities. Using fundamental equations of transition state theory the 1-atm chemical diffusivities of non-alkalies, and alkalies too, can be calculated from thermodynamic data and melt structure models. There are, however, discrepancies in the calculated and measured activation energies and pre-exponential factors. Application of diffusivity measurements to magma chamber processes demonstrates that diffusion is not an effective process for compositional modification and can only begin to have a significant effect on melt compositions if the dacitic and rhyolitic melts are convecting separately and separated by a thin, static zone where diffusive transport is occurring; even in this case diffusion is likely to modify alkali concentrations only, and perhaps isotopic ratios in small magma chambers, or chambers with large aspect ratios (width/height). If the dacitic melt forms enclaves which are mixed into the rhyolitic melt, then diffusion coupled with the physical mixing of enclaves has the potential to rapidly affect alkali and isotopic ratios of the rhyolite melt and dacitic enclaves. Non-alkali concentrations in both dacite enclaves and rhyolite are, however, unlikely to be significantly affected. Because of the ineffectiveness of diffusion, once a magma chamber becomes zoned in major and trace elments it will remain zoned, with the exception of alkalies and possibly isotopic ratios, unless physical mixing between the different compositions occurs.

Solubility of C-O-H mixturesin natural melts: new experimental data and application range of recent models

The effect of pressure, temperature, and melt composition on CO2 and H2O solubilities in aluminosilicate melts, coexisting with CO2-H2O fluids, is discussed on the basis of previously published and new experimental data. The datasets have been chosen so that CO2 and H2O are the main fluid components and the conclusions are only valid for relatively oxidizing conditions. The most important parameters controlling the solubilities of H2O and CO2 are pressure and composition of melt and fluid. On the other hand, the effect of temperature on volatile solubilities is relatively small. At pressures up to 200 MPa, intermediate compositions such as dacite, in which both molecular CO2 and carbonate species can be dissolved, show higher volatile solubilities than rhyolite and basalt. At higher pressures (0.5 to 1 GPa), basaltic melts can incorporate higher amounts of carbon dioxide (by a factor of 2 to 3) than rhyolitic and dacitic melts. Henrian behavior is observed only for CO2 solubility in equilibrium with H2O-CO2 fluids at pressures <100 MPa, whereas at higher pressures CO2 solubility varies nonlinearly with CO2 fugacity. The positive deviation from linearity with almost constant CO2 solubility at low water activity indicates that dissolved water strongly enhances the solubility of CO2. Water always shows non-Henrian solubility behavior because of its complex dissolution mechanism (incorporation of OH-groups and H2O molecules in the melt). The model of Newman and Lowenstern (2002), in which ideal mixing between volatiles in both fluid and melt phases is assumed, reproduces adequately the experimental data for rhyolitic and basaltic compositions at pressures below 200 MPa but shows noticeable disagreement at higher pressures, especially for basalt. The empirical model of Liu et al. (2004) is applicable to rhyolitic melts in a wide range of pressure (0-500 MPa) and temperature (7001200°C) but cannot be used for other melt compositions. The thermodynamic approach of Papale (1999) allows to calculate the effect of melt composition on volatile solubilities but needs an update to account for more recent experimental data. A disadvantage of this model is that it is not available as a program code. The review indicates a crucial need of new experimental data for scarcely investigated field of pressures and fluid compositions and new models describing evident non-ideality of H-C-O fluid solubility in silicate melts at high pressures.

Early Archean sialic crust of the Siberian craton: Its composition and origin of magmatic protoliths

This study demonstrates that the base of the Archean deep-seated granulite complexes within the Siberian craton consists of a metabasite-enderbite association. The major and trace element distribution patterns revealed that the protoliths of this association are represented by calc-alkaline andesites and dacites, containing several minor sequences of komatiitic-tholeiitic volcanic rocks. The origin of the primary volcanic rocks of the metabasite-enderbite association is inferred on the basis of a model of mantle plume magmatism, which postulates that both andesitic and dacitic melts were derived from the primary basitic crust at the expense of heat generated by ascending mantle plumes. The formation of the protoliths of the Archen metabasite-enderbite association of the Siberian craton began at 3.4 Ga and continued until the late Archean.

Water speciation and diffusion in haploandesitic melts at 743–873 K and 100 MPa

Water is an important volatile component in andesitic eruptions and deep-seated andesitic magma chambers. We report an investigation of H 2O speciation and diffusion by dehydrating haploandesitic melts containing ⩽2.5 wt.% water at 743–873 K and 100 MPa in cold-seal pressure vessels. FTIR microspectroscopy was utilized to measure species [molecular H 2O (H 2O m) and hydroxyl group (OH)] and total H 2O (H 2O t) concentration profiles on the quenched glasses from the dehydration experiments. The equilibrium constant of the H 2O speciation reaction H 2 O m + O ⇌ 2 OH , K = ( X OH) 2/( X H 2 O m X O ) where X means mole fraction on a single oxygen basis, in this Fe-free andesite varies with temperature as ln K = 1.547–2453/ T where T is in K. Comparison with previous speciation data on rhyolitic and dacitic melts indicates that, for a given water concentration, Fe-free andesitic melt contains more hydroxyl groups. Water diffusivity at the experimental conditions increases rapidly with H 2O concentration, contrary to previous H 2O diffusion data in an andesitic melt at 1608–1848 K. The diffusion profiles are consistent with the model that molecular H 2O is the diffusion species. Based on the above speciation model, H 2O m and H 2O t diffusivity (in m 2/s) in haploandesite at 743–873 K, 100 MPa, and H 2O t ⩽ 2.5 wt.% can be formulated as D H 2 O m = exp - 12.273 - 13.905 X - 18172 - 73136 X T and D H 2 O t = D H 2 O m 1 + 2 X - 1 4 X ( X - 1 ) ( 1 - 4 / K ) + 1 , where T is in K, X = C/18.015/[ C/18.015 + (100 − C)/33.84] is mole fraction of H 2O t with C being H 2O t in wt.%, and K is the equilibrium constant of H 2O speciation reaction. By comparison with previous water diffusion studies, H 2O diffusivity at T < 873 K in calc-alkaline silicate melts is found to increase with degree of polymerization (andesite < dacite < rhyolite), opposite to the trend at superliquidus temperatures.

Water diffusion in dacitic melt

H 2O diffusion in dacitic melt was investigated at 0.48–0.95 GPa and 786–893 K in a piston-cylinder apparatus. The diffusion couple design was used, in which a nominally dry dacitic glass makes one half and is juxtaposed with a hydrous dacitic glass containing up to ∼8 wt.% total water (H 2O t). H 2O concentration profiles were measured on quenched glasses with infrared microspectroscopy. The H 2O diffusivity in dacite increases rapidly with water content under experimental conditions, similar to previous measurements at the same temperature but at pressure <0.15 GPa. However, compared with the low-pressure data, H 2O diffusion at high pressure is systematically slower. H 2O diffusion profiles in dacite can be modeled by assuming molecular H 2O (H 2O m) is the diffusing species. Total H 2O diffusivity D H 2 O t within 786–1798 K, 0–1 GPa, and 0–8 wt.% H 2O t can be expressed as: D H 2 O t = 1 + 2 X - 1 4 X ( X - 1 ) ( 1 - 4 / K ) + 1 exp - 9.423 - 62.38 X - 19064 - 108882 X + 1476.7 P T , where D H 2 O t is in m 2/s, T is temperature in K, P is pressure in GPa, K = exp(1.49 − 2634/ T) is the equilibrium constant of speciation reaction ( H 2 O m + O ⇌ 2 OH ) in the melt, X = C/18.015/[ C/18.015 + (100 − C)/33.82], C is wt.% of H 2O t, and 18.015 and 33.82 g/mol correspond to the molar masses of H 2O and anhydrous dacite on a single oxygen basis. Compared to H 2O diffusion in rhyolite, diffusivity in dacite is lower at intermediate temperatures but higher at superliquidus temperatures. This general H 2O diffusivity expression can be applied to a broad range of geological conditions, including both magma chamber processes and volcanic eruption dynamics from conduit to the surface.

Partitioning behavior of trace elements between dacitic melt and plagioclase, orthopyroxene, and clinopyroxene based on laser ablation ICPMS analysis of silicate melt inclusions

Partitioning behavior of Sc, Ti, V, Mn, Sr, Y, Zr, Nb, Ba, La, Nd, Sm, Eu, Gd, Dy, Ho, Yb, Hf, and Pb between dacitic silicate melt and clinopyroxene, orthopyroxene, and plagioclase has been determined based on laser ablation-inductively coupled plasma mass spectrometric (LA-ICPMS) analysis of melt inclusions and the immediately adjacent host mineral. Samples from the 1988 eruption of White Island, New Zealand were selected because petrographic evidence suggests that all three mineral phases are in equilibrium with each other and with the melt inclusions. All three phenocryst types are found as mineral inclusions within each of the other phases, and mineral inclusions often coexist with melt inclusions in growth-zone assemblages. Compositions of melt inclusions do not vary between the different host minerals, suggesting that boundary layer processes did not affect compositions of melt inclusions and that post-trapping modifications have not occurred. Partition coefficients were calculated from the host and melt inclusion compositions and results were compared to published values. All trace elements examined in this study except Sr are incompatible in plagioclase, and all measured trace elements except for Mn are incompatible in orthopyroxene. In clinopyroxene, Sc, V, and Mn are compatible, and Y, Ti, HREE, and the MREE are only slightly incompatible. Most partition coefficients overlap the wide range of values reported in the literature, but the White Island data are consistently at the lower end of the range in published values. Results from the literature obtained using modern microanalytical techniques such as secondary ion mass spectrometry (SIMS) or proton induced X-ray emission spectroscopy (PIXE) also fall at the lower end of the published values, whereas partition coefficients determined from bulk analysis of glass and crystals separated from volcanic rocks typically extend to higher values. Rapid crystal growth-rates, crystal zonation, or the presence of accessory mineral inclusions in phenocrysts likely accounts for the wide range and generally higher partition coefficients obtained using bulk sampling techniques. The results for 3+ cations from this study are consistent with theoretical predictions based on a lattice strain model for site occupancy. The results also confirm that the melt inclusion-mineral (MIM) technique is a reliable method for determining partition coefficients, as long as the melt inclusions have not experienced post-entrapment reequilibration.

Assimilation of Plutonic Roots, Formation of High-K ‘Exotic’ Melt Inclusions and Genesis of Andesitic Magmas at Volcán De Colima, Mexico

Phenocryst-hosted melt inclusions from the 1998^2005 andesite eruptions of Volcan de Colima (Mexico) show broad ranges of major and trace element contents that do not overlap with the bulk- rock compositions and indicate that melt inclusions can be formed by and record a range of processes involved in the genesis of andesites. The melt inclusions that demonstrably record the evolution of the melt feeding the eruption indicate low-pressure (130^10 MPa) crys- tallization of a dacitic melt despite the monotonous bulk andesitic composition of historical magmas at Volcan de Colima. Mingling of dacite melt with gabbroic fragments in the shallow sub-volcanic system is the process responsible for generating the bulk andesitic composition of the magmas. A significant proportion of the melt inclusions have distinctive high large ion lithophile element (LILE) signatures. These 'exotic' high-K melt inclusions in pyrox- enes are thought to result from incongruent melting of interstitial bio- tite during assimilation of gabbroic fragments in the dacitic melt. A second group of exotic high-K melt inclusions found in plagioclase are likely to result from dissolution of higher-pressure (4200 MPa) amphibole, plagioclase, magnetite and biotite cumulates during assimilation in the ascending dacitic melt. Although they are not volumetrically abundant, high-K melts formed during assimilation of plutonic fragments and crystal cumulates made a significant con- tribution to the LILE contents of the magmas and represent a poten- tial source for this group of elements. The range of melt inclusion compositions in Volcan de Colima magmas emphasizes the impor- tance of mixing between ascending evolved melts and crystal popula- tions formed during previous episodes of magmatism over a range of pressures, temperatures and volatile contents. Cannibalization of plutonic roots appears to be a fundamental process in the genesis of andesite magmas and melt inclusions at continental arc volcanoes.

Iron and lithium isotope systematics of the Hekla volcano, Iceland — Evidence for Fe isotope fractionation during magma differentiation

In this study potential iron isotope fractionation by magmatic processes in the Earth's crust was systematically investigated. High precision iron isotope analyses by MC-ICP-MS were performed on a suite of rock samples representative for the volcanic evolution of the Hekla volcano, Iceland. The whole series of Hekla's rocks results from several processes. (i) Basaltic magmas rise and induce partial melting of meta-basalts in the lower part of the Icelandic crust. The resulting dacitic magma evolves to rhyolitic composition through crystal fractionation. During this differentiation the δ 56/54Fe IRMM-014 values increase successively from 0.051 ± 0.021‰ for the primitive dacites to 0.168 ± 0.021‰ for the rhyolites. This increase can be described by a Rayleigh fractionation model using a constant bulk fractionation factor between all mineral phases (M) and the silicate liquid (L) of Δ 56/54Fe M–L = − 0.1‰. (ii) The basaltic magma itself differentiates by crystal fractionation to basaltic andesite composition. No Fe isotope fractionation was found in this series. All basalts and basaltic andesites have an average δ 56/54Fe IRMM-014 value of 0.062 ± 0.042‰ (2SD, n = 9), identical to mean terrestrial basaltic values reported in previous studies. This observation is consistent with the limited removal of iron from the remaining silicate melt through crystal fractionation and small mineral-melt Fe isotope fractionation factors expected at temperatures in excess of 1050 °C. (iii) Andesites are produced by mixing of basaltic andesite with dacitic melts. The iron isotope composition of the andesites is matching that of the basaltic andesites and the less evolved dacites, in agreement with a mixing process. In the Hekla volcanic suite Li concentrations are positively correlated with indicators of magma differentiation. All Hekla rocks have δ 7Li values typical for the upper mantle and demonstrate the absence of resolvable Li isotope fractionation during crystal fractionation. As a fluid-mobile trace element, Li concentrations and isotopes are a potential tracer of magma/fluid interaction. At Hekla, Li concentrations and isotope compositions do not indicate any extensive fluid exsolution. Hence, the heavy Fe isotope composition of the dacites and rhyolites can be predominately attributed to fractional crystallisation. Iron isotope analyses on single samples from other Icelandic volcanoes (Torfajökull, Vestmannaeyjar) confirm heavy Fe isotope enrichment in evolving magmas. Our results suggest that the iron isotope composition of highly evolved crust can be slightly modified by magmatic processes.

Heterogeneous bubble nucleation and disequilibrium H 2O exsolution in Vesuvius K-phonolite melts

This study focuses on constraining bubble nucleation and H 2O exsolution processes in alkalic K-phonolite melts, using “white pumice” of the 79 AD eruption of Vesuvius as starting material. The first set of experiments consisted of H 2O solubility runs at 1153 to 1250 K and pressures between 50 and 200 MPa, to constrain equilibrium water concentrations along the decompression pathways. The decompression experiments were equilibrated with H 2O at 150 MPa and 1173 and 1223 K, and then decompressed at 3 to 17 MPa/s before rapid quenching. Experiments nucleated bubbles within the first 50 MPa pressure drop, producing maximum bubble number densities (N V), corrected to melt volume, of 3.8 × 10 14 m − 3 at 1173 K and 4.3 × 10 13 m − 3 at 1223 K. Most bubbles were not visibly attached to crystals, except for a subset attached to pyroxenes primarily in the 1173 K experiments. When compared with prior bubble nucleation studies, the reduced nucleation ΔP and relatively low N V observed indicate predominantly a heterogeneous nucleation mechanism. Melt–vapor–crystal wetting angles measured in 1173 K experiments from bubbles attached to pyroxene crystals are 36 to 69°, which are similar to those measured on titanomagnetite crystals in calc-alkaline dacite melts. The 1223 K experiments have porosities and water concentrations that largely track equilibrium, despite the rapid decompression rate. The 1173 K experiments deviate strongly from equilibrium trends in both porosity and water concentration, and slower H 2O diffusion rates are likely the cause of the inhibited bubble growth. Bubble number densities from 79 AD Vesuvius natural EU2 pumice are relatively high (2 to 4 × 10 15 m − 3 ; [Gurioli, L., Houghton, B.F., Cashman, K.V., Cioni, R., 2005. Complex changes in eruption dynamics during the 79 AD eruption of Vesuvius. Bull. Volcanol. 67: 144–159.]) when corrected to vesicularity. In comparison, corrected N V's from homogeneous and heterogeneous bubble nucleation experiments from this study and prior work are at least factor of 5 lower, indicating perhaps that the natural magmas initially nucleated bubbles in the presence of CO 2. The disequilibrium H 2O exsolution seen in the 1173 K experiments indicates that inhibited bubble growth could lead to delayed exsolution in the conduit in cooler K-phonolite magmas.