Effect of oxygen fugacity and water on phase equilibria of a hydrous tholeiitic basalt

The influence of oxygen fugacity and water on phase equilibria and the link between redox conditions and water activity were investigated experimentally using a primitive tholeiitic basalt composition relevant to the ocean crust. The crystallization experiments were performed in internally heated pressure vessels at 200 MPa in the temperature range 940–1,220°C. The oxygen fugacity was measured using the H₂-membrane technique. To study the effect of oxygen fugacity, three sets of experiments with different hydrogen fugacities were performed, showing systematic effects on the phase relations and compositions. In each experimental series, the water content of the system was varied from nominally dry to water-saturated conditions, causing a range of oxygen fugacities varying by ~3 log units per series. The range in oxygen fugacity investigated spans ~7 log units. Systematic effects of oxygen fugacity on the stability and composition of the mafic silicate phases, Cr–spinel and Fe–Ti oxides, under varying water contents were recorded. The Mg# of the melt, and therefore also the Mg# of olivine and clinopyroxene, changed systematically as a function of oxygen fugacity. An example of the link between oxygen fugacity and water activity under hydrogen-buffered conditions is the change in the crystallization sequence (olivine and Cr–spinel) due to a change in the oxygen fugacity caused by an increase in the water activity. The stability of magnetite is restricted to highly oxidizing conditions. The absence of magnetite in most of the experiments allows the determination of differentiation trends as a function of oxygen fugacity and water content, demonstrating that in an oxide-free crystallization sequence, water systematically affects the differentiation trend, while oxygen fugacity seems to have a negligible effect.     

Effect of water on tholeiitic basalt phase equilibria: an experimental study under oxidizing conditions

To investigate the effect of water on phase relations and compositions in a basaltic system, we performed crystallization experiments at pressures of 100, 200 and 500 MPa in a temperature range of 940 to 1,220°C using four different water contents. Depending on the water activity, the oxygen fugacity varied between 1 and 4 log units above the quartz-magnetite-fayalite buffer. Addition of water to the dry system shifts the solidus > 250°C to lower temperatures and increases the amount of melt drastically. For instance, at 1,100°C and 200 MPa, the melt fraction increases from 12.5 wt% at a water content of 1.6 wt% to 96.3% at a water content of 5 wt% in the melt. The compositions of the experimental phases also show a strong effect of water. Plagioclase is shifted to higher anorthite contents by the addition of water. Olivine and clinopyroxene show generally higher MgO/FeO ratios with added water, which could also be related to the increasing oxygen fugacity with water. Moreover, water affects the partitioning of certain elements between minerals and melts, e.g., the Ca partitioning between olivine and melt. Plagioclase shows a characteristic change in the order of crystallization with water that may help to explain the formation of wehrlites intruding the lower oceanic crust (e.g., in Oman, Macquarie Island). At 100 MPa, plagioclase crystallizes before clinopyroxene at all water contents. At pressures > 100 MPa, plagioclase crystallizes before clinopyroxene at low water contents (e.g. < 3 wt%), but after clinopyroxene at H₂O in the melt > 3 wt%. This change in crystallization order indicates that a paragenesis typical for wehrlites (olivine–clinopyroxene–without plagioclase) is stabilized at low pressures typical of the oceanic crust only at high water contents. This opens the possibility that typical wehrlites in the oceanic crust can be formed by the fractionation and accumulation of olivine and clinopyroxene at 1,060°C and > 100 MPa in a primitive tholeiitic basaltic system containing more than 3 wt% water. The comparison of the experimental results with evolution trends calculated by the thermodynamic models “MELTS” and “Comagmat” shows that neither model predicts the experimental phase relations with sufficient accuracy.Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.     

The significance of phenocryst diversity in tephra from recent eruptions at Popocatepetl volcano (central Mexico)

Tephra lapilli from six explosive eruptions between April 1996 and February 1998 at Popocatepetl volcano (=Popo) in central Mexico have been studied to investigate the causes of magma diversification in thick-crusted volcanic arcs. The tephra particles are sparsely porphyritic (≈5 vol%) magnesian andesites (SiO₂=58–65 wt%; MgO=2.6–5.9 wt%) that contain phenocrysts of NiO-rich (up to 0.67 wt% NiO) magnesian olivine (Fo_89–91 cores) with inclusions of Cr-spinel (cr#=59–70), orthopyroxene (mg#=63–76), clinopyroxene (mg#=68–86), intermediate to sodic plagioclase (An_33–66), and traces of amphibole. Major and trace element systematics indicate magma mixing. The liquid mg#_melt ratios inferred from the ferromagnesian phenocrysts suggest the existence of a mafic (mg#_melt ≈ 72–76) and an evolved component magma (mg#_melt ≈ 35–40). These component magmas form a hybrid magnesian andesite with an intermediate range of mg#_melt=50–72. The mafic end member (mg#_melt ≈ 72–75) is saturated with olivine and spinel and crystallizes at temperatures ≈1170–1085 °C with oxygen fugacities close to the fayalite–magnetite–quartz buffer and elevated water contents of several wt% H₂O. A likely location of crystallization is at lower crustal levels, possibly at the Moho. Olivine is followed by high-mg# clinopyroxene which could start to crystallize during magma ascent. At depths of ≈4 to 13 km, the mafic magma mixes with an evolved composition containing low-mg# clino- and orthopyroxene and plagioclase at a temperature of ≈950 °C. The repetitive ascent of batches of mafic magmas spaced days to weeks apart implies multiple episodes of crystallization and magma mixing. The tephra is similar to the Popo magnesian andesites, suggesting similar generic processes for the common lavas of the volcano. The advantage of the tephra is that it can be used to reconstruct the composition of the mafic magma. Building on the elemental systematics of the tephra and a comparison to the near-primary basalts from the surrounding monogenetic fields, we infer that the Popo mafic end member is a magnesian andesite with variable, but high SiO₂ contents of ≈55–62 wt% and near-primary characteristics, such as high-mg#_melt of 72–75, FeO*/MgO ratios <1 (if extrapolated to an mg#_melt of 72–75), and high Ni contents (=200 ppm Ni). This model implies that the typical elemental signature of the Popo andesites, such as the low CaO, Al₂O₃, FeO*, high Na₂O contents, and the depletion in high-field strength elements (e.g., P, Zr, Ti), are mantle source phenomena. Thus, determining the elemental budget of the magnesian andesite, as it is prior to the modifications by crustal differentiation, is central to quantifying the subcrustal mass fluxes beneath Popo. Received: 13 December 1999 / Accepted: 11 August 2000     

Liquidus phase relations on the join diopside-forsterite-anorthite from 1 atm to 20 kbar: Their bearing on the generation and crystallization of basaltic magma

In the system CaO-MgO-Al₂O₃-SiO₂, the tetrahedron CaMgSi₂O₆(di)-Mg₂SiO₄(fo)-SiO₂-CaAl₂ SiO₆(CaTs) forms a simplified basalt tetrahedron, and within this tetrahedron, the plane di-fo-CaAl₂Si₂O₈(an) separates simplified tholeiitic from alkalic basalts. Liquidus phase relations on this join have been studied at 1 atm and at 7, 10, 15, and 20 kbar. The temperature maximum on the 1 atm isobaric quaternary univariant line along which forsterite, diopside, anorthite, and liquid are in equilibrium lies to the SiO₂-rich side of the join di-fo-an. The isobaric quaternary invariant point at which forsterite, diopside, anorthite, spinel, and liquid are in equilibrium passes, with increasing pressure, from the silica-poor to the silica-rich side of the join di-fo-an, which causes the piercing points on this join to change from forsterite+diopside+anorthite+liquid and forsterite +spinel+anorthite+liquid below 5 kbar to forsterite +diopside+spinel+liquid and diopside +spinel+anorthite+liquid above 5 kbar. As pressure increases, the forsterite and anorthite fields contract and the diopside and corundum fields expand. The anorthite primary phase field disappears entirely from the join di-fo-an between 15 and 20 kbar. Below about 4 kbar, the join di-fo-an represents, in simplified form, a thermal divide between alkalic and tholeiitic basalts. From about 4 to at least 12 kbar, alkalic basalts can produce tholeiitic basalts by fractional crystallization, and at pressures above about 12 kbar, it is possible for alkalic basalt to be produced from oceanite by crystallization of both olivine and orthopyroxene. If alkalic basalts are primary melts from a lherzolite mantle, they must be produced at high pressures, probably greater than about 12 kbar.Department of Geosciences, University of Texas at Dallas Contribution No. 327. Hawaii Institute of Geophysics Contribution No. 814.     

Phase equilibria of phlogopite lamprophyres from western Mexico: biotite-liquid equilibria and P-T estimates for biotite-bearing igneous rocks

 Olivine and augite minette powders have been equilibrated from one bar to nearly 2.0 kbar (water-saturated), and from 900 to 1300° C, and then quenched rapidly, at oxygen fugacities controlled between the nickel-nickel oxide (NNO) and hematite-magnetite (HM) oxygen buffers. The liquidus of both samples is suppressed ∼100° C at water-saturated conditions and 1500 bar. Both lavas contained between 3 and 4 wt% water at the stage of phenocryst precipitation. The partitioning of ferric and ferrous iron between phlogopite and liquid has been determined on eight samples across 3 log f _O2 units; when these determinations are combined with previous studies, Fe₂O₃/(Σ FeO total) of Mg-rich biotite can be calculated knowing log f _O2, T, and X _Fe. Thermodynamic modelling of biotite-liquid equilibria results in two expressions for calculating activity coefficients (γ) for annite and phlogopite in natural biotites. Based on the partitioning of BaO and TiO₂ between biotite and liquid, we have formulated a thermometer and barometer. Over the range of 400° C, TiO₂ partitioning between phlogopite and liquid is a function of temperature (±50° C), and is insensitive to pressure and H₂O and O₂ activities. BaO partitioning between phlogopite and liquid is a function of both temperature and pressure (±4 kbar), the latter being most important. Applying the TiO₂ and BaO partitioning expressions to lamprophyre and lamproite suites shows that Mexican minettes equilibrated at low pressures (5 to 15 kbar;±4 kbar) and temperatures (1090 to 1160° C; ±50° C), while Australian lamproites equilibrated at higher P (up to 30 kbar; ±4 kbar) and T (1125 to 1400° C; ±50° C). Experimental glass compositions and phenocryst fractionation calculations, together with the BaO- and TiO₂- based pressure calculations indicate that felsic minettes from the Mexican suite of lavas can be generated by simple fractionation of a more mafic parent minette at mid to lower crustal pressures. Received: 1 August 1994/Accepted: 30 June 1995     

Sr-Nd-Pb isotopes from the Radicofani Volcano, Central Italy: constraints on heterogeneities in a veined mantle responsible for the shift from ultrapotassic shoshonite to basaltic andesite magmas in a post-collisional setting

The Radicofani Volcano is characterised by few lava flows, a cinder cone and a denudated neck, and is part of the Tuscan Magmatic Province, the northernmost volcanic region of the Italian peninsula. In spite of the short time span of activity, a large time-dependant chemical and isotopic variability is observed. Most of the rocks of the Radicofani volcano are ultrapotassic shoshonites associated to younger basaltic andesites, found at the bottom of the neck. K₂O contents are positively correlated with trace element and isotopic variations. Shoshonitic and high-K calc-alkaline rocks of the Radicofani volcano are significantly different from shoshonites occurring in association with leucite-bearing ultrapotassic rocks in the southernmost portion of the Roman Magmatic Province. The studied rocks are characterised by high, but variable, levels of incompatible trace elements with a subduction-related signature, with troughs at Ba, Ta, Nb, and Ti, and peaks at Cs, K, Th, U, and Pb. Initial values of ⁸⁷Sr/⁸⁶Sr range from 0.71333 to 0.71588, ¹⁴³Nd/¹⁴⁴Nd ranges from 0.512050 to 0.512183, while the lead isotope ratios vary between 18.672 and 18.716 for ²⁰⁶Pb/²⁰⁴Pb, 15.665 to 15.696 for ²⁰⁷Pb/²⁰⁴Pb, and 39.981 to 39.081 for ²⁰⁸Pb/²⁰⁴Pb. Ultrapotassic shoshonites show the highest incompatible trace element contents coupled with the highest ⁸⁷Sr/⁸⁶Sr and the lowest ¹⁴³Nd/¹⁴⁴Nd. On the basis of geochemical and isotopic signatures it is argued that magmas were generated in a modified lithospheric peridotitic source containing metasomatic veins generated by K-rich melts from recycled sediments within the mantle via subduction. A further metasomatic event generated by slab-derived fluids pervasively enriched the peridotitic source. Partial melting of the veins produced leucite-free ultrapotassic magmas (i.e. lamproite), and was triggered by rising of the isotherms after the orogenic front migrated eastward in the Italian Peninsula. Further rise of the isotherms induced larger degrees of partial melting inducing melting of the surrounding wall peridotite. The variation of the degree of partial melting of such a heterogeneous peridotitic source produced a wide spectrum of magma compositions, which mimic a mixing line between two components: ultrapotassic magma from partial melting of the metasomatic vein and a basaltic andesitic magma from partial melting of the surrounding peridotite.     

The andesite aqueduct: perspectives on the evolution of intermediate magmatism in west-central (105–99°W) Mexico

Intermediate calc-alkaline magma (52-65% SiO₂) in western-central Mexico is the focus of this paper, and the typically porphyritic andesites (57-65% SiO₂) form large central volcanoes, whereas basaltic andesites (52-57% SiO₂) are less porphyritic, and they are found as cones and flows but are absent from central volcanoes. Several studies of experimental phase equilibria on these lavas relate water concentration to the phenocryst assemblages and to the degree of crystallinity, so that the abundance, composition and variety of phenocrysts can be used to constrain the amount of water dissolved in the magmas. Thus, the plagioclase-rich andesites of Volcan Colima, Mexico, become so as a result of decompressional crystallisation at ~950 °C (the pyroxene phenocryst temperature), and lose their dissolved water (2.5 to 4.5 wt% H₂O) which is inversely proportional to the modal abundance of plagioclase. The feeding magma to V. Colima, North America's most productive central volcano, is represented by hornblende lamprophyre, a lava type without plagioclase phenocrysts which requires at least 6 wt% water to reproduce the phenocryst assemblage. Thus, degassing of the V. Colima magmas, and of those of the other central volcanoes in the western-central Mexican volcanic belt, contributes essentially all their dissolved water to the conduit or to the atmosphere. The source of this magmatic water is related to the source of the intermediate magmas. For some this must lie in the mantle, as the incorporation of hornblende-lherzolite nodules in a hydrous andesite with hornblende phenocrysts could only have occurred while ascending through the mantle. Consistent with a mantle source is the composition of the olivine phenocrysts in Mexican lavas with 10 to 5% MgO, which is in the mantle range of Fo_88-92. Accordingly, basaltic andesites and andesites with >5% MgO are candidates for a mantle source. The equilibration of intermediate magmas with the mantle, as illustrated by the experiments of various workers, requires that the magmas be hydrous at pressure. An additional constraint is that the activity of silica in the mantle must be equal to that in the hydrous magma at equilibrium. Using published and new experiments to define RTln%_SiO2 in hydrous liquids, this quantity is shown to vary as a function of liquid composition (H₂O, MgO, Na₂O+K₂O), and it approaches zero for quartz-saturated hydrous liquids. Using appropriate values of RTln%_SiO2 for three intermediate lavas, the amount of water required to equilibrate with an olivine-orthopyroxene mantle source is calculated, and within error indicates that only the most silica-rich magma is at water saturation in the mantle, in agreement with published experimental work. Hydrous intermediate magmas, ascending from their hornblende-lherzolite source regions (~1 to 1.5 GPa) along the hydrous adiabat, may not encounter any phase boundaries until 0.2-0.4 GPa because of the increase in the thermal stability of hornblende in water-undersaturated magmas. Therefore, the phenocryst assemblages of hornblende-free andesites equilibrate at low pressures. The virtual absence of basalt in west-central Mexico (<4 Ma) is considered to be related to the large increase in crystallinity found in isobaric hydrous experiments crystallising hornblende at pressures close to those at the base of the crust. As a large proportion of the ferromagnesian components of basalt is acceptable to hornblende, it does not take a significant cooling interval (~40-50 °C) below the liquidus for hydrous basaltic magma to acquire >50% crystallinity, evidently also an eruptible limit for V. Colima andesitic lavas. If the lower limit of water dissolved in Mexican intermediate magmas is accepted as that required for phenocryst equilibration (~6 wt% water), and the upper limit as saturation in the mantle source at 1 GPa (~16 wt%) then, with an estimate of the volcanic and plutonic magma delivery rate (km³/10⁶ year) per km of volcanic arc, the flux of water returned from the mantle along the 35,000-km, global subduction-related arc system can be estimated. Measurements of the volcanic flux are woefully few, and estimates from Mexico, the Lesser Antilles and central America show a range from 4 to 20 km³/10⁶ year2km which, if subtracted from the isotopically constrained continental growth rate, gives the plutonic flux rate. This suggests that, of the magma flux ascending to the continental crust, only about a fifth reaches the surface. If the dissolved magmatic water limits are coupled with the volcanic and plutonic emplacement rates, then the amount of water returned by magmatism to the crust is crudely in balance with that subducted.     

Hydrothermal petroleum of Lake Chapala,Citala Rift,western Mexico: Bitumen compositions from source sediments and application of hydrous pyrolysis

Hydrothermal simulation experiments were performed with contemporary sediments from Lake Chapala to assess the source of the lake tars. The precursor-product relationships of the organic compounds were determined for the source sediments and their hydrous pyrolysis products. The pyrolysis products contained major unresolved complex mixtures of branched and cyclic hydrocarbons, low amounts of n-alkanes, dinosterane, gammacerane, and immature and mature hopane biomarkers derived from lacustrine biomass sources. The results support the proposal that the tar manifestations in the lake are not biodegraded petroleum, but were hydrothermally generated from lacustrine organic matter at temperatures not exceeding about 250 °C over brief geological times.     

The solubility of alumina in enstatite and the phase equilibria in the join MgSiO3-MgAl2SiO6 at 10–25 kbar

The solubility of alumina in enstatite was determined in the range of 1100–1500° C and 10–25 kbar. The alumina content in enstatite coexisting with sapphirine and quartz increases with increasing temperature and pressure, while that in enstatite coexisting with sapphirine and sillimanite or with pyrope decreases with increasing pressure and decreasing temperature. Two univariant lines, pyrope = enstatite_ss + sillimanite + sapphirine_ss and enstatite_ss + sillimanite =sapphirine_ss + quartz were confirmed. The invariant point involving these phases is metastable. The alumina content of orthopyroxene can not be used either as a pressure indicator or as a temperature indicator without taking the mineral assemblage into account.     

The magmatic plumbing system beneath El Hierro (Canary Islands): constraints from phenocrysts and naturally quenched basaltic glasses in submarine rocks

A thermobarometric and petrologic study of basanites erupted from young volcanic cones along the submarine portions of the three El Hierro rift zones (NE-Rift, NW-Rift and S-Ridge) has been performed to reconstruct magma plumbing and storage beneath the island. Mineral-melt thermobarometry applied to naturally quenched glass and clinopyroxene rims yields pressures ranging from 350 to 1070 MPa with about 80% of the calculated pressures being in the range of 600–800 MPa. This corresponds to a depth range of 19–26 km, implying that the main level of final crystal fractionation is within the uppermost mantle. No systematic dependence between sample locality and fractionation pressures could be observed. Olivine and clinopyroxene crystals in the rocks are complexly zoned and have, on an inter-sample as well as on an intra-sample scale, highly variable core and rim compositions. This can best be explained by mixing of multiply saturated (olivine, magnetite, clinopyroxene, ilmenite), moderately evolved magmas with more mafic magmas being either only saturated with olivine + spinel or with olivine + spinel + clinopyroxene. The inter-sample differences indicate derivation from small, isolated magma chambers which have undergone distinct fractionation and mixing histories. This is in contrast to oceanic intraplate volcanoes situated on plumes with high melt supply rates, e.g. Kilauea Volcano (Hawaii), where magma is mainly transported through a central conduit system and stored in a shallow magma chamber prior to injection into the rift zones. The plumbing system beneath El Hierro rather resembles the magma storage systems beneath, e.g. Madeira or La Palma, indicating that small, intermittent magma chambers might be a common feature of oceanic islands fed by plumes with relatively low fluxes, which results in only limited and periodic magma supply.     

Anhydrous partial melting of an iron-rich mantle I: subsolidus phase assemblages and partial melting phase relations at 10 to 30 kbar

Anhydrous partial melting experiments, at 10 to 30 kbar from solidus to near liquidus temperature, have been performed on an iron-rich martian mantle composition, DW. The DW subsolidus assemblage from 5 kbar to at least 24 kbar is a spinel lherzolite. At 25 kbar garnet is stable at the solidus along with spinel. The clinopyroxene stable on the DW solidus at and above 10 kbar is a pigeonitic clinopyroxene. Pigeonitic clinopyroxene is the first phase to melt out of the spinel lherzolite assemblage at less than 20°C above the solidus. Spinel melts out of the assemblage about 50°C above the solidus followed by a 150° to 200°C temperature interval where melts are in equilibrium with orthopyroxene and olivine. The temperature interval over which pigeonitic clinopyroxene melts out of an iron-rich spinel lherzolite assemblage is smaller than the temperature interval over which augite melts out of an iron-poor spinel lherzolite assemblage. The dominant solidus assemblage in the source regions of the Tharsis plateau, and for a large percentage of the martian mantle, is a spinel lherzolite.     

Phase equilibria constraints on melting of stromatic migmatites from Ronda (S. Spain): insights on the formation of peritectic garnet

Stromatic metatexites occurring structurally below the contact with the Ronda peridotite (Ojén nappe, Betic Cordillera, S Spain) are characterized by the mineral assemblage Qtz+Pl+Kfs+Bt+Sil+Grt+Ap+Gr+Ilm. Garnet occurs in low modal amount (2–5 vol.%). Very rare muscovite is present as armoured inclusions, indicating prograde exhaustion. Microstructural evidence of melting in the migmatites includes pseudomorphs after melt films and nanogranite and glassy inclusions hosted in garnet cores. The latter microstructure demonstrates that garnet crystallized in the presence of melt. Re‐melted nanogranites and preserved glassy inclusions show leucogranitic compositions. Phase equilibria modelling of the stromatic migmatite in the MnO–Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂–O₂–C (MnNCaKFMASHOC) system with graphite‐saturated fluid shows P–T conditions of equilibration of 4.5–5 kbar, 660–700 °C. These results are consistent with the complete experimental re‐melting of nanogranites at 700 °C and indicate that nanogranites represent the anatectic melt generated immediately after entering supersolidus conditions. The P–T estimate for garnet and melt development does not, however, overlap with the low‐temperature tip of the pure melt field in the phase diagram calculated for the composition of preserved glassy inclusions in garnet in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O (NCKFMASH) system. A comparison of measured melt compositions formed immediately beyond the solidus with results of phase equilibria modelling points to the systematic underestimation of FeO, MgO and CaO in the calculated melt. These discrepancies are present also when calculated melts are compared with low‐T natural and experimental melts from the literature. Under such conditions, the available melt model does not perform well. Given the presence of melt inclusions in garnet cores and the P–T estimates for their formation, we argue that small amounts (<5 vol.%) of peritectic garnet may grow at low temperatures (≤700 °C), as a result of continuous melting reactions consuming biotite.     

The ZnSiO3 clinopyroxene-ilmenite transition: Heat capacity,enthalpy of transition,and phase equilibria

ZnSiO₃ clinopyroxene stable above 3 GPa transforms to ilmenite at 10–12 GPa, which further decomposes into ZnO (rock salt) plus stishovite at 20–30 GPa. The enthalpy of the clinopyroxene-ilmenite transition was measured by high-temperature solution calorimetry, giving ΔH⁰=51.71 ±3.18 kJ/mol at 298 K. The heat capacities of clinopyroxene and ilmenite were measured by differential scanning calorimetry at 343–733 and 343–633 K, respectively. The C _p of ilmenite is 3–5% smaller than that of clinopyroxene. The entropy of transition was calculated using the measured enthalpy and the free energy calculated from the phase equilibrium data. The enthalpy, entropy and volume changes of the pyroxene-ilmenite transition in ZnSiO₃ are similar in magnitude to those in MgSiO₃. The present thermochemical data are used to calculate the phase boundary of the ZnSiO₃ clinopyroxene-ilmenite transition. The calculated boundary,

Magmato-sedimentary Carboniferous to Jurassic evolution of the western Tauern window,Eastern Alps (constraints from U-Pb zircon dating and geochemistry)

New geochronological U-Pb (LA-ICP-MS) zircon data and geochemical analyses from the Variscan orthogneisses and metavolcanic rocks in the western Tauern window are presented and used to reconstruct the pre-Alpine evolution of this area. The late- and post-Variscan stage in the Tauern window was characterised by distinct magmatic pulses accompanied by the formation of volcano-sedimentary basins. The magmatic activity started in the Visean (335.4 ± 1.5 Ma) with the intrusion of a K-rich, durbachitic biotite-granite (protolith of the Ahorn gneiss). Following a period of exhumation and erosion, Westfalian–Stefanian volcanics were deposited (Grierkar meta-rhyodacite: 309.8 ± 1.5 Ma; Venntal meta-rhyolite: 304.0 ± 3.0 Ma). A renewed magmatic pulse occurred in the Early Permian, producing large volumes of tonalites and granodiorites (Tux meta-granodiorite: 292.1 ± 1.9 Ma). The youngest magmatism is characterised by pyroclastic and tuffitic deposits (Pfitsch meta-rhyolite: 280.5 ± 2.6 Ma; Schönach valley meta-andesite: 279.0 ± 4.8 Ma). This volcanism was probably related to crustal extensional faulting within an intra-continental graben and horst setting, asthenospheric upwelling and heat flow increase due to the onset of the Permian rifting. The Permo-Triassic peneplanation and subsidence is documented by shallow marine and evaporitic deposits. Probably in the Middle Jurassic times, the area was flooded and in the Late Jurassic the whole area was covered by limestones, representing post-rift sediments on the southern European continental margin.     

P-T-X conditions of calc-silicate formation: evidence from fluid inclusions and phase equilibria; Llano Uplift, central Texas, USA

Abstract The Llano Uplift in central Texas is a Grenville aged (c. 1.1 Ga) metamorphic terrane consisting predominantly of amphibolite facies mineral assemblages. The formation of these assemblages has been attributed to the emplacement of relatively late granite plutons throughout the area. Two types of granitic intrusion have previously been recognized: (1) Town Mountain Granites, which occur as relatively large, circular-shaped bodies of coarse-grained granite, and (2) Younger Granites which are present as smaller and more irregular bodies of finer-grained granite. In the central part of the uplift, wollastonite-bearing calc-silicate rocks occur within the Valley Spring Gneiss. The development of these calc-silicate rocks has been linked to infiltrating fluids presumably derived from spatially associated Younger Granites. The stability of coexisting quartz, calcite, wollastonite, grossular and anorthite and coexisting quartz, calcite, wollastonite, andradite and hedenbergite shows that the calc-silicate rocks equilibrated under H₂O-rich conditions with χCO₂ <0.10. Fluid inclusions present within the calc-silicate minerals are H₂O-rich with salinities of <17 wt% equivalent NaCl. The absence of any detectable CO₂ in the fluid inclusions may indicate entrapment of the inclusions at lower pressures and more H₂O-rich conditions compared to the stability of the peak metamorphic mineral assemblage. Homogenization temperatures, measured for texturally primary inclusions, range from 360 to 368° C corresponding to a density range from 0.53 to 0.82 g/cm³. Isochores for these fluid inclusions, when combined with the stability of the solid-solid equilibria Grs + Qtz = Wo + An, yield formation conditions of 500–550° C at 1–2 kbar. This indicates that the granitic intrusions involved in the formation of the Blount Mountain calc-silicates were emplaced at a pressure of at least 1–2 kbar.     

Preliminary phase equilibria of the nepheline-diopside system under variable pressures (up to 28 kb) and temperatures

The nepheline-diopside join defines the ultra-alkaline portion of the basalt tetrahedron and the bulk composition of nephelinitic rocks lie in this join. Schairer and others established that under atmospheric pressure, the join cuts through the primary phase volumes of olivine_ss, carnegieite_ss and nepheline_ss. Melilite coexists with nepheline_ss, olivine_ss and diopside_ss below 1160±10°C and olivine reacts out at low temperature. Experimental studies on seven compositions show the presence of a pseudoeutectic at Ne₇₀Di₃₀ and 1420°C, where diopside_ss, nepheline_ss and liquid are in equilibrium. Olivine and melilite do not appear in the system and the assemblage below 1225±20°C is diopside_ss+nepheline_ss.