Peter J. Wyllie

Dehydration-melting of amphibolite at 10 kbar: the effects of temperature and time

We have simulated the dehydration-melting of a natural, low-K, calcic amphibolite (67.4% hornblende, 32.5% anorthite) in piston-cylinder experiments at 10 kbar and 750–1000°C, for 1–9 days. The solidus temperature is lower than 750°C; garnet appears at 850°C. The overall reaction is: Hb+P→L+Cpx+Al-Hb+Ca-Hb+Ga+Opx. Three stages of reaction are: (1) melting dominated by the growth of clinopyroxene and garnet, with little change in composition of liquid or garnet, (2) a reversal of this reaction between 875°C and 900°C, with decreases in the amounts of liquid and garnet, and (3) a large increase in liquid along with the loss of hornblende and decrease of plagioclase while clinopyroxene and garnet increase. Garnet is enriched in pyrope and zoned from Fe-cores to Mg-edges (range ∼3 mol % pyrope); liquid composition is enriched first in An (to ∼950°C) and then in Ab. The liquids are more calcic and aluminous than natural tonalites, which is attributed to the plagioclase composition (An90). The formation of peraluminous liquid from the metaluminous amphibolite is caused by anorthite — not H2O-saturated conditions. The results are consistent with an amphibolite phase diagram with relatively high solidus temperatures in the garnet-absent field (900–1000°C), but with a solidus backbend at ∼7–9 kbar, coincident with the garnet-in boundary. Hornblende breakdown due to garnet formation in a closed system must make H2O available for H2O-undersaturated melting right down to the H2O-saturated solidus, below 700°C, which defines a large low-temperature PT area where hydrous granitoid melts can be generated with residual garnet and hornblende.

Crustal anatexis: An experimental review

Review of experimental studies in synthetic systems An—Ab—Or—Qz—H_2O and K_2O—Al_2O_3—SiO_2—H_2O illustrates the dominance of feldspar—quartz assemblages in crustal anatectic processes, and the role of hydrous minerals such as muscovite. H_2O-undersaturated liquids can exist with quartz—feldspar assemblages through hundreds of degrees with little change in composition in terms of anhydrous components. Review of the phase relationships in the rock series gabbro—tonalite—granodiorite—granite—H_2O to 15 kbar is used as a basis for interpreting anatexis of deep crustal rocks, including metamorphosed grey wackes and pelitic rocks. For individual rocks, diagrams include PT projections with excess H_2O, with hydrous minerals but no excess H_2O, of H_2O-undersaturated liquidus surfaces, and isobaric T-X_(H_2O) sections. For the rock series, 10 kbar diagrams show the melting interval with excess H_2O, the H_2O-undersaturated liquidus surface, and the melting interval with 2% H_2O. The normal product of regional metamorphism is H_2O-undersaturated granitic liquid; H_2O-saturated liquids exist only through narrow temperature intervals. Liquids of granite composition trend towards granodiorite with increasing temperature or pressure, but compositions do not reach tonalite unless metamorphic temperatures approach 1100°C. Tonalite plutons represent mushes of granitic liquid with refractory residual crystals, or recrystallized residual masses from which the granitic liquid escaped. Some tonalite plutons may be derived from magmas with source in subducted ocean crust or mantle.

Melting of Gabbro (Quartz Eclogite) with Excess Water to 35 Kilobars, with Geological Applications

Crystalline, fine-grained, high-alumina olivine tholeiite with excess water was reacted in sealed platinum capsules in piston-cylinder apparatus between 10 and 35 kbar pressure. Runs were planned to determine the curve for the beginning of melting, but combining these with published results at lower pressures permitted delineation of the major features of the phase diagram through the melting interval. Amphibolite melts below 10 kbar; quartz eclogite melts above 25 kbar; between them is a melting interval dominated by the breakdown of amphibole and formation of garnet and jadeitic pyroxene. The results introduce two features for geological applications. The solidus changes slope at about 13.5 kbar; the amphibole maximum-stability curve changes slope in the interval 12.5-15 kbar to such an extent that the amphibole stability field is more restricted at high pressures than anticipated from previous studies. With free water, eclogite is Stable only at depths greater than about 70 km, and amphibolite is Stable in the deep crust. Amphibolite crust thickened in the depth range 40-60 km with aqueous pore fluid melts, forming a liquid enriched in silica and albitic plagioclase; this is a potential source of water-undersaturated liquids for batholiths. The upper boundary of the mantle low-velocity zone could be the boundary between rocks with interstitial amphibole and those with interstitial hydrous silicate liquid. In oceanic crust forming the upper part of a subducted lithosphere slab, it appears that most hydrous minerals dehydrate or melt before they reach 100 km depth. If so, dehydration of subducted oceanic crust does not supply water for andesitic magmatism beyond the arc-trench gap, nor contribute to the chemical variations recorded in andesites across arc complexes (

Partitioning of Cu, Sn, Mo, W, U, and Th between melt and aqueous fluid in the systems haplogranite-H2O−HCl and haplogranite-H2O−HF

K_{2}O

Subsolidus and melting relationships for calcite, magnesite and the join CaCO3-MgCO3 36 kb

, K/Rb).

Melting of vapour-absent tonalite at 10 kbar to simulate dehydration–melting in the deep crust

Bowens petrogenetic grid was based initially on a series of decarbonation reactions in the system CaO-MgO-SiO2-CO2 with starting assemblages including calcite, dolomite, magnesite and quartz, and products including enstatite, forsterite, diopside and wollastonite. We review the positions of 14 decarbonation reactions, experimentally determined or estimated, extending the grid to mantle pressures to evaluate the effect of CO2 on model mantle peridotite composed of forsterite(Fo)+orthopyroxene(Opx)+clinopyroxene(Cpx). Each reaction terminates at an invariant point involving a liquid, CO2, carbonates, and silicates. The fusion curves for the mantle mineral assemblages in the presence of excess CO2 also terminate at these invariant points. The points are connected by a series of reactions involving liquidus relationships among the carbonates and mantle silicates, at temperatures lower (1,100–1,300° C) than the silicate-CO2 melting reactions (1,400–1,600° C). Review of experimental data in the bounding ternary systems together with preliminary data for the system CaO-MgO-SiO2-CO2 permits construction of a partly schematic framework for decarbonation and melting reactions at upper mantle pressures. The key to several problems in the peridotite-CO2 subsystem is the intersection of a subsolidus carbonation reaction with a melting reaction at an invariant point near 24 kb and 1,200°C. There is an intricate series of reactions between 25 kb and 35 kb involving changes in silicate and carbonate phase fields on the CO2-saturated liquidus surfaces. Conclusions include the following: (1) Peridotite Fo+Opx+Cpx can be carbonated with increasing pressure, or decreasing temperature, to yield Fo+Opx+Cpx+Cd (Cd=calcic dolomite), Fo+Opx+Cd, Fo+Opx+Cm (Cm=calcic magnesite), and finally Qz+Cm. (2) Free CO2 cannot exist in subsolidus mantle peridotite with normal temperature distributions; it is stored as carbonate, Cd. (3) The CO2 bubbles in peridotite nodules do not represent free CO2 in mantle peridotite along normal geotherms. (4) CO2 is as effective as H2O in causing incipient melting, our preferred explanation for the low-velocity zone. (5) Fusion of peridotite with CO2 at depths shallower than 80 km produces basic magmas, becoming more SiO2-undersaturated with depth. (6) The solubility of CO2 in mantle magmas is less than about 5 wt% at depths to 80 km, increasing abruptly to about 40 wt% at 80 km and deeper. (7) Deeper than 80 km, the first liquids produced are carbonatitic, changing towards kimberlitic and eventually, at considerably higher temperatures, to basic magmas. (8) Kimberlite and carbonatite magmas rising from the asthenosphere must evolve CO2 at depths 100-80 km, which contributes to their explosive emplacement. (9) Fractional crystallization of CO2-bearing SiO2-undersaturated basic magmas at most pressures can yield residual kimberlite and carbonatite magmas.

Mantle Fluid Compositions Buffered in Peridotite-CO_2-H_2O by Carbonates, Amphibole, and Phlogopite

The partition coefficients KD=cfluid/cmelt of Cu, Sn, Mo, W, U, and Th between aqueous fluid and melt were measured in the systems haplogranite-H2O−HCl and haplogranite-H2O−HF at 2kbars, 750°C, and Ni−NiO buffer conditions using rapid-quench cold seal bombs, with many reversed runs. Concentrations of trace elements (1–1000 ppm) in the quenched aqueous fluid and in the glass were determined by plasma emission spectrometry (DCP). KD of F is close to 1 in the system studied. KD of Cu and Sn strongly increases with increasing Cl concentration due to the formation of chloride complexes in the aqueous fluid, while HF has no effect. However, in 2M HCl, KD of Cu approaches 100, while KD of Sn is below 0.1 under the same conditions. The partition coefficients of Mo and W are high if water is the only volatile present (Mo: 5.5, W: 3.5), but strongly decrease with increasing HCl and HF, due to the destabilization of hydroxy complexes. KD of U and Th is very low in the absence of complexing agents, but strongly increases with increasing HF concentration. KD of U also increases with increasing HCl concentration and with increasing CO2 concentration in the system haplogranite-H2O−CO2, indicating the stability of chloride and carbonate complexes of U at magmatic temperatures. The data suggest a stoichiometric ratio of Cl: U=3:1 and of F:U=2:1 in these complexes. Cl-rich fluids are responsible for the formation of porphyry Cu deposits, but are much less effective in the transport of Sn. F appears not to be essential for the concentration of Mo and W in fluids evolving from a granitic magma. The different complexing behavior of U and Th in aqueous fluids may account for their fractionation during magma genesis.

Constraints imposed by experimental petrology on possible and impossible magma sources and products

Extrapolation and extension of phase equilibria in the model system KAlSiO4-Mg2SiO4-SiO2-H2O suggests that at depths greater than 100 km (deeper than amphibole stability), hybridism between cool hydrous siliceous magma, rising from subducted oceanic crust, and the hotter overlying mantle peridotite produces a series of discrete masses composed largely of phlogopite, orthopyroxene, and clinopyroxene (enriched in Jadeite). Quartz (or coesite) may occur with phlogopite in the lowest part of the masses. The heterogeneous layer thus produced above the subducted oceanic crust provides: (1) aqueous fluids expelled during hybridization and solidification, which rise to generate in overlying mantle (given suitable thermal structure) H2O-undersaturated basic magma, which is the parent of the calc-alkalic rock series erupted at the volcanic front; (2) masses of phlogopite-pyroxenites which melt when they cross a deeper, high-temperature solidus, yielding the parents of alkalic magmas erupted behind the volcanic front; and (3) blocks of phlogopite-pyroxenites which may rise diapirically for long-term residence in continental lithosphere, and later contribute to the potassium (and geochemically-related elements) involved in some of the continental magmatism with geochemistry ascribed to mantle metasomatism.