Solubility of cassiterite in evolved granitic melts: effect of T, fO2, and additional volatiles

The aim of this experimental study was to determine the solubility of cassiterite in natural topaz- and cassiterite-bearing granite melts at temperatures close to the solidus. Profiles of Sn concentrations at glass–crystal (SnO₂) interface were determined following the method of (Harrison, T.M., Watson, E.B., 1983. Kinetics of zircon dissolution and zirconium diffusion in granitic melts of variable water content. Contributions to Mineralogy and Petrology 84, 66–72). The cassiterite concentration calculated at the SnO₂–glass interface is the SnO₂ solubility. Experiments were performed at 700–850 °C and 2 kbar using a natural F-bearing peraluminous granitic melt with 2.8 wt.% normative corundum. Slightly H₂O-undersaturated to H₂O-saturated melt compositions were chosen in order to minimize the loss of Sn to the noble element capsule walls. At the nickel–nickel oxide assemblage (Ni–NiO) oxygen fugacity buffer, the solubility of cassiterite in melts containing 1.12 wt.% F increases from 0.32 to 1.20 wt.% SnO₂ with an increasing temperature from 700 to 850 °C. At the Ni–NiO buffer and a given corundum content, SnO₂ solubility increases by 10% to 20% relative to an increase of F from 0 to 1.12 wt.%. SnO₂ solubility increases by 20% relative to increasing Cl content from 0 to 0.37 wt.% in synthetic granitic melts at 850 °C. We show that Cl is at least as important as F in controlling SnO₂ solubility in evolved peraluminous melts at oxygen fugacities close to the Ni–NiO buffer. In addition to the strong effects of temperature and fO₂ on SnO₂ solubility, an additional controlling parameter is the amount of excess Al (corundum content). At Ni–NiO and 850 °C, SnO₂ solubility increases from 0.47 to 1.10 wt.% SnO₂ as the normative corundum content increases from 0.1 to 2.8 wt.%. At oxidizing conditions (Ni–NiO +2 to +3), Sn is mainly incorporated as Sn⁴⁺ and the effect of excess Al seems to be significantly weaker than at reducing conditions.     

Formation and ascent of granitic magmas

New results obtained by the investigation of liquidus and solidus phase relationships in the haplogranite system Qz-Ab-Or are used to discuss the evolution of magmas during their ascent in the crust. It is assumed that the magmas are formed at 720°C, 820°C, 920°C and at a depth corresponding to a pressure of 8 kbar. The starting composition of the magma is taken as 50% melt plus 50% quartz and feldspars. In case of a closed system (no heat exchange and no transfer of elements) the melt fraction of magmas, the water activity and the viscosity increase with decreasing pressure. The temperature slightly decreases. At 700°C the viscosity is approximatively 2 orders of magnitude lower than at 900°C. This is related to the higher amount of water in the (H₂O-undersaturated) melt at low T. It is also shown that dehydration melting is only realistic at high T (900°C). At lower temperatures water has to be added from outside to obtain an intrusive magma with approximatively 50% melt.

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Zusammenfassung Neue Ergebnisse, erzielt durch Untersuchungen von Liquidus und Solidus Phasenbeziehungen des Granitsystems Qz-Ab-Or, werden benutzt, um die Entwicklung eines granitoiden Magmas während seines Aufstiegs zu diskutieren. Es wird vorausgesetzt, daß die Magmen bei Temperaturen von 720°C, 820°C und 920°C gebildet werden, sowie in einer Tiefe die einem Druck von 8 kbar entspricht. Die anfängliche Zusammensetzung des Magmas wird mit einem Verhältnis von 50% Schmelze sowie 50% Quarz und Feldspäten angenommen. Im Falle eines geschlossenen Systems (kein Austausch von Wärme und Elementen) steigt die Teilschmelzbildung von Magmen, die Aktivität des Wassers und die Viskosität bei abnehmenden Druck; hierbei sinkt die Temperatur leicht. Bei 700°C ist die Viskosität um ca. 2 Größenordnungen geringer als bei 900°C. Dies wird bedingt durch den höheren Gehalt an Wasser in der (H₂O-untersättigten) Schmelze bei tieferen Temperaturen. Es wird außerdem gezeigt, daß Magmenbildung durch Dehydratation nur bei hohen Temperaturen realistisch ist (900°C). Bei tieferen Temperaturen muß Wasser von außen zugeführt werden um ein intrusives Magma zu erhalten, das ungefähr 50% Schmelze besitzt.

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Résumé L'évolution des magmas granitiques au cours de leur ascension dans la croûte est discutée à la lumière de données nouvelles relatives aux relations entre phases liquides et solides dans le système Q-Ab-Or. On suppose que les magmas se forment à des températures de 720°C, 820°C, 920°C et à une profondeur correspondant à une pression de 8 Kb. On admet pour leur composition initiale un mélange de 50% de liquide et 50% de quartz + feldspaths. Dans le cas d'un système fermé (pas d'échange de chaleur ni de matière), la fraction liquide du magma, l'activité de l'eau et la viscosité augmentent quand la pression diminue; en même temps, la température décroît légèrement. A 700°C, la viscosité est d'environ 2 ordres de grandeur plus basse qu'à 900°C. Cette propriété est en relation avec la teneur en eau plus élevée dans le liquide (sous-saturé en eau) à basse température. On peut également montrer qu'une fusion déshydratante n'est vraisemblable qu'à haute température (900°C). Aux températures plus basses, de l'eau doit être apportée de l'extérieur pour l'obtention d'un magma à 50% de liquide.

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Storage conditions of Bezymianny Volcano parental magmas: results of phase equilibria experiments at 100 and 700 MPa

The crystallization sequence of a basaltic andesite from Bezymianny Volcano, Kamchatka, Russia, was simulated experimentally at 100 and 700 MPa at various water activities (aH₂O) to investigate the compositional evolution of residual liquids. The temperature (T) range of the experiments was 950–1,150 °C, aH₂O varied between 0.1 and 1, and the log of oxygen fugacity (fO₂) varied between quartz–fayalite–magnetite (QFM) and QFM + 4.1. The comparison of the experimentally produced liquids and natural samples was used to constrain the pressure (P)–T–aH₂O–fO₂ conditions of the Bezymianny parental magma in the intra-crustal magma plumbing system. The phase equilibria constraints suggest that parental basaltic andesite magmas should contain ~2–2.5 wt% H₂O; they can be stored in upper crustal levels at a depth of ~15 km, and at this depth they start to crystallize at ~1,110 °C. The subsequent chemical evolution of this parental magma most probably proceeded as decompressional crystallization occurred during magma ascent. The final depths at which crystallization products accumulated prior to eruption are not well constrained experimentally but should not be shallower than 3–4 km because amphibole is present in natural magmas (>150 MPa). Thus, the major volume of Bezymianny andesites was produced in a mid-crustal magma chamber as a result of decompressional crystallization of parental basaltic andesites, accompanied by mixing with silicic products from the earlier stages of magma fractionation. In addition, these processes are complicated by the release of volatiles due to magma degassing, which occurs at various stages during magma ascent.     

Liquidus temperatures and phase compositions in the system Qz-Ab-Or at 5 kbar and very low water activities

Liquidus phase relations have been experimentally determined in the systems Qz-Ab-Or-(H₂O), Qz-Ab-(H₂O) and Qz-Or-(H₂O) at H₂O-undersaturated conditions (a _H2O = 0.07) and P = 5 kbar. Starting materials were homogeneous synthetic glasses containing 1 wt% H₂O. The liquidus temperatures were bracketed by crystallization and dissolution experiments. The results of kinetic studies showed that crushed glasses are the best starting materials to overcome undercooling and to minimize the temperature difference between the lowest temperature of complete dissolution (melting) and the highest temperature at which crystallization can be observed. At P = 5 kbar and a _H2O = 0.07, the Qz-Ab eutectic composition is Qz₃₂Ab₆₈ at 1095 °C (±10 °C) and the Qz-Or eutectic is Qz₃₈Or₆₂ at 1030 °C (±10 °C). The minimum temperature of the ternary system Qz-Ab-Or is 990 °C (±10 °C) and the minimum composition is Qz₃₂Ab₃₅‐ Or₃₃. The Qz content of the minimum composition in the system Qz-Ab-Or-H₂O remains constant with changing a _H2O. The normative Or content, however, increases by approximately 10 wt% with decreasing a _H2O from 1 to 0.07. Such an increase has already been observed in the system Qz-Ab-Or-H₂O-CO₂ at high a _H2O and it is concluded that the use of CO₂ to reduce water activities does not influence the composition of the minima in quartz-feldspar systems. The determined liquidus temperature in melts with 1 wt% H₂O is very similar to that obtained in previous nominally “dry” experiments. This discrepancy is interpreted to be due to problems in obtaining absolutely dry conditions. Thus, the hitherto published solidus and liquidus temperatures for “dry” conditions are probably underestimated. Received: 27 March 1997 / Accepted: 1 October 1997     

Differentiation and crystallization conditions of basalts from the Kerguelen large igneous province: an experimental study

Phase relations of basalts from the Kerguelen large igneous province have been investigated experimentally to understand the effect of temperature, fO₂, and fugacity of volatiles (e.g., H₂O and CO₂) on the differentiation path of LIP basalts. The starting rock samples were a tholeiitic basalt from the Northern Kerguelen Plateau (ODP Leg 183 Site 1140) and mildly alkalic basalt evolved from the Kerguelen Archipelago (Mt. Crozier on the Courbet Peninsula), representing different differentiation stages of basalts related to the Kerguelen mantle plume. The influence of temperature, water and oxygen fugacity on phase stability and composition was investigated at 500 MPa and all experiments were fluid-saturated. Crystallization experiments were performed at temperatures between 900 and 1,160°C under oxidizing (log fO₂ ~ ΔQFM + 4) and reducing conditions (log fO₂ ~ QFM) in an internally heated gas-pressure vessel equipped with a rapid quench device and a Pt-Membrane for monitoring the fH₂. In all experiments, a significant influence of the fO₂ on the composition and stability of the Mg/Fe-bearing mineral phases could be observed. Under reducing conditions, the residual melts follow a tholeiitic differentiation trend. In contrast, melts have high Mg# [Mg²⁺/(Mg²⁺ + Fe²⁺)] and follow a calk-alkalic differentiation trend at oxidizing conditions. The comparison of the natural phenocryst assemblages with the experimental products allows us to constrain the differentiation and pre-eruptive conditions of these magmas. The pre-eruptive temperature of the alkalic basalt was about 950–1,050°C. The water content of the melt was below 2.5 wt% H₂O and strongly oxidizing conditions (log fO₂ ~ ΔQFM + 2) were prevailing in the magma chamber prior to eruption. The temperature of the tholeiitic melt was above 1,060°C, with a water content below 2 wt% H₂O and a log fO₂ ~ ΔQFM + 1. Early fractionation of clinopyroxene is a crucial step resulting in the generation of silica-poor and alkali-rich residual melts (e.g., alkali basalt). The enrichment of alkalis in residual melts is enhanced at high fO₂ and low aH₂O.     

Water solubility in haplogranitic melts coexisting with H2O-H2 fluids

The water solubility in haplogranitic melts (normative composition Ab₃₉Or₃₂Qz₂₉) coexisting with H₂O-H₂ fluids at 800 and 950 °C and 1, 2 and 3 kbar vapour pressure has been determined using IR spectroscopy. The experiments were performed in internally heated pressure vessels and the hydrogen fugacity (f _H2) was controlled using the double capsule technique and oxygen buffer assemblages (WM and IW). Due to the limited lifetimes of these oxygen buffers the water solubility was determined from diffusion profiles (concentration-distance profiles) measured with IR spectroscopy in the quenched glasses. The reliability of the experimental strategy was demonstrated by comparing the results of short- and long-duration experiments performed with pure H₂O fluids. The water solubility in Ab₃₉Or₃₂Qz₂₉ melts equilibrated with H₂O-H₂ fluids decreases progressively with decreasing f _H2O, as f _H2 (or X _H2) increases in the fluid phase. The effect of H₂ on the evolution of the water solubility is similar to that of CO₂ or another volatile with a low solubility in the melt and can be calculated in a first approximation with the Burnham water solubility model. Recalculation of high temperature water speciation for AOQ melts coexisting with H₂O-H₂ fluids at 800 °C, 2 kbar suggests that the concentrations of molecular H₂O are proportional to f _H2O (calculated using available mixing models), indicating Henrian behaviour for the solubility of molecular H₂O in haplogranitic melts. Received: 29 June 1998 / Accepted: 10 March 1999     

Crystallization conditions in the Upper Pollara magma chamber, Salina Island, Southern Tyrrhenian Sea

Summary Pyroclastites erupted from the Upper Pollara magma chamber (13 ka, Salina Island, Aeolian Archipelago) resulted from mingling and mixing of rhyolitic and andesitic magmas. An experimental study has been conducted on the rhyolitic end-member to constrain the pre-eruptive conditions of the magma. In order to check for the role of mixing on the equilibrium phase assemblage, three different starting compositions, corresponding to three different mixing degrees, have been used. The crystallization experiments were conducted at two different oxygen fugacities and at variable temperature and fluid contents. The results indicate that the natural mineralogical assemblage can only be reproduced from a composition showing a certain degree of mixing. Assuming a pressure of 200 MPa (generally accepted for the Aeolian Islands), the pre-eruptive temperature of the magmas is estimated between 755 and 800 °C and the water content of the melt was higher than 4–4.5 wt.%. The Upper Pollara magma crystallized at relatively high fO₂ (ΔlogfO₂ = Ni–NiO + 1 log unit), compared to rhyolitic magmas from Lipari and Vulcano. As this difference has not been observed for the most primitive magmas the difference in fO₂ could be related to different degassing processes operating in Salina and Lipari – Vulcano magmas.     

Viscosity of flux-rich pegmatitic melts

Viscosity experiments were conducted with two flux-rich pegmatitic melts PEG0 and PEG2. The Li₂O, F, B₂O₃ and P₂O₅ contents of these melts were 1.04, 4.06, 2.30 and 1.68 and 1.68, 5.46, 2.75 and 2.46 wt%, respectively. The water contents varied from dry to 9.04 wt% H₂O. The viscosity was determined in internally heated gas pressure vessels using the falling sphere method in the temperature range 873–1,373 K at 200 and 320 MPa pressure. At 1,073 K, the viscosity of water-rich (~9 wt% H₂O) melts is in the range of 3–60 Pa s, depending on the melt composition. Extrapolations to lower temperature assuming an Arrhenian behavior indicate that highly fluxed pegmatite melts may reach viscosities of ~30 Pa s at 773 K. However, this value is a minimum estimation considering the strongly non-Arrhenian behavior of hydrous silicate melts. The experimentally determined melt viscosities are lower than the prediction of current models taking compositional parameters into account. Thus, these models need to be improved to predict accurately the viscosity of flux-rich water bearing melts. The data also indicate that Li influences significantly the melt viscosity. Decreasing the molar Al/(Na + K + Li) ratio results in a strong viscosity decrease, and highly fluxed melts with low Al/(Na + K + Li) ratios (~0.8) have a rheological behavior which is very close to that of supercritical fluids.     

REE distribution in some layered migmatites: constraints on their petrogenesis

The REE distributions in mesosomes, neosomes, leucosomes and melanosomes of four layered migmatites have been investigated. In one example (Arvika migmatites) the REE patterns in adjacent paragneisses, the presumed parent rock of the migmatites, were also determined. REE patterns of neosomes and mesosomes of Arvika migmatites are similar to the finegrained layers and coarse-grained layers, respectively, observed in the adjacent paragneiss. This is in agreement with the layer-by-layer paragneiss-migmatite transformation model.

The REE patterns of mesosomes and neosomes indicate that these lithologies may have been closed systems (for REE) during the formation of the migmatites. No indication of metasomatic reactions, melt segregation or injection could be detected. Within the neosomes, leucosomes are depleted and melanosomes enriched in REE contents. This is interpreted to be due to separation and concentration of accessory minerals (monazite, epidote, allanite, zircon, sphene, apatite, garnet) into the melanosomes. The behaviour of accessory minerals during migmatite formation is closely allied to that of biotite, which is also concentrated in the melanosomes.     

The formation of SiO<Subscript>2</Subscript>-rich melts within the deep oceanic crust by hydrous partial melting of gabbros

Small amounts of felsic, evolved plutonic rocks, often called oceanic plagiogranites, always occur as veins or small stocks within the gabbroic section of the oceanic crust. Four major models are under debate to explain the formation of these rocks: (1) late-stage differentiation of a parental MORB melt, (2) partial melting of gabbroic rocks, (3) immiscibility in an evolved tholeiitic liquid, and (4) assimilation and partial melting of previously altered dikes. Recent experimental data in hydrous MORB-type systems are used to evaluate the petrogenesis of oceanic plagiogranites within the deep oceanic crust. Experiments show that TiO₂ is a key parameter for the discrimination between different processes: TiO₂ is relatively low in melts generated by anatexis of gabbros which is a consequence of the low TiO₂ contents of the protolith, due to the depleted nature of typical cumulate gabbros formed in the oceanic crust. On the other hand, TiO₂ is relatively high in those melts generated by MORB differentiation or liquid immiscibility. Since the TiO₂ content of many oceanic plagiogranites is far below that expected in case of a generation by simple MORB differentiation or immiscibility, these rocks may be regarded as products of anatexis. This may indicate that partial melting processes triggered by water-rich fluids are more common in the deep oceanic crust than believed up to now. At slow-spreading ridges, seawater may be transported via high-temperature shear zones deeply into the crust and thus made available for melting processes.