The Solubility of Sulphur in Hydrous Rhyolitic Melts

Experiments performed at 2 kbar, in the temperature range 800–1000°C,with fO₂ between NNO–2·3 and NNO+2·9 (whereNNO is the nickel–nickel oxide buffer), and varying amountsof sulphur added to hydrous metaluminous rhyolite bulk compositions,were used to constrain the solubility of sulphur in rhyolitemelts. The results show that fS₂ exerts a dominant control onthe sulphur solubility in hydrous silicate melts and that, dependingon fO₂, a rhyolitic melt can reach sulphur contents close to1000 ppm at high fS₂. At fO₂ below NNO+1, the addition of ironto a sulphur-bearing rhyolite magma produces massive crystallizationof pyrrhotite and does not enhance the sulphur solubility ofthe melt. For a given fO₂, the melt-sulphur-content increaseswith fS₂. For fixed fO₂ and fS₂, temperature exerts a positivecontrol on sulphur solubilities, at least for fO₂ below NNO+1.The mole fraction of dissolved sulphur exhibits essentiallylinear dependence on fH₂S at low fO₂ and, although the experimentalevidence is less clear, on fSO₂ at high fO₂. The minimum insulphur solubility corresponds to the redox range where bothfH₂S and fSO₂ are approximately equal. A thermodynamic modelof sulphur solubility in hydrous rhyolite melts is derived assumingthat total dissolved sulphur results from the additive effectsof H₂S and SO₂ dissolution reactions. The model reproduces wellthe minimum of sulphur solubility at around NNO+1, in additionto the variation of the sulphide to sulphate ratio with fO₂.A simple empirical model of sulphur solubility in rhyoliticmelts is derived, and shows good correspondence between modeland observations for high-silica rhyolites. KEY WORDS: sulphur; solubility; rhyolite; thermodynamics; fO₂; fS₂     

Phase Equilibria of the Lyngdal Granodiorite (Norway): Implications for the Origin of Metaluminous Ferroan Granitoids

The Proterozoic (950 Ma) Lyngdal granodiorite of southern Norwaybelongs to a series of hornblende–biotite metaluminousferroan granitoids (HBG suite) coeval with the post-collisionalRogaland Anorthosite–Mangerite–Charnockite (AMC)suite. This granitoid massif shares many geochemical characteristicswith rapakivi granitoids, yet granodiorites dominate over granites.To constrain both crystallization (P, T, fO₂, H₂O in melt) andmagma generation conditions, we performed crystallization experimentson two samples of the Lyngdal granodiorite (with 60 and 65 wt% SiO₂) at 4–2 kbar, mainly at fO₂ of NNO (nickel–nickeloxide) to NNO + 1, and under fluid-saturated conditions withvarious H₂O–CO₂ ratios for each temperature. Comparisonbetween experimental phase equilibria and the mineral assemblagein the Lyngdal granodiorite indicates that it crystallized between4 and 2 kbar, from a magma with 5–6 wt % H₂O at an fO₂of NNO to NNO + 1. These oxidized and wet conditions sharplycontrast with the dry and reduced conditions inferred for thepetrogenesis of the AMC suite and many other rapakivi granitesworldwide. The high liquidus temperature and H₂O content ofthe Lyngdal granodiorite imply that it is not a primary magmaproduced by the partial melting of the crust but is derivedby the fractionation of a mafic magma. Lyngdal-type magmas appearto have volcanic equivalents in the geological record. In particular,our results show that oxidized high-silica rhyolites, such asthe Bishop Tuff, could be derived via fractionation of oxidizedintermediate magmas and do not necessarily represent primarycrustal melts. This study underlines the great variability ofcrystallization conditions (from anhydrous to hydrous and reducedto oxidized) and petrogenetic processes among the metaluminousferroan magmas of intermediate compositions (granodiorites,quartz mangerites, quartz latites), suggesting that there isnot a single model to explain these rocks. KEY WORDS: ferroan granitoids; crystallization conditions; experiments; Norway; Sveconorwegian; Bishop Tuff     

Experimental Crystallization of Leucogranite Magmas

Both crystallization and melting experiments have been carriedout on two natural, biotite-muscovite (DK) and tourmaline-muscovite(GB) High Himalayan leucogranites (HHL) at 4 kbar, logfO₂ =FMQ–05, aH₂O = 1–0•03, and at five temperaturesbetween 803 and 663C H₂O contents of the quenched glasses wereanalysed by ion microprobe. Plagioclase and biotite are theliquidus phases for reduced melt H₂O contents and H₂O-rich conditions,respectively. H₂O saturation limits range from 8 to 10 wt%.DK has a wider crystallization interval than GB (150 vs 80Cfor conditions close to H₂O saturation), and a slightly higherH₂O-saturated solidus (645 compared with 630C for GB). Tourmalinenever crystallized spontaneously from the melt. Tourmaline seedsalways reacted out to biotite in the biotite-muscovite sample,whereas they remained stable in the tourmaline-muscovite sample.Biotite is replaced by hercynite as the main ferromagnesianphase at high temperature and reduced aH₂O. Muscovite crystallizationis restricted to near-solidus conditions. The compositions ofplagioclase, alkali feldspar, biotite and muscovite are givenas a function of bulk composition, temperature and aH₂O. Glasscompositions are richer in normative quartz than the 4 kbarH₂O-saturated Qz–Ab–Or eutectic, and become moreperaluminous and less mafic with increasing fractionation. Biotitecrystallization in peraluminous liquids is favoured by elevatedFe, Mg and Ti contents. Muscovite crystallization is not promotedunder H₂O-saturated conditions. Tourmaline stability is stronglydependent on aH₂O. For GB, tourmaline is present at elevatedtemperatures for intermediate values of aH₂O (803 C, 0–7),but not above 650C for H₂O-saturated conditions. Comparisonof the natural crystallization sequence with experiments suggestsinitial water contents between 5 and 75 wt % for the DK magma,and > 7 wt% for the GB magma. Plagioclase core compositionsgive minimum temperatures of 700C for GB and 750C for DK,consistent with an emplacement of these HHL as almost entirelyliquid bodies. The restricted occurrence of biotite in the GBgranite suggests that it reacted out during the magmatic evolution,owing to a marked change in fO₂ toward more oxidizing conditions.Tourmaline leucogranites can be generated from biotite leucogranitesby fractional crystallization under conditions of increasingdegree of oxidation. KEY WORDS: leucogranite; melting experiments; crystlization experiments; Himalayas; phase relations ^*Corresponding author     

Experimental Constraints on the Origin of the 1991 Pinatubo Dacite

Crystallization (dacite) and interaction (dacite–peridotite)experiments have been performed on the 1991 Pinatubo dacite(Luzon Island, Philippines) to constrain its petrogenesis. Inthe dacite–H₂O system at 960 MPa, magnetite and eitherclinopyroxene (low H₂O) or amphibole (high H₂O) are the liquidusphases. No garnet is observed at this pressure. Dacite–peridotite interaction at 920 MPa produces massive orthopyroxenecrystallization, in addition to amphibole ± phlogopite.Amphibole crystallizing in dacite at 960 MPa has the same compositionas the aluminium-rich hornblende preserved in the cores of amphibolephenocrysts in the 1991 dacite, suggesting a high-pressure stageof dacite crystallization with high melt H₂O contents (>10wt %) at relatively low temperature (<950°C). The compositionsof plagioclase, amphibole and melt inclusion suggest that thePinatubo dacite was water-rich, oxidized and not much hotterthan 900°C, when emplaced into the shallow magma reservoirin which most phenocrysts precipitated before the onset of the1991 eruption. The LREE-enriched REE pattern of the whole-rockdacite demands garnet somewhere during its petrogenesis, whichin turn suggests high-pressure derivation. Partial melting ofsubducted oceanic crust yields melts unlike the Pinatubo dacite.Interaction of these slab melts with sub-arc peridotite is unableto produce a Pinatubo type of dacite, nor is a direct mantleorigin conceivable on the basis of our peridotite–daciteinteraction experimental results. Dehydration melting of underplatedbasalts requires unrealistically high temperatures and doesnot yield dacite with the low FeO/MgO, and high H₂O, Ni andCr contents typical of the Pinatubo dacite. The most plausibleorigin of the Pinatubo dacite is via high-pressure fractionationof a hydrous, oxidized, primitive basalt that crystallized amphiboleand garnet upon cooling. Dacite melts produced in this way weredirectly expelled from the uppermost mantle or lower crust toshallow-level reservoirs from which they erupted occasionally.Magmas such as the Pinatubo dacite may provide evidence forthe existence of particularly H₂O-rich conditions in the sub-arcmantle wedge rather than the melting of the young, hot subductingoceanic plate. KEY WORDS: Pinatubo dacite; slab melt; experimental petrology; arc magmas     

Thermal Constraints on the Emplacement Rate of a Large Intrusive Complex: The Manaslu Leucogranite, Nepal Himalaya

The emplacement of the Manaslu leucogranite body (Nepal, Himalaya)has been modelled as the accretion of successive sills. Theleucogranite is characterized by isotopic heterogeneities suggestinglimited magma convection, and by a thin (<100 m) upper thermalaureole. These characteristics were used to constrain the maximummagma emplacement rate. Models were tested with sills injectedregularly over the whole duration of emplacement and with twoemplacement sequences separated by a repose period. Additionally,the hypothesis of a tectonic top contact, with unroofing limitingheat transfer during magma emplacement, was evaluated. In thislatter case, the upper limit for the emplacement rate was estimatedat 3·4 mm/year (or 1·5 Myr for 5 km of granite).Geological and thermobarometric data, however, argue againsta major role of fault activity in magma cooling during the leucograniteemplacement. The best model in agreement with available geochronologicaldata suggests an emplacement rate of 1 mm/year for a relativelyshallow level of emplacement (granite top at 10 km), uninterruptedby a long repose period. The thermal aureole temperature andthickness, and the isotopic heterogeneities within the leucogranite,can be explained by the accretion of 20–60 m thick sillsintruded every 20 000–60 000 years over a period of 5Myr. Under such conditions, the thermal effects of granite intrusionon the underlying rocks appear limited and cannot be invokedas a cause for the formation of migmatites. KEY WORDS: granite emplacement; heat transfer modelling; High Himalayan Leucogranite; Manaslu; thermal aureole     

Experimental Crystallization of a High-K Arc Basalt: the Golden Pumice, Stromboli Volcano (Italy)

The near-liquidus crystallization of a high-K basalt (PST-9golden pumice, 49·4 wt % SiO₂, 1·85 wt % K₂O,7·96 wt % MgO) from the present-day activity of Stromboli(Aeolian Islands, Italy) has been experimentally investigatedbetween 1050 and 1175°C, at pressures from 50 to 400 MPa,for melt H₂O concentrations between 1·2 and 5·5wt % and NNO ranging from –0·07 to +2·32.A drop-quench device was systematically used. AuPd alloys wereused as containers in most cases, resulting in an average Feloss of 13% for the 34 charges studied. Major crystallizingphases include clinopyroxene, olivine and plagioclase. Fe–Tioxide was encountered in a few charges. Clinopyroxene is theliquidus phase at 400 MPa down to at least 200 MPa, followedby olivine and plagioclase. The compositions of all major phasesand glass vary systematically with the proportion of crystals.Ca in clinopyroxene sensitively depends on the H₂O concentrationof the coexisting melt, and clinopyroxene Mg-number shows aweak negative correlation with NNO. The experimental data allowthe liquidus surface of PST-9 to be defined. When used in combinationwith melt inclusion data, a consistent set of pre-eruptive pressures(100–270 MPa), temperatures (1140–1160°C) andmelt H₂O concentrations is obtained. Near-liquidus phase equilibriaand clinopyroxene Ca contents require melt H₂O concentrations<2·7–3·6 and 3 ± 1 wt %, respectively,overlapping with the maximum frequency of glass inclusion data(2·5–2·7 wt % H₂O). For olivine to crystallizeclose to the liquidus, pressures close to 200 MPa are needed.Redox conditions around NNO = +0·5 are inferred fromclinopyroxene compositions. The determined pre-eruptive parametersrefer to the storage region of golden pumice melts, which islocated at a depth of around 7·5 km, within the metamorphicarc crust. Golden pumice melts ascending from their storagezone along an adiabat will not experience crystallization ontheir way to the surface. KEY WORDS: basalt; pumice; experiment; phase equilibria; Stromboli     

Experimental and Thermodynamic Constraints on the Sulphur Yield of Peralkaline and Metaluminous Silicic Flood Eruptions

Many basaltic flood provinces are characterized by the existenceof voluminous amounts of silicic magmas, yet the role of thesilicic component in sulphur emissions associated with trapactivity remains poorly known. We have performed experimentsand theoretical calculations to address this issue. The meltsulphur content and fluid/melt partitioning at saturation witheither sulphide or sulphate or both have been experimentallydetermined in three peralkaline rhyolites, which are a majorcomponent of some flood provinces. Experiments were performedat 150 MPa, 800–900°C, fO₂ in the range NNO –2 to NNO + 3 and under water-rich conditions. The sulphur contentis strongly dependent on the peralkalinity of the melt, in additionto fO₂, and reaches 1000 ppm at NNO + 1 in the most stronglyperalkaline composition at 800°C. At all values of fO₂,peralkaline melts can carry 5–20 times more sulphur thantheir metaluminous equivalents. Mildly peralkaline compositionsshow little variation in fluid/melt sulphur partitioning withchanging fO₂ (D_S 270). In the most peralkaline melt, D_S risessharply at fO₂ > NNO + 1 to values of >500. The partitioncoefficient increases steadily for S_bulk between 1 and 6 wt% but remains about constant for S_bulk between 0·5 and1 wt %. At bulk sulphur contents lower than 4 wt %, a temperatureincrease from 800 to 900°C decreases D_S by 10%. These results,along with (1) thermodynamic calculations on the behaviour ofsulphur during the crystallization of basalt and partial meltingof the crust and (2) recent experimental constraints on sulphursolubility in metaluminous rhyolites, show that basalt fractionationcan produce rhyolitic magmas having much more sulphur than rhyolitesderived from crustal anatexis. In particular, hot and dry metaluminoussilicic magmas produced by melting of dehydrated lower crustare virtually devoid of sulphur. In contrast, peralkaline rhyolitesformed by crystal fractionation of alkali basalt can concentrateup to 90% of the original sulphur content of the parental magmas,especially when the basalt is CO₂-rich. On this basis, we estimatethe amounts of sulphur potentially released to the atmosphereby the silicic component of flood eruptive sequences. The peralkalineEthiopian and Deccan rhyolites could have produced 10¹⁷ and10¹⁸ g of S, respectively, which are comparable amounts to publishedestimates for the basaltic activity of each province. In contrast,despite similar erupted volumes, the metaluminous Paraná–Etendekasilicic eruptives could have injected only 4·6 x 10¹⁵g of S in the atmosphere. Peralkaline flood sequences may thushave greater environmental effects than those of metaluminousaffinity, in agreement with evidence available from mass extinctionsand oceanic anoxic events. KEY WORDS: silicic flood eruptions; sulphur; experiment; Ethiopia; Deccan     

Phase Relations of Peralkaline Silicic Magmas and Petrogenetic Implications

The phase relationships of three peralkaline rhyolites fromthe Kenya Rift have been established at 150 and 50 MPa, at oxygenfugacities of NNO - 1·6 and NNO + 3·6 (log fO₂relative to the Ni–NiO solid buffer), between 800 and660°C and for melt H₂O contents ranging between saturationand nominally anhydrous. The stability fields of fayalite, sodicamphiboles, chevkinite and fluorite in natural hydrous silicicmagmas are established. Additional phases include quartz, alkalifeldspar, ferrohedenbergite, biotite, aegirine, titanite, montdoriteand oxides. Ferrohedenbergite crystallization is restrictedto the least peralkaline rock, together with fayalite; it isreplaced at low melt water contents by ferrorichterite. Riebeckite–arfvedsoniteappears only in the more peralkaline rocks, at temperaturesbelow 750°C (dry) and below 670°C at H₂O saturation.Under oxidizing conditions, it breaks down to aegirine. In themore peralkaline rocks, biotite is restricted to temperaturesbelow 700°C and conditions close to H₂O saturation. At 50MPa, the tectosilicate liquidus temperatures are raised by 50–60°C,and that of amphibole by 30°C. Riebeckite–arfvedsonitestability extends down nearly to atmospheric pressure, as aresult of its F-rich character. The solidi of all three rocksare depressed by 40–100°C compared with the solidusof the metaluminous granite system, as a result of the abundanceof F and Cl. Low fO₂ lowers solidus temperatures by at least30°C. Comparison with studies of metaluminous and peraluminousfelsic magmas shows that plagioclase crystallization is suppressedas soon as the melt becomes peralkaline, whatever its CaO orvolatile contents. In contrast, at 100 MPa and H₂O saturation,the liquidus temperatures of quartz and alkali feldspar arenot significantly affected by changes in rock peralkalinity,showing that the incorporation of water in peralkaline meltsdiminishes the depression of liquidus temperatures in dry peralkalinesilicic melts compared with dry metaluminous or peraluminousvarieties. At 150 MPa, pre-eruptive melt H₂O contents rangefrom 4 wt % in the least peralkaline rock to nearly 6 wt % inthe two more peralkaline compositions, in broad agreement withprevious melt inclusion data. The experimental results implymagmatic fO₂ at or below the fayalite–quartz–magnetitesolid buffer, temperatures between 740 and 660°C, and meltevolution under near H₂O saturation conditions. KEY WORDS: peralkaline; rhyolite; phase equilibria     

Experimental Constraints on the Relationships between Peralkaline Rhyolites of the Kenya Rift Valley

Crystallization experiments on three comendites provide evidencefor the genetic relationships between peralkaline rhyolitesin the central Kenya rift valley. The crystallization of calcicclinopyroxene in slightly peralkaline rhyolites inhibits increasein peralkalinity by counteracting the effects of feldspar. Fractionationunder high fO₂ conditions produces residual liquids that areless, or only slightly more, peralkaline than the bulk composition.In contrast, crystallization under reduced conditions (<FMQ,where FMQ is the fayalite–magnetite–quartz buffer)and at high fF₂ inhibits calcic clinopyroxene and yields residualliquids that are more peralkaline than coexisting alkali feldspar,whose subsequent crystallization increases the peralkalinityof the liquid. A marginally peralkaline rhyolite [molar (Na₂O+ K₂O)/Al₂O₃ (NK/A) = 1·05] can yield a more typicallycomenditic rhyolite (NK/A = 1·28) after 95 wt % of crystallization.This comendite yields pantelleritic derivatives (NK/A >1·4)after 25 wt % crystallization. Upon further crystallization,extreme peralkaline compositions (NK/A     

Petrological and Experimental Constraints on the Pre-eruption Conditions of Holocene Dacite from Volcan San Pedro (36{degrees}S, Chilean Andes) and the Importance of Sulphur in Silicic Subduction-related Magmas

We present an experimental and petrological study aimed at estimatingthe pre-eruptive conditions of a Holocene dacitic lava fromVolcán San Pedro (36°S, Chilean Andes). Phase-equilibriumexperiments were performed at temperatures (T) from 800 to 950°C,and mainly at 200 MPa, but also at 55, 150, and 406 MPa. Oxygenfugacity (fO₂) ranged from the Ni–NiO buffer (NNO) to3·5 log units above (NNO + 3·5), and water contentsfrom