Melting of plagioclase-quartz assemblages at 2 kbar water pressure

The melting of plagioclase and quartz has been investigated at P _H2O =2kb. A single crystal of plagioclase was surrounded by quartz powder and water. A reaction rim consisting of glass and of An-rich plagioclase developed around unchanged starting plagioclase. Microprobe determinations of melt and coexisting plagioclase compositions reveal a strong fractionation of plagioclase components between melt and new plagioclase. For example at 850° C the approximate X _An of melt is 0.3 and that of plagioclase is 0.8. The temperature interval between beginning of melting and complete melting of cotectic compositions is 100° C or more for quartz-plagioclase mixtures with plagioclases between An 40 and An 75. In comparison to the system Ab-An-H₂O the plagioclase melting loop is somewhat wider in the investigated system Qz-Ab-An-H₂O but the temperature interval is much smaller (100° C) than in the system Ab-An-H₂O (200° C). The solidus data indicated by the new plagioclase compositions are practically identical with those observed in beginning of melting experiments. The results show that fractionation of plagioclase components between partial melts and restite plagioclase can be more pronounced in multi-component rocks than in the pure plagioclase system. This finding is important for the development of albite rich rocks from more basic compositions.     

Beginning of melting in the granite system Qz-Or-Ab-An-H2O

The beginning of melting in the system Qz-Or-Ab-An-H₂ O was experimentally reversed in the pressure range kbar using starting materials made up of mixtures of quartz and synthetic feldspars. With increasing pressure the melting temperature decreases from 690° C at 2 kbar to 630° C at 17 kbar in the An-free alkalifeldspar granite system Qz-Or-Ab-H₂O. In the granite system Qz-Or-Ab-An-H₂O the increase of the solidus temperature with increasing An-content is only very small. In comparison to the alkalifeldspar granite system the solidus temperature increases by 3° C (7° C) if albite is replaced by plagioclase An 20 (An 40). The difference between the solidus temperatures of the alkalifeldspar granite system and of quartz — anorthite — sanidine assemblages (system Qz-Or-An-H₂O) is approximately 50° C. With increasing water pressures plagioclase and plagioclase-alkalifeldspar assemblages become unstable and are replaced by zoisite+kyanite+quartz and zoisite+muscovite-paragonite_ss +quartz, respectively. The pressure stability limits of these assemblages are found to lie between 6 and 16 kbar at 600° C. At high water pressures (10–18 kbar) zoisite — muscovite — quartz assemblages are stable up to 700 and 720° C. The solidus curve of this assemblage is 10–20° C above the beginning of melting of sanidine — zoisite — muscovite — quartz mixtures. The amount of water necessary to produce sufficient amounts of melt to change a metamorphic rock into a magmatic looking one is only small. In case of layered migmatites it is shown that 1 % of water (or even less) is sufficient to transform portions of a gneiss into (magmatic looking) leucosomes. High grade metamorphic rocks were probably relatively dry, and anatectic magmas of granitic or granodioritic composition are usually not saturated with water.     

Experiments on the kinetics of partial melting of a leucogranite at 200 MPa H<Subscript>2</Subscript>O and 690–800°C: compositional variability of melts during the onset of H<Subscript>2</Subscript>O-saturated crustal anatexis

We have experimentally investigated the kinetics of melting of an aplitic leucogranite (quartz+sodic plagioclase of ≈Ab₉₀+K-feldspar+traces of biotite) at 690, 740, and 800°C, all at 200 MPa H₂O. Leucogranite cylinders, 3.5 mm in diameter and 7 mm in length, were run in the presence of excess H₂O using cold-seal pressure vessels for 11–2,925 h. At 690 and 740°C and any experimental time, and 800°C and short run times, silicate glass (melt at run conditions) occurs as interconnected films along most of the mineral boundaries and in fractures, with the predominant volume occurring along quartz/feldspars boundaries and quartz/plagioclase/K-feldspar triple junctions. Glass film thickness is roughly constant throughout a given experimental charge and increases with experimental temperature and run duration. The results indicate that H₂O-saturated partial melting of a quartzo-feldspathic protolith will produce an interconnected melt phase even at very low degrees (<5 vol%) of partial melting. Crystal grain boundaries are therefore completely occluded with melt films even at the lowest degrees of partial melting, resulting in a change in the mechanism of mass transport through the rock from advection of aqueous vapor to diffusion through silicate melt. At 690 and 740°C the compositions of glasses are homogeneous and (at both temperatures) close to, but not on, the H₂O-saturated 200 MPa haplogranite eutectic; glass compositions do not change with run duration. At 800°C glasses are heterogeneous and plot away from the minimum, although their molar ratios ASI (=mol Al₂O₃/CaO+Na₂O+K₂O) and Al/Na are constant throughout the entire charge at any experimental time. Glass compositions within individual 800°C experiments form linear trends in (wt%) normative quartz–albite–orthoclase space. The linear trends are oriented perpendicular to the 200 MPa H₂O haplogranite cotectic line, reflecting nearly constant albite/orthoclase ratio versus variable quartz/feldspar ratio, and have endpoints between the 800°C isotherms on the quartz and feldspar liquidus surfaces. With increasing experimental duration the trends migrate from the potassic side of the minimum toward the bulk rock composition located on the sodic side, due to more rapid (and complete) dissolution of K-feldspar relative to plagioclase. The results indicate that partial melting at or slightly above the solidus (690–740°C) is interface reaction-controlled, and produces disequilibrium melts of near-minimum composition that persist metastably for up to at least 3 months. Relict feldspars show no change in composition or texture, and equilibration between melt and feldspars might take from a few to tens of millions of years. Partial melting at temperatures well above the solidus (800°C) produces heterogeneous, disequilibrium liquids whose compositions are determined by the diffusive transport properties of the melt and local equilibrium with neighboring mineral phases. Feldspars recrystallize and change composition rapidly. Partial melting and equilibration between liquids and feldspars might take from a few to tens of years (H₂O-saturated conditions) at these temperatures well above the solidus.     

Retrograde processes in migmatites and granulites revisited

Many migmatites and granulites preserve evidence of a clockwise P–T evolution involving decompression (decrease in P) while close to the thermal peak. The extent of post‐thermal peak reaction is influenced by several factors, including: (1) the P–T path in relation to invariants in the system and the Clapeyron slopes of the equilibria; (2) the rate of cooling; and (3) the availability of fluid (H₂O‐rich volatile phase or melt) for fluid‐consuming reactions. Reaction may occur between products of a prograde (increasing T) fluid‐generating reaction as the same equilibrium is re‐crossed in the retrograde (decreasing T) sense. In general, reaction reversal or ‘back reaction’ requires the P–T path to approximate isobaric heating and cooling, without significant decompression, and evolved fluid to remain within the equilibration volume. The larger the decompression segment in the P–T evolution, the more chance there is of crossing different reactions along the retrograde segment from those crossed along the prograde segment. For common pelite compositions, we may generalize by considering three pressure regimes separated by the [Spl, Ms, H₂O] invariant in KFMASH (approximately 9 kbar) and the intersection of muscovite breakdown with the H₂O‐rich volatile phase‐saturated solidus (approximately 4 kbar). Reaction reversal cannot occur along P–T paths that traverse around one of these points, but may occur along P–T paths confined to one of the three regimes in between. Additionally, above the solidus, melt segregation and loss potentially change the composition of the equilibration volume; and, the size of the equilibration volume shrinks with decreasing T. Since the proportion of melt to residue in the equilibration volume may change with decreasing size, the composition of the equilibration volume may change throughout the supra‐solidus part of the retrograde segment of the P–T evolution. If melt has been lost from the equilibration volume, reaction reversal may not be possible or may be only partial; indeed, the common preservation of close‐to‐peak mineral assemblages in migmatite and granulite demonstrates that extensive reaction with melt is uncommon, which implies melt isolation or loss prior to crossing potential melt‐consuming reactions. Water dissolved in melt is transported through the crust to be exsolved on crystallization at the solidus appropriate to the intrinsic a(H₂O). This recycled water causes retrogression at subsolidus conditions. Consideration of the evidence for supra‐solidus decompression‐dehydration reactions, and review of microstructures that have proven controversial, such as corona and related microstructures, selvage microstructures and ‘late’ muscovite, leads to the conclusion that there is more than one way for these microstructures to form and reminds us that we should always consider multiple working hypotheses!     

Melting and subsolidus reactions in the system K2O-CaO-Al2O3-SiO2-H2O

Beginning of melting and subsolidus relationships in the system K₂O-CaO-Al₂O₃-SiO₂-H₂O have been experimentally investigated at pressures up to 20 kbars. The equilibria discussed involve the phases anorthite, sanidine, zoisite, muscovite, quartz, kyanite, gas, and melt and two invariant points: Point [Ky] with the phases An, Or, Zo, Ms, Qz, Vapor, and Melt; point [Or] with An, Zo, Ms, Ky, Qz, Vapor, and Melt.The invariant point [Ky] at 675° C and 8.7 kbars marks the lowest solidus temperature of the system investigated. At pressures above this point the hydrated phases zoisite and muscovite are liquidus phases and the solidus temperatures increase with increasing pressure. At 20 kbars beginning of melting occurs at 740 °C. The solidus temperatures of the quinary system K₂O-CaO-Al₂O₃-SiO₂-H₂O are almost 60° C (at 20 kbars) and 170° C (at 2kbars) below those of the limiting quaternary system CaO-Al₂O₃-SiO₂-H₂O.The maximum water pressure at which anorthite is stable is lowered from 14 to 8.7 kbars in the presence of sanidine. The stability limits of anorthite+ vapor and anorthite+sanidine+vapor at temperatures below 700° C are almost parallel and do not intersect. In the wide temperature — pressure range at pressures above the reaction An+Or+Vapor = Zo+Ms+Qz and temperatures below the melting curve of Zo+Ms+Ky+Qz+Vapor, the feldspar assemblage anorthite+sanidine is replaced by the hydrated phases zoisite and muscovite plus quartz. CaO-Al₂O₃-SiO₂-H₂O. Knowledge of the melting relationships involving the minerals zoisite and muscovite contributes to our understanding of the melting processes occuring in the deeper parts of the crust. Beginning of melting in granites and granodiorites depends on the composition of plagioclase. The solidus temperatures of all granites and granodiorites containing plagioclases of intermediate composition are higher than those of the Ca-free alkali feldspar granite system and below those of the Na-free system discussed in this paper.The investigated system also provides information about the width of the P-T field in which zoisite can be stable together with an Al₂SiO₅ polymorph plus quartz and in which zoisite plus muscovite and quartz can be formed at the expense of anorthite and potassium feldspar. Addition of sodium will shift the boundaries of these fields to higher pressures (at given temperatures), because the pressure stability of albite is almost 10kbars above that of anorthite. Assemblages with zoisite+muscovite or zoisite+kyanite are often considered to be products of secondary or retrograde reactions. The P-T range in which hydration of granitic compositions may occur in nature is of special interest. The present paper documents the highest temperatures at which this hydration can occur in the earth's crust.     

The role of oxidation-reduction and C-H-O fluids in determining melting conditions and magma compositions in the upper mantle

High pressure experimental studies of the melting of lherzolitic upper mantle in the absence of carbon and hydrogen have shown that the lherzolite solidus has a positive dP/dT and that the percentage melting increases quite rapidly above the solidus. In contrast, the presence of carbon and hydrogen in the mantle results in a region of ‘incipient’ melting at temperatures below the C,H-free solidus. In this region the presence or absence of melt and the composition of the melt are dependent on the amount and nature of volatiles, particularly the CO₂, H₂O, and CH₄ contents of the potential C-H-O fluid. Under conditions of low (IW to IW + 1 log unit atP ∼ 20–35kb), fluids such as CH₄+H₂O and CH₄+H₂ inhibit melting, having a low solubility in silicate melts. Under these conditions, carbon and hydrogen are mobile elements in the upper mantle. At slightly higher oxygen fugacity (IW+2 log units,P∼20–35 kb) fluids in equilibrium with graphite or diamond in peridotite C-H-O are extremely water-rich. Carbon is thus not mobile in the mantle in this range and the melting and phase relations for the upper mantle lherzolite approximate closely to the peridotite-H₂O system. Pargasitic amphibole is stable to solidus temperatures in fertile lherzolite compositions and causes a distinctive peridotite solidus, the ‘dehydration solidus’, with a marked change in slope (a ‘back bend’) at 29–30kb due to instability of pargasite at high pressure. Intersections of geothermal gradients with the peridotite-H₂O solidi define the boundary between lithosphere (subsolidus) and asthenosphere (incipient melt region). This boundary is thus sensitive to changes in [affecting CH₄:H₂O:CO₂ ratios] and to the amount of H₂O and carbon (CO₂, CH₄) present. At higher conditions (IW + 3 log units), CO₂-rich fluids occur at low pressures but there is a marked depression of the solidus at 20–21 kb due to intersection with the carbonation reaction, producing the low temperature solidus for dolomite amphibole lherzolite (T∼925°C, 21 to >31kb). Melting of dolomite (or magnesite) amphibole lherzolite yields primary sodic dolomitic carbonatite melt with low H₂O content, in equilibrium with amphibole garnet lherzolite. The complexity of melting in peridotite-C-H-O provides possible explanations for a wide range of observations on lithosphere/asthenosphere relations, on mantle melt and fluid compositions, and on processes of mantle metasomatism and magma genesis in the upper mantle.     

Water content of a granite magma deduced from the sequence of crystallization determined experimentally with water-undersaturated conditions

The sequence of crystallization in a biotite-granite from the Bohus batholith of Norway and Sweden, deduced from its texture, was magnetite, plagioclase, microcline, quartz, and finally biotite. Several sequences of crystallization were determined experimentally at 2 kb in the presence of varying only for H₂O contents below 1.2% by weight. The rock was fused to a homogeneous glass, and each experiment included samples of finely crushed rock and glass. The samples were reacted in Ag-Pd capsules with measured H₂O content in coldseal pressure vessels with NNO buffer. With excess H₂O (more than 6.5%) the crystallization interval extends from 865° C to 705° C. In the H₂O-deficient region, the solidus temperature remains unchanged as long as a trace of vapor is present, but the liquidus temperature increases as H₂O content decreases; with 0.8 % H₂O the liquidus temperature is 1125° C, the crystallization interval is 420° C, and a separate aqueous vapor phase is evolved only a few degrees above the solidus at 705° C. The biotite phase boundary increases slightly from 845° C with excess H₂O to 875° C with 1% H₂O, and it intersects the steep phase boundaries for quartz and feldspars; the sequence of crystallization changes at each intersection point. Similar diagrams at various pressures for related rock compositions involving muscovite, biotite and amphibole will provide grids useful in defining limits for the water content of granitic and dioritic magmas. Applications are considered for the Bohus batholith, other granitic rocks, and rhyolites. The Bohus magma could have been formed by crustal anatexis as a mobile assemblage of H₂O-undersaturated liquid and residual crystals with initial total H₂O content less than 1.2%, or it could have been derived by fractionation of a more basic parent with low H₂O content from mantle or subduction zone, but it could not have been derived from a primary andesite generated from mantle peridotite. We consider it unlikely that the H₂O content of large granitic magma bodies exceeds about 1.5% H₂O; these magmas are H₂O-undersaturated through most of their histories. Uprise and progressive crystallization of magma bodies produces H₂O-saturation around margins and in the upper regions of magma chambers. H₂O-saturated rhyolitic and dacitic magmas with phenocrysts can be tapped from the upper parts of the magma chambers.     

Behavior and effects of phosphorus in the system Na2O−K2O−Al2O3−SiO2−P2O5−H2O at 200 MPa(H2O)

The addition of phosphorus to H₂O-saturated and initially subaluminous haplogranitic (Qz–Ab–Or) compositions at 200 MPa(H₂O) promotes expansion of the liquidus field of quartz, a marked decrease of the solidus temperature, increased solubility limits of H₂O in melt at low phosphorus concentrations, and fractionation of melt out of the haplogranite plane (projected along an Or₂₈ isopleth) toward a peralkaline, silica-poor but quartz-saturated minimum composition. The partition coefficient for P₂O₅ between aqueous vapor and melt with an ASI (aluminum saturation index, mol Al/[mol Na+K])=1 is negligible (0.06), and consequently so are the effects of phosphorus on other melt-vapor relations involving major components. Phosphorus becomes more soluble in vapor, however, as the concentration of a NaPO₃ component increases via the fractionation of melt by crystallization of quartz and feldspar. The experimental results here corroborate existing concepts regarding the interaction of phosphorus with alkali aluminosilicate melt: phosphorus has an affinity for alkalis and Al, but not Si. Phosphorus is incorporated into alkali feldspars by the exchange component AlPSi_-2. For subaluminous compositions (ASI=1), the distribution coefficient of phosphorus between alkali feldspar and melt, D[P]Af/m, is 0.3. This value increases to D[P]Af/m=1.0 at a melt ASI value of 1.3. The increase in D[P]Af/m with ASI is expected from the fact that excess Al promotes the AlPSi_-2 exchange. With this experimental data, the P₂O₅ content of feldspars and whole rocks can reveal important facets of crystallization and phosphorus geochemistry in subaluminous to peraluminous granitic systems.     

The beginnings of hydrous mantle wedge melting

This study presents new phase equilibrium data on primitive mantle peridotite (0.33 wt% Na₂O, 0.03 wt% K₂O) in the presence of excess H₂O (14.5 wt% H₂O) from 740 to 1,200°C at 3.2–6 GPa. Based on textural and chemical evidence, we find that the H₂O-saturated peridotite solidus remains isothermal between 800 and 820°C at 3–6 GPa. We identify both quenched solute from the H₂O-rich fluid phase and quenched silicate melt in supersolidus experiments. Chlorite is stable on and above the H₂O-saturated solidus from 2 to 3.6 GPa, and chlorite peridotite melting experiments (containing ~6 wt% chlorite) show that melting occurs at the chlorite-out boundary over this pressure range, which is within 20°C of the H₂O-saturated melting curve. Chlorite can therefore provide sufficient H₂O upon breakdown to trigger dehydration melting in the mantle wedge or perpetuate ongoing H₂O-saturated melting. Constraints from recent geodynamic models of hot subduction zones like Cascadia suggest that significantly more H₂O is fluxed from the subducting slab near 100 km depth than can be bound in a layer of chloritized peridotite ~ 1 km thick at the base of the mantle wedge. Therefore, the dehydration of serpentinized mantle in the subducted lithosphere supplies free H₂O to trigger melting at the H₂O-saturated solidus in the lowermost mantle wedge. Alternatively, in cool subduction zones like the Northern Marianas, a layer of chloritized peridotite up to 1.5 km thick could contain all the H₂O fluxed from the slab every million years near 100 km depth, which suggests that the dominant form of melting below arcs in cool subduction zones is chlorite dehydration melting. Slab P–T paths from recent geodynamic models also allow for melts of subducted sediment, oceanic crust, and/or sediment diapirs to interact with hydrous mantle melts within the mantle wedge at intermediate to hot subduction zones.     

The breakdown of potassium feldspar at high water pressures

The equilibrium position of the reaction between sanidine and water to form “sanidine hydrate” has been determined by reversal experiments on well characterised synthetic starting materials in a piston cylinder apparatus. The reaction was found to lie between four reversed brackets of 2.35 and 2.50 GPa at 450 °C, 2.40 and 2.59 GPa at 550 °C, 2.67 and 2.74 GPa at 650 °C, and 2.70 and 2.72 GPa at 680 °C. Infrared spectroscopy showed that the dominant water species in sanidine hydrate was structural H₂O. The minimum quantity of this structural H₂O, measured by thermogravimetric analysis, varied between 4.42 and 5.85 wt% over the pressure range of 2.7 to 3.2 GPa and the temperature range of 450 to 680 °C. Systematic variation in water content with pressure and temperature was not clearly established. The maximum value was below 6.07 wt%, the equivalent of 1 molecule of H₂O per formula unit. The water could be removed entirely by heating at atmospheric pressure to produce a metastable, anhydrous, hexagonal KAlSi₃O₈ phase (“hexasanidine”) implying that the structural H₂O content of sanidine hydrate can vary. The unit cell parameters for sanidine hydrate, measured by powder X-ray diffraction, were a = 0.53366 (±0.00022) nm and c = 0.77141 (±0.00052) nm, and those for hexasanidine were a = 0.52893 (±0.00016) nm and c = 0.78185 (±0.00036) nm. The behaviour and properties of sanidine hydrate appear to be analogous to those of the hydrate phase cymrite in the equivalent barium system. The occurrence of sanidine hydrate in the Earth would be limited to high pressure but very low temperature conditions and hence it could be a potential reservoir for water in cold subduction zones. However, sanidine hydrate would probably be constrained to granitic rock compositions at these pressures and temperatures. Received: 6 May 1997 / Accepted: 2 October 1997     

Metastable melting in the granite system Qz-Or-Ab-An-H2O

Time studies were performed in the quinary system Qz-Or-Ab-An-H₂O at kbars and T=665 ° and 660 ° C. Starting material was a mixture of quartz, alkali feldspar Or₈₀ and plagioclase An₃₁. The compositions of plagioclases of run products were determined and compared with the plagioclase of stable solidus conditions.The solidus of the granite system was fixed at P _HäO=5 kbars using various plagioclase — and appropriate alkali feldspar — compositions besides quartz in the starting mixture (Fig. 1).The results of time studies (Table 3 and Fig. 3) reveal metastable melting in the granite system Qz-Or-Ab-An-H₂O. Plagioclase melts almost stoichiometrically. The new plagioclase compositions formed during melting of cotectic compositions approach the theoretically expected stable plagioclase compositions only extremely slowly. An extrapolation of the data achieved in run times of 5–1,500 h indicates attainment of equilibrium after 10¹⁴ years. Metastable melting of granitic compositions is not only considered as an experimental problem but also as a rock forming process in nature.     

Alkali Feldspars with Water at 5 kb Pressure

Alkali feldspars with water at 5 kb begin to melt at an isobariceutectic: 703±2 °C, Or ₂₈.₅ (wt. per cent) recalculatedanhydrous. The liquidus of albite-H₂O at 5 kb is 758±3°C. The K feldspar-rich, water-saturated liquidus is essentiallythat of Yoder, Stewart, & Smith (1957), who furthermorefound orthoclase-H₂O to melt at 876 °C. The alkali feldspar solvus, determined by synthesis from glassand a few reversals using crystalline material, has a calculatedcritical temperature of 730 °C and a critical compositionof Or₃₁ (wt. per cent) using parametric equations (Thompson& Waldbaum, 1969). The Margules equation yields T_c = 738°C. The feldspars produced are structural equivalents oflow sanidine on the basis of their 060 and 04 powder X-ray diffractionpeaks. The critical line intersects the beginning of meltingcurve for the system Ab-Or-H₂O at 4.2 kb, 715 °C, the minimumconditions for the coexistence of two feldspars and liquid inthis system. The slope of the critical line, using Orville's (1963) 2 kbresults, is 18.3 °C/kb, leading to an intersection withthe kyanite-sillimanite curve of Richardson, Bell, & Gilbert(1968) at about 10.6 kb, 834 °C. The intersection with theandalusite-sillimanite curve of these authors (1969) falls atabout 3.5 kb, 703 °C. Such intersections may be used toestimate limits of P and T for a variety of crustal rocks. Because isobaric crystallization of feldspars in the water-deficientregion must enrich liquids in H₂O to the saturation point, haplosyeniticliquids with a finite initial water content must, at 5 kb totalpressure, eventually crystallize two feldspars.     

Solution of H2O in diopside melts: a thermodynamic model

Structural similarities between dry diopside melt and superhydrous albite melt (X _w >0.5) — both lack three-dimensional silicate units — suggest that thermodynamic relations may be similar. A model based on that assumption successfully predicts diopside melting relations and H₂O solubilities. For the model, the three partial differential equations describing solution of H₂O in albite melt for X _w >0.5 have been integrated for diopside melt from X _w =0 to X _w at least as large as 0.76, with two exceptions: an alternative partial differential equation for Henrian solution of H₂O in dilute melts was applied for X _w <0.20, and an alternative differential equation for the pressure dependence of a _w at pressures below 2 kbar was developed. The latter alternative equation yields relatively small ¯V_w's at low pressures rather than the large ¯V_w's calculated from the equation from the albite system. Available experimental solubility data are not precise enough to offer a choice between the small-¯V_w and large-¯V_w equations. Integration of all the partial differential equations was constrained solely by the P and T of a single experimentally-determined point on the H₂O-saturated solidus.Solubilities calculated by a Henrian-analogue solution model (a _di=X _di ² ) from the experimental H₂O saturated solidus lie outside experimental solubility constraints for dilute melts. On the other hand, a Henrian model (a _di=X_di) successfully predicts solubilities in dilute melts. The formulation of the Henrian model and magnitudes of model molar entropies of solution are consistent with the hypothesis that H₂O dissolves in diopside melt as an essentially undissociated species with little ordering on melt structural sites. That species could in turn be consistently, if not uniquely, interpreted to be molecular H₂O or a hydroxylation (OH^–) complex formed from nonbridging oxygens.     

A model for garnet and plagioclase growth in pelitic schists: implications for thermobarometry and P-T path determinations

Numerical models of the progressive evolution of pelitic schists in the NCMnKFMASH system with the assemblage garnet + biotite + chlorite ± staurolite + plagioclase + muscovite + quartz + H₂O are presented with the goal of predicting compositional changes in garnet and plagioclase along different P-T paths. The numerical models support several conclusions that should prove useful for interpreting the P-T paths of natural parageneses: (i) Garnet may grow along P-T vectors ranging from heating with decompression to cooling with compression. P-T paths deduced from garnet zoning that are inconsistent with these growth vectors are self-contradictory. (ii) There is a systematic relation between garnet and plagioclase composition and growth such that for most P-T paths, garnet growth requires plagioclase consumption. Furthermore, mass balance in a closed system requires that as plagioclase is consumed the remaining plagioclase becomes increasingly albitic. Inclusions of plagioclase in the core of garnet should be more anorthitic than those near the rim and zoned matrix plagioclase should have rims that are more albitic than the cores. Complex plagioclase textures may arise from the local variability of growth and precipitation kinetics. (iii) A decrease of Fe/(Fe + Mg) in a garnet zoning profile is a reliable indicator of increasing temperature for the assemblage modelled. However, there is no single reliable ΔP monitor and inferences about ΔP can only be made by considering plagioclase and garnet together. (iv) Consumption of garnet during the production of staurolite removes material from the outer shell of a garnet and may make recovery of peak metamorphic compositions and P-T conditions impossible. Low ‘peak’temperatures typically recorded by staurolite-bearing assemblages may reflect this phenomenon. (v) Diffusional homogenization of garnet affects the computed P-T path and results in a clockwise rotation of the computed P-T vector relative to the true P-T path.     

The influence of H2O-H2 fluids and redox conditions on melting temperatures in the haplogranite system

Solidus temperatures of quartz–alkali feldspar assemblages in the haplogranite system (Qz-Ab-Or) and subsystems in the presence of H₂O-H₂ fluids have been determined at 1, 2, 5 and 8 kbar vapour pressure to constrain the effects of redox conditions on phase relations in quartzofeldspathic assemblages. The hydrogen fugacity (f _H2) in the fluid phase has been controlled using the Shaw membrane technique for moderately reducing conditions (f _H2 < 60 bars) at 1 and 2 kbar total pressure. Solid oxygen buffer assemblages in double capsule experiments have been used to obtain more reducing conditions at 1 and 2 kbar and for all investigations at 5 and 8 kbar. The systems Qz-Or-H₂O-H₂ and Qz-Ab-H₂O-H₂ have only been investigated at moderately reducing conditions (1 and 5 kbar) and the system Qz-Ab-Or-H₂O-H₂ has been investigated at redox conditions down to IW (1 to 8 kbar). The results obtained for the water saturated solidi are in good agreement with those of previous studies. At a given pressure, the solidus temperature is found to be constant (within the experimental precision of ± 5°C) in the f _H2 range of 0–75 bars. At higher f _H2, generated by the oxygen buffers FeO-Fe₃O₄ (WM) and Fe-FeO (IW), the solidus temperatures increase with increasing H₂ content in the vapour phase. The solidus curves obtained at 2 and 5 kbar have similar shapes to those determined for the same quartz - alkali feldspar assemblages with H₂O-CO₂- or H₂O-N₂-bearing systems. This suggests that H₂ has the behaviour of an inert diluent of the fluid phase and that H₂ solubility in aluminosilicate melts is very low. The application of the results to geological relevant conditions [HM (hematite-magnetite) > f _O2 > WM] shows that increasing f _H2 produces a slight increase of the solidus temperatures (up to 30 °C) of quartz–alkali feldspar assemblages in the presence of H₂O-H₂ fluids between 1 and 5 kbar total pressure. Received: 4 March 1996 / Accepted: 22 August 1996     

Garnets in volcanic breccias of the Phlegraean Fields (southern Italy): mineralogical, geochemical and genetic features

Summary ?Post-magmatic garnets occur in volcanic breccias at the base of the Neapolitan Yellow Tuff (NYT) formation in the north-western area of the Phlegraean Fields. We report the results of a comprehensive study of these grandites. Garnet is found on the surfaces of tuffaceous blocks or inside their micropores, and is associated with sodalite, sanidine, marialite and amorphous silica. Garnet samples were examined by scanning electron microscopy (SEM), electron probe microanalysis (EPMA), powder and single-crystal X-ray diffraction (XRD) and infrared spectroscopy (IR). SEM observations on morphology showed typical dodecahedral and icositetrahedral habits. EPM analysis showed that they are close to grossular or andradite end members, with only moderate solid solution between them. X-ray study of single crystals showed cubic cell dimensions a_o of 11.86 ? (grossular) and 12.04 ? (andradite). IR spectroscopy confirmed the presence of hydroxyls in coexisting garnet and sanidine, 0.06 wt% H₂O (garnet) and 0.05–0.07 wt% H₂O (sanidine), respectively. Well-crystallized sanidine of an earlier generation showed significantly higher water contents, in the range 0.13–0.23 wt% H₂O. Type of occurrence and mineralogical features suggest a post-magmatic (pneumatolitic) genesis for these garnets. This is consistent with the physico-chemical processes linked to the eruptive dynamics of the breccias. Experimental studies of garnet synthesis at 550 °C and 2 kbar provide further support for this concept. Received January 16, 2002; accepted March 18, 2002     

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     

Phase equilibria modelling of kyanite‐bearing anatectic paragneisses from the central Grenville Province

Kyanite‐bearing paragneisses from the Manicouagan Imbricate Zone and its footwall (high‐P belt of the central Grenville Province) preserve evidence of partial melting with development of metamorphic textures involving biotite–garnet ± kyanite ± plagioclase ± K‐feldspar–quartz. Garnet in these rocks displays a variety of zoning patterns with respect to Ca. Pseudosection modelling in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (NCKFMASHTO) system using measured bulk rock compositions accounts for the textural evolution of two aluminous and two sub‐aluminous samples from the presumed thermal peak to conditions at which retained melt solidified. The prograde features are best explained by pseudosections calculated with compositions to account for melt loss. The intersection of isopleths of grossular content and Fe/(Fe + Mg) relating to large porphyroblasts of garnet provide constraints on the P–T conditions of the metamorphic peak. These P–T estimates are considered to be minima because of the potential for diffusional modification of the composition of garnet at high‐T and during the early stages of cooling. However, they are consistent with textural observations and pseudosection topology, with peak assemblages best preserved in rocks for which the calculated pseudosections predict only small changes in mineral proportions in the P–T interval, in which retrograde reactions are inferred to have occurred between the thermal peak and the solidus. Maximum P–T conditions (14.5–15.5 kbar and 840–890 °C) and steep retrograde P–T paths inferred for rocks from the Manicouagan Imbricate Zone are comparable with those determined for mafic rocks from the same area. In contrast, maximum P–T conditions of 12.5–13 kbar and 815–830 °C and flatter P–T paths are inferred for the rocks of the footwall to the Manicouagan Imbricate Zone. The general consistency between textures, mineral compositions and the topologies of the calculated pseudosections suggests that the pseudosection approach is an appropriate tool for inferring the P–T evolution of high‐P anatectic quartzo‐feldspathic rocks.     

Experimental investigations of the role of H2O in calc-alkaline differentiation and subduction zone magmatism

Phase relations of natural aphyric high-alumina basalts and their intrusive equivalents were determined through rock-melting experiments at 2 kb, H₂O-saturated with fO₂ buffered at NNO. Experimental liquids are low-MgO high-alumina basalt or basaltic andesite, and most are saturated with olivine, calcic plagioclase, and either high-calcium pyroxene or hornblende (±magnetite). Cr-spinel or magnetite appear near the liquidus of wet high-alumina basalts because H₂O lowers the appearance temperature of crystalline silicates but has a lesser effect on spinel. As a consequence, experimental liquids follow calcalkaline differentiation trends. Hornblende stability is sensitive to the Na₂O content of the bulk composition as well as to H₂O content, with the result that hornblende can form as a near liquidus mineral in wet sodic basalts, but does not appear until liquids reach andesitic compositions in moderate Na₂O basalts. Therefore, the absence of hornblende in basalts with low-to-moderate Na₂O contents is not evidence that those basalts are nearly dry. Very calcic plagioclase (>An₉₀) forms from basaltic melts with high H₂O contents but cannot form from dry melts with normal are Na₂O and CaO abundances. The presence of anorthite-rich plagioclase in high-alumina basalts indicates high magmatic H₂O contents. In sum, moderate pressure H₂O-saturated phase relations show that magmatic H₂O leads to the early crystallization of spinel, produces calcic plagioclase, and reduces the total proportion of plagioclase in the crystallizing assemblage, thereby promoting the development of the calc-alkaline differentiation trend.     

Inference of a detailed P–T path from P–T pseudosections using metapelitic rocks of variable composition from a single outcrop, Shackleton Range, Antarctica

Generally, P–T pseudosections for reduced compositional systems, such as K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O, Na₂O–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O and MnO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O, are well suited for inferring detailed P–T paths, comparing mineral assemblages observed in natural rocks with those calculated. Examples are provided by P–T paths inferred for four metapelitic samples from a 1 m² wide outcrop of the Herbert Mountains in the Shackleton Range, Antarctica. The method works well if the bulk composition used is reconstituted from average mineral modes and mineral compositions (AMC) or when X‐ray fluorescence (XRF) data are corrected for Al₂O₃ and FeO. A plagioclase correction is suitable for Al₂O₃. Correction for FeO is dependent on additional microscopic observations, e.g. the kind and amount of opaque minerals. In some cases, all iron can be treated as FeO^tot, whereas in others a magnetite or hematite correction yields much better results. Comparison between calculated and observed mineral modes and mineral compositions shows that the AMC bulk composition is best suited to the interpretation of rock textures using P–T pseudosections, whereas corrected XRF data yield good results only when the investigated sample has few opaque minerals. The results indicate that metapelitic rocks from the Herbert Mountains of the Northern Shackleton Range underwent a prograde P–T evolution from about 600 °C/5.5 kbar to 660 °C/7 kbar, followed by nearly adiabatic cooling to about 600 °C at 4.5 kbar.