Garnet and spinel lherzolite assemblages in MgO–Al2O3–SiO2 and CaO–MgO–Al2O3–SiO2: thermodynamic models and an experimental conflict

The recent publication of an updated thermodynamic dataset for petrological calculations provides an opportunity to illustrate the relationship between experimental data and the dataset, in the context of a new set of activity–composition models for several key minerals. These models represent orthopyroxene, clinopyroxene and garnet in the system CaO–MgO–Al₂O₃–SiO₂ (CMAS), and are valid up to 50 kbar and at least 1800 °C; they are the first high‐temperature models for these phases to be developed for the Holland & Powell dataset. The models are calibrated with reference to phase‐relation data in the subsystems CaO–MgO–SiO₂ (CMS) and MgO–Al₂O₃–SiO₂ (MAS), and will themselves form the basis of models in larger systems, suitable for calculating phase equilibria in the crust and mantle. In the course of calibrating the models, it was necessary to consider the reaction orthopyroxene + clinopyroxene + spinel = garnet + forsterite in CMAS, representing a univariant transition between simple spinel and garnet lherzolite assemblages. The high‐temperature segment of this reaction has been much disputed. We offer a powerful thermodynamic argument relating this reaction to the equivalent reaction in MAS, that forces us to choose between good model fits to the data in MAS or to the more recent data in CMAS. We favour the fit to the MAS data, preserving conformity with a large body of experimental and thermodynamic data that are incorporated as constraints on the activity–composition modelling via the internally consistent thermodynamic dataset.     

Calculation of partial melting equilibria in the system Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O (NCKFMASH)

A thermodynamic model for haplogranitic melts in the system Na₂O–CaO–K₂O–Al₂O₃–SiO₂–H₂O (NCKASH) is extended by the addition of FeO and MgO, with the data for the additional end‐members of the liquid incorporated in the Holland & Powell (1998) internally consistent thermodynamic dataset. The resulting dataset, with the software thermocalc , is then used to calculate melting relationships for metapelitic rock compositions. The main forms for this are P–T and T–X pseudosections calculated for particular rock compositions and composition ranges. The relationships in these full‐system pseudosections are controlled by the low‐variance equilibria in subsystems of NCKFMASH. In particular, the solidus relationships are controlled by the solidus relationships in NKASH, and the ferromagnesian mineral relationships are controlled by those in KFMASH. However, calculations in NCKFMASH allow the relationships between the common metapelitic minerals and silicate melt to be determined. In particular, the production of silicate melt and melt loss from such rocks allow observations to be made about the processes involved in producing granulite facies rocks, particularly relating to open‐system behaviour of rocks under high‐grade conditions.     

The stability of sapphirine + quartz: calculated phase equilibria in FeO–MgO–Al2O3–SiO2–TiO2–O

The presence in rocks of coexisting sapphirine + quartz has been widely used to diagnose conditions of ultra‐high‐temperature (UHT) metamorphism (>900 °C), an inference based on the restriction of this assemblage to temperatures >980 °C in the conventionally considered FeO–MgO–Al₂O₃–SiO₂ (FMAS) chemical system. With a new thermodynamic model for sapphirine that includes Fe₂O₃, phase equilibra modelling using thermocalc software has been undertaken in the FeO–MgO–Al₂O₃–SiO₂–O (FMASO) and FeO–MgO–Al₂O₃–SiO₂– TiO₂–O (FMASTO) chemical systems. Using a variety of calculated phase diagrams for quartz‐saturated systems, the effects of Fe₂O₃ and TiO₂ on FMAS phase relations are shown to be considerable. Importantly, the stability field of sapphirine + quartz assemblages extends down temperature to 850 °C in oxidized systems and thus out of the UHT range.     

Garnet–chloritoid–kyanite assemblages: eclogite facies indicators of subduction constraints in orogenic belts

The assemblage garnet–chloritoid–kyanite is shown to be quite common in high‐pressure eclogite facies metapelites from orogenic belts around the world, and occurs over a narrowly restricted range of temperature ～550–600 °C, between 20 and 25 kbar. This assemblage is favoured particularly by large Al₂O₃:K₂O ratios allowing the development of kyanite in addition to garnet and chloritoid. Additionally, ferric iron and manganese also help stabilize chloritoid in this assemblage. Pseudosections for several bulk compositions illustrate these high‐pressure assemblages, and a new thermodynamic model for white mica to include calcium and ferric iron was required to complete the calculations. It is extraordinary that so many orogenic eclogite facies rocks, both mafic eclogites sensu stricto as well as metapelites with the above assemblage, all yield temperatures within the range of 520–600 °C and peak pressures ～23±3 kbar. Subduction of oceanic crust and its entrained associated sedimentary material must involve the top of the slab, where mafic and pelitic rocks may easily coexist, passing through these P–T conditions, such that rocks, if they proceed to further depths, are generally not returned to the surface. This, together with the tightly constrained range in peak temperatures which such eclogites experience, suggests thermal weakening being a major control on the depths at which crustal material is decoupled from the downgoing slab.     

Internally consistent data for sulphur‐bearing phases and application to the construction of pseudosections for mafic greenschist facies rocks in Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–CO2–O–S–H2O

The Holland and Powell internally consistent data set version 5.5 has been augmented to include pyrite, troilite, trov (Fe_0.875S), anhydrite, H₂S, elemental S and S₂ gas. Phase changes in troilite and pyrrhotite are modelled with a combination of multiple end‐members and a Landau tricritical model. Pyrrhotite is modelled as a solid solution between hypothetical end‐member troilite (trot) and Fe_0.875S (trov); observed activity–composition relationships fit well to a symmetric formalism model with a value for w_trot?trov of ?3.19 kJ mol^?1. The hypothetical end‐member approach is required to compensate for iron distribution irregularities in compositions close to troilite. Mixing in fluids is described with the van Laar asymmetric formalism model with a_ij values for H₂O–H₂S, H₂S–CH₄ and H₂S–CO₂ of 6.5, 4.15 and 0.045 kJ mol^?1 respectively. The derived data set is statistically acceptable and replicates the input data and data from experiments that were not included in the initial regression. The new data set is applied to the construction of pseudosections for the bulk composition of mafic greenschist facies rocks from the Golden Mile, Kalgoorlie, Western Australia. The sequence of mineral assemblages is replicated successfully, with observed assemblages predicted to be stable at X(CO₂) increasing with increasing degree of hydrothermal alteration. Results are compatible with those of previous work. Assemblages are insensitive to the S bulk content at S contents of less than 1 wt%, which means that volatilization of S‐bearing fluids and sulphidation are unlikely to have had major effects on the stable mineral assemblage in less metasomatized rocks. The sequence of sulphide and oxide phases is predicted successfully and there is potential to use these phases qualitatively for geobarometry. Increases in X(CO₂) stabilized, in turn, pyrite–magnetite, pyrite–hematite and anhydrite–pyrite. Magnetite–pyrrhotite is predicted at temperatures greater than 410 °C. The prediction of a variety of sulphide and oxide phases in a rock of fixed bulk composition as a function of changes in fluid composition and temperature is of particular interest because it has been proposed that such a variation in phase assemblage is produced by the infiltration of multiple fluids with contrasting redox state. The work presented here shows that this need not be the case.     

Melts of garnet lherzolite: experiments, models and comparison to melts of pyroxenite and carbonated lherzolite

Phase equilibrium experiments on a compositionally modified olivine leucitite from the Tibetan plateau have been carried out from 2.2 to 2.8 GPa and 1,380–1,480 °C. The experiments-produced liquids multiply saturated with spinel and garnet lherzolite phase assemblages (olivine, orthopyroxene, clinopyroxene and spinel ± garnet) under nominally anhydrous conditions. These SiO₂-undersaturated liquids and published experimental data are utilized to develop a predictive model for garnet lherzolite melting of compositionally variable mantle under anhydrous conditions over the pressure range of 1.9–6 GPa. The model estimates the major element compositions of garnet-saturated melts for a range of mantle lherzolite compositions and predicts the conditions of the spinel to garnet lherzolite phase transition for natural peridotite compositions at above-solidus temperatures and pressures. We compare our predicted garnet lherzolite melts to those of pyroxenite and carbonated lherzolite and develop criteria for distinguishing among melts of these different source types. We also use the model in conjunction with a published predictive model for plagioclase and spinel lherzolite to characterize the differences in major element composition for melts in the plagioclase, spinel and garnet facies and develop tests to distinguish between melts of these three lherzolite facies based on major elements. The model is applied to understand the source materials and conditions of melting for high-K lavas erupted in the Tibetan plateau, basanite–nephelinite lavas erupted early in the evolution of Kilauea volcano, Hawaii, as well as younger tholeiitic to alkali lavas from Kilauea.     

An enlarged and updated internally consistent thermodynamic dataset with uncertainties and correlations: the system K2O–Na2O–CaO–MgO–MnO–FeO–Fe2O3–Al2O3–TiO2–SiO2–C–H2–O2

We present, as a progress report, a revised and much enlarged version of the thermodynamic dataset given earlier (Holland & Powell, 1985). This new set includes data for 123 mineral and fluid end-members made consistent with over 200 P–T–X_CO2–f_O2 phase equilibrium experiments. Several improvements and advances have been made, in addition to the increased coverage of mineral phases: the data are now presented in three groups ranked according to reliability; a large number of iron-bearing phases has been included through experimental and, in some cases, natural Fe:Mg partitioning data; H₂O and CO₂ contents of cordierites are accounted for with the solution model of Kurepin (1985); simple Landau theory is used to model lambda anomalies in heat capacity and the Al/Si order–disorder behaviour in some silicates, and Tschermak-substituted end-members have been derived for iron and magnesium end-members of chlorite, talc, muscovite, biotite, pyroxene and amphibole. For the subset of data which overlap those of Berman (1988), it is encouraging to find both (1) very substantial agreement between the two sets of thermodynamic data and (2) that the two sets reproduce the phase equilibrium experimental brackets to a very similar degree of accuracy. The main differences in the two datasets involve size (123 as compared to 67 end-members), the methods used in data reduction (least squares as compared to linear programming), and the provision for estimation of uncertainties with this dataset. For calculations on mineral assemblages in rocks, we aim to maximize the information available from the dataset, by combining the equilibria from all the reactions which can be written between the end-members in the minerals. For phase diagram calculations, we calculate the compositions of complex solid solutions (together with P and T) involved in invariant, univariant and divariant assemblages. Moreover we strongly believe in attempting to assess the probable uncertainties in calculated equilibria and hence provide a framework for performing simple error propagation in all calculations in thermocalc, the computer program we offer for an effective use of the dataset and the calculation methods we advocate.     

The near-solidus transition from garnet lherzolite to spinel lherzolite

The position of the transition from spinel lherzolite to garnet lherzolite in the system CaO-MgO-Al₂O₃-SiO₂ (CMAS) has been determined experimentally at near-solidus temperatures. In reversed experiments, the transition occurs between 18 and 20 kbar at 1200 °C and between 26 and 27 kbar at 1500 °C, corresponding to higher pressures than previously envisaged. A position for the transition deeper within the Earth further complicates the explanation of the so-called garnet signatures in the trace element and isotope patterns of mid-ocean ridge basalts. If melting during adiabatic upwelling beneath a mid-ocean ridge begins at the depth required for the stability of garnet in peridotitic compositions, simple melting models predict that the amount of melt produced should be much greater than the observed thickness of the oceanic crust. A partial solution to the apparent conflict might be that (1) the rather simplistic melting models are in error, (2) that melting begins in garnet pyroxenite veins that are believed to be stable at lower pressures than garnet lherzolite or (3) that melting does not involve garnet at all, but it is clinopyroxene causing the trace element patterns observed in basalts erupted at mid-ocean ridges. A second set of reversal experiments were conducted to investigate the solubility of alumina in both orthopyroxenes and clinopyroxenes at the high temperatures near the solidus in the system CMAS. The results are compatible with most previous studies, and may be used as a starting point to calibrate thermodynamic models for pyroxenes in chemical systems, approximating upper mantle chemistry. Received: 9 August 1999 / Accepted: 29 October 1999     

Structural,petrological and chemical analysis of syn‐kinematic migmatites: insights from the Western Gneiss Region,Norway

Evidence of melting is presented from the Western Gneiss Region (WGR) in the core of the Caledonian orogen, Western Norway and the dynamic significance of melting for the evolution of orogens is evaluated. Multiphase inclusions in garnet that comprise plagioclase, potassic feldspar and biotite are interpreted to be formed from melt trapped during garnet growth in the eclogite facies. The multiphase inclusions are associated with rocks that preserve macroscopic evidence of melting, such as segregations in mafic rocks, leucosomes and pegmatites hosted in mafic rocks and in gneisses. Based on field studies, these lithologies are found in three structural positions: (i) as zoned segregations found in high‐P (ultra)mafic bodies; (ii) as leucosomes along amphibolite facies foliation and in a variety of discordant structures in gneiss; and (iii) as undeformed pegmatites cutting the main Caledonian structures. Segregations post‐date the eclogite facies foliation and pre‐date the amphibolite facies deformation, whereas leucosomes are contemporaneous with the amphibolite facies deformation, and undeformed pegmatites are post‐kinematic and were formed at the end of the deformation history. The geochemistry of the segregations, leucosomes and pegmatites in the WGR defines two trends, which correlate with the mafic or felsic nature of the host rocks. The first trend with Ca‐poor compositions represents leucosome and pegmatite hosted in felsic gneiss, whereas the second group with K‐poor compositions corresponds to segregation hosted in (ultra)mafic rocks. These trends suggest partial melting of two separate sources: the felsic gneisses and also the included mafic eclogites. The REE patterns of the samples allow distinction between melt compositions, fractionated liquids and cumulates. Melting began at high pressure and affected most lithologies in the WGR before or during their retrogression in the amphibolite facies. During this stage, the presence of melt may have acted as a weakening mechanism that enabled decoupling of the exhuming crust around the peak pressure conditions triggering exhumation of the upward‐buoyant crust. Partial melting of both felsic and mafic sources at temperatures below 800 °C implies the presence of an H₂O‐rich fluid phase at great depth to facilitate H₂O‐present partial melting.     

Amphibolites with staurolite and other aluminous minerals: calculated mineral equilibria in NCFMASH

Amphibolite facies mafic rocks that consist mainly of hornblende, plagioclase and quartz may also contain combinations of chlorite, garnet, epidote, and, more unusually, staurolite, kyanite, sillimanite, cordierite and orthoamphiboles. Such assemblages can provide tighter constraints on the pressure and temperature evolution of metamorphic terranes than is usually possible from metabasites. Because of the high variance of most of the assemblages, the phase relationships in amphibolites depend on rock composition, in addition to pressure, temperature and fluid composition. The mineral equilibria in the Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O (NCFMASH) model system demonstrate that aluminium content is critical in controlling the occurrence of assemblages involving hornblende with aluminous minerals such as sillimanite, kyanite, staurolite and cordierite. Except in aluminous compositions, these assemblages are restricted to higher pressures. The iron to magnesium ratio (X_Fe), and to a lesser extent, sodium to calcium ratio, have important roles in determining which (if any) of the aluminous minerals occur under particular pressure–temperature conditions. Where aluminous minerals occur in amphibolites, the P–T–X dependence of their phase relationships is remarkably similar to that in metapelitic rocks. The mineral assemblages of Fe‐rich amphibolites are typically dominated by garnet‐ and staurolite‐bearing assemblages, whereas their more Mg‐rich counterparts contain chlorite and cordierite. Assemblages involving staurolite–hornblende can occur over a wide range of pressures (4–10 kbar) at temperatures of 560–650 °C; however, except in the more aluminous, iron‐rich compositions, they occupy a narrow pressure–temperature window. Thus, although their occurrence in ‘typical’ amphibolites may be indicative of relatively high pressure metamorphism, in more aluminous compositions their interpretation is less straightforward.     

Low‐P melting of metapelitic rocks and the role of H2O: Insights from phase equilibria modelling

Water‐fluxed melting has long been thought to have a minor influence on the thermal and chemical structure of the crust. We report here on amphibolite facies metasedimentary rocks from the 490–450 Ma Famatinian Orogen, in northwest Argentina, that have undergone water‐fluxed incongruent biotite melting at relatively low temperature, which have produced and lost a significant volume of melt. The protoliths consist of the turbiditic Puncoviscana Formation (Neoproterozoic to Early Cambrian). The field area exhibits a condensed metamorphic field gradient, from greenschist to amphibolite facies suprasolidus conditions, recording a low pressure almost isobaric path, reaching peak conditions estimated at 700°C at 4 kbar. Thermodynamic modelling in the MnNCKFMASHTO system is applied to investigate melting at such low pressure as a function of water content. Calculations using a typical turbidite composition show how small amounts of added free H₂O may increase significantly the melt fraction with little or no change in either the melt or residual phase compositions. They indicate negligible difference in normative An–Ab–Or proportions and ferromagnesian contents between melts derived by dehydration and water‐fluxed melts. The same is true for the content of H₂O dissolved in melts, which remains constant and the melt produced is granitic whether or not aqueous fluids are present. Thus, neither the residue nor the melt composition are indicators of the presence of aqueous fluids during anatexis. Recognizing the impact of small additions of H₂O to an anatectic terrane may therefore be difficult. The most significant change related to water‐fluxing is the relative proportions of minerals and melt fraction, rather than the actual mineral assemblage. The modal proportion of feldspar decreased while those of cordierite and biotite increased in the residual assemblages, as <5 mol.% of free H₂O was added. The impact of this addition is to more than double the proportion of water‐undersaturated melt to 25–30 mol.%. We have also developed a simple way to estimate how much melt a residual rock has lost, if the compositional trends of the protoliths are known. In summary, we find that even though the addition of small amounts of free H₂O impacts significantly on rock fertility, there is little obvious record in the field. The combined application of careful petrological investigation and thermodynamic modelling is the key to identify the influence of aqueous fluids, and exploit systems that became open not only to fluid influx but also to the extraction of melt.     

High‐grade metamorphism and partial melting in Archean composite grey gneiss complexes

Much of the exposed Archean crust is composed of composite gneiss which includes a large proportion of intermediate to tonalitic material. These gneiss terranes were typically metamorphosed to amphibolite to granulite facies conditions, with evidence for substantial partial melting at higher grade. Recently published activity–composition (a?x) models for partial melting of metabasic to intermediate compositions allows calculation of the stable metamorphic minerals, melt production and melt composition in such rocks for the first time. Calculated P?T pseudosections are presented for six bulk rock compositions taken from the literature, comprising two metabasic compositions, two intermediate/dioritic compositions and two tonalitic compositions. This range of bulk compositions captures much of the diversity of rock types found in Archean banded gneiss terranes, enabling us to present an overview of metamorphism and partial melting in such terranes. If such rocks are fluid saturated at the solidus, they first begin to melt in the upper amphibolite facies. However, at such conditions, very little (< 5%) melt is produced and this melt is granitic in composition for all rocks. The production of greater proportions of melt requires temperatures ～800–850 °C and is associated with the first appearance of orthopyroxene at pressures below 8–9 kbar or with the appearance and growth of garnet at higher pressures. The temperature at which orthopyroxene appears varies little with composition providing a robust estimate of the amphibolite–granulite facies boundary. Across this boundary, melt production is coincident with the breakdown of hornblende and/or biotite. Melts produced at granulite facies range from tonalite–trondhjemite–granodiorite for the metabasic protoliths, granodiorite to granite for the intermediate protoliths and granite for the tonalitic protoliths. Under fluid‐absent conditions the melt fertility of the different protoliths is largely controlled by the relative proportions of hornblende and quartz at high grade, with the intermediate compositions being the most fertile. The least fertile rocks are the most leucocratic tonalites due to their relatively small proportions of hydrous mafic phases such as hornblende or biotite. In the metabasic rocks, melt production becomes limited by the complete consumption of quartz to higher temperatures. The use of phase equilibrium forward‐modelling provides a thermodynamic framework for understanding melt production, melt loss and intracrustal differentiation during the Archean.     

Upper‐amphibolite facies partial melting of paragneisses from the Epupa Complex,NW Namibia,and relations to Mesoproterozoic anorthosite magmatism

The evolution of the mineral assemblages and P–T conditions during partial melting of upper‐amphibolite facies paragneisses in the Orue Unit, Epupa Complex, NW Namibia, is modelled with calculated P–T–X phase diagrams in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O system. The close concordance of predictions from the phase diagrams to petrographic observations and thermobarometric results documents that quantitative phase diagrams are suitable to explain the phase relationships in migmatitic upper‐amphibolite facies low‐ and medium‐pressure metapelites, which occur in many high‐grade metamorphic terranes worldwide. Different mineral assemblages in the migmatitic metapelites of the Orue Unit reflect regional discrepancies in the metamorphic grade: in a Northern Zone, early biotite–sillimanite–quartz assemblages were replaced via melt‐producing reactions by cordierite‐bearing assemblages. In a Southern Zone, they were replaced via melt‐producing reactions by garnet‐bearing assemblages while cordierite is restricted to rare metapelitic granofelses, which preserve Grt–Sil–Crd–Bt peak assemblages. Peak‐metamorphic conditions of 700–750 °C at 5.5–6.7 kbar in the Southern Zone and of ～750 °C at 4.5 kbar in the Northern Zone are estimated by integrating thermobarometric calculations with data from calculated mineral composition isopleths. Retrograde back‐reactions between restite and crystallizing melt are recorded by the replacement of garnet by biotite–sillimanite and/or biotite–muscovite intergrowths. Upper‐amphibolite facies metamorphism and partial melting (c. 1340–1320 Ma) in the rocks of the Southern Zone of the Orue Unit, which underwent probably near‐isobaric heating–cooling paths, are attributed to contact metamorphism induced by the coeval (c. 1385–1319 Ma) emplacement of the Kunene Intrusive Complex, a huge massif‐type anorthosite body. The lower‐pressure metapelites of the Northern Zone are interpreted to record contact metamorphism at an upper crustal level.     

Melting Behaviour of Model Lherzolite in the System CaO-MgO-Al2O3-SiO2-FeO at 0{middle dot}7-2{middle dot}8 GPa

Fe–Mg exchange is the most important solid solution involvedin partial melting of spinel lherzolite, and the system CaO–MgO–Al₂O₃–SiO₂–FeO(CMASF) is ideally suited to explore this type of exchange duringmantle melting. Also, if primary mid-ocean ridge basalts arelargely generated in the spinel lherzolite stability field bynear-fractional fusion, then Na and other highly incompatibleelements will early on become depleted in the source, and themelting behaviour of mantle lherzolite should resemble the meltingbehaviour of simplified lherzolite in the CMASF system. We havedetermined the isobarically univariant melting relations ofthe lherzolite phase assemblage in the CMASF system in the 0·7–2·8GPa pressure range. Isobarically, for every 1 wt % increasein the FeO content of the melt in equilibrium with the lherzolitephase assemblage, the equilibrium temperature is lower by about3–5°C. Relative to the solidus of model lherzolitein the CaO–MgO–Al₂O₃–SiO₂ system, melt compositionsin the CMASF system are displaced slightly towards the alkalicside of the basalt tetrahedron. The transition on the solidusfrom spinel to plagioclase lherzolite has a positive Clapeyronslope with the spinel lherzolite assemblage on the high-temperatureside, and has an almost identical position in P–T spaceto the comparable transition in the CaO–MgO–Al₂O₃–SiO₂–Na₂O(CMASN) system. When the compositions of all phases are describedmathematically and used to model the generation of primary basalts,temperature and melt composition changes are small as percentmelting increases. More specifically, 10% melting takes placeover 1·5–2°C, melt compositions are relativelyinsensitive to the degree of melting and bulk composition, andequilibrium and near-fractional melting yield similar melt compositions.FeO and MgO are the oxides that exhibit the greatest changein the melt with degree of melting and bulk composition. Theamount of FeO decreases with increasing degree of melting, whereasthe amount of MgO increases. The coefficients for Fe–Mgexchange between the coexisting crystalline phases and melt,K_dFe–Mg^xl–liq, show a relatively simple and predictablebehaviour with pressure and temperature: the coefficients forolivine and spinel do not show significant dependence on temperature,whereas the coefficients for orthopyroxene and clinopyroxeneincrease with pressure and temperature. When melting of lherzoliteis modeled in the CMASF system, a strong linear correlationis observed between the mg-number of the lherzolite and themg-number of the near-solidus melts. Comparison with meltingin the CMASN system indicates that Na₂O has a strong effecton lherzolite melting behaviour only at small degrees of melting. KEY WORDS: CMASF; lherzolite solidus; mantle melting     

Anatectic melt volumes in the thermal aureole of the Etive Complex,Scotland: the roles of fluid‐present and fluid‐absent melting

Pelitic hornfelses within the inner thermal aureole of the Etive igneous complex underwent limited partial melting, generating agmatic micro‐stromatic migmatites. In this study, observed volume proportions of vein leucosomes in the migmatites are compared with modelled melt volumes in an attempt to constrain the controls on melting processes. Petrogenetic modelling in the MnNCKFMASHT system was performed on the compositions of 15 analysed Etive pelite samples using THERMOCALC. Melt modes were calculated at 2.2 kbar (the estimated pressure in the southern Etive aureole) from solidus temperatures to 800 °C for both fluid‐absent and fluid‐present conditions. Volume changes accompanying fluid‐absent melting at 2.2 kbar were also calculated. P–T pseudosections reproduce the zonal sequence of the southern Etive aureole fairly well. The modelled solidus temperatures of silica‐rich pelitic compositions are close to 680 °C at 2.2 kbar and, in the absence of free fluid, melt modes in such compositions rise to between 12 and 29% at 800 °C, half of which is typically produced over the narrow reaction interval in which orthopyroxene first appears. Silica‐poor compositions have solidus temperatures of up to ～770 °C and yield <11.4% melt at 800 °C under fluid‐absent conditions. For conditions of excess H₂O, modelled melt modes increase dramatically within ～13 °C of the solidus, in some cases to >60%; by 800 °C they range from 61 to 88% and from 29 to 74% in silica‐rich and silica‐poor compositions, respectively. Calculated volume changes for fluid‐absent melting are positive for all modelled compositions and reach 4.5% in some silica‐rich compositions by 800 °C. Orthopyroxene formation is accompanied by a volume increase of up to 1.48% over a temperature increase of as little as 2.7 °C, supporting the arguments for melt‐induced ‘hydrofracturing’ as a viable melt‐escape mechanism in low‐P metamorphism. Mineral assemblages in the innermost aureole support previous conclusions that partial melting took place predominantly under fluid‐absent conditions. However, vein leucosome proportions, estimated by image analysis, do not show the expected correlation with grade, and are locally greatly in excess of melt modes predicted by fluid‐absent models, particularly close to the melt‐in isograd. Melting of interlayered psammites, addition of H₂O from interlayered melt‐free rocks, and metastable persistence of muscovite are ruled out as major causes of the excess melt anomaly. The most likely cause, we believe, is that local variations existed in the amount of fluid available at the onset of melting, promoted by focussing of fluid released by dehydration in the middle and outer aureole; however, some redistribution of melt by compaction‐driven flow through the vein channel network cannot be ruled out. The formation of melt‐filled fractures in the inner Etive aureole was assisted by stresses that caused extension at high angles to the igneous contact. The fractures were probably caused either by transient pressure reduction in the diorite magma chamber associated with a second phase of intrusion, or by sub‐solidus thermal contraction in the diorite pluton during the early stages of inner‐aureole cooling.     

High‐grade metamorphism and partial melting of basic and intermediate rocks

Rocks of basic and intermediate bulk composition occur in orogenic terranes from all geological time periods and are thought to represent significant petrological components of the middle and lower continental crust. However, the former lack of appropriate thermodynamic models for silicate melt, amphibole and clinopyroxene that can be applied to such lithologies at high temperature has inhibited effective phase equilibrium modelling of their petrological evolution during amphibolite‐ and granulite facies metamorphism. In this work, we present phase diagrams calculated in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O₂ (NCKFMASHTO) compositional system for a range of natural basic and intermediate bulk compositions for conditions of 2–12 kbar and 600–1050 ^°C using newly parameterized activity–composition relationships detailed in a companion paper by Green et al. in this issue. Particular attention is given to mid‐ocean ridge basalt (MORB) and diorite protolith bulk compositions. Calculated subsolidus mineral assemblages in all basic and intermediate rock types are modally dominated by hornblende and plagioclase, with variable proportions of epidote, clinopyroxene, garnet, biotite, muscovite, quartz, titanite or ilmenite present at different pressures. The H₂O‐saturated (wet) solidus has a negative P?T slope and occurs between ～620–690 ^°C at mid‐ to lower‐crustal pressures of 5–10 kbar. The lowest‐T melts generated close to the wet solidus are calculated to have granitic major‐element oxide compositions. Melting at higher temperature is attributed primarily to multivariate hydrate‐breakdown reactions involving biotite and/or hornblende. Partial melt compositions calculated at 800–1050 ^°C for MORB show good correlation with analysed compositions of experimental glasses produced via hydrate‐breakdown melting of natural and synthetic basic protoliths, with Niggli norms indicating that they would crystallize to trondhjemite or tonalite. Diorite is shown to be significantly more fertile than MORB and is calculated to produce high‐T melts (>800 ^°C) of granodioritic composition. Subsolidus and suprasolidus mineral assemblages show no significant variation between different members of the basalt family, although the P?T conditions at which orthopyroxene stabilizes, thus defining the prograde amphibolite–granulite transition, is strongly dependent on bulk‐rock oxidation state and water content. The petrological effects of open‐ and closed‐system processes on the mineral assemblages produced during prograde metamorphism and preserved during retrograde metamorphism are also examined via a case‐study analysis of a natural Archean amphibolite from the Lewisian Complex, northwest Scotland.     

The effect of TiO2 and Fe2O3 on metapelitic assemblages at greenschist and amphibolite facies conditions: mineral equilibria calculations in the system K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–Fe2O3

Mineral equilibria calculations in the system K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃ (KFMASHTO) using thermocalc and its internally consistent thermodynamic dataset constrain the effect of TiO₂ and Fe₂O₃ on greenschist and amphibolite facies mineral equilibria in metapelites. The end‐member data and activity–composition relationships for biotite and chloritoid, calibrated with natural rock data, and activity–composition data for garnet, calibrated using experimental data, provide new constraints on the effects of TiO₂ and Fe₂O₃ on the stability of these minerals. Thermodynamic models for ilmenite–hematite and magnetite–ulvospinel solid solutions accounting for order–disorder in these phases allow the distribution of TiO₂ and Fe₂O₃ between oxide minerals and silicate minerals to be calculated. The calculations indicate that small to moderate amounts of TiO₂ and Fe₂O₃ in typical metapelitic bulk compositions have little effect on silicate mineral equilibria in metapelites at greenschist to amphibolite facies, compared with those calculated in KFMASH. The addition of large amounts of TiO₂ to typical pelitic bulk compositions has little effect on the stability of silicate assemblages; in contrast, rocks rich in Fe₂O₃ develop a markedly different metamorphic succession from that of common Barrovian sequences. In particular, Fe₂O₃‐rich metapelites show a marked reduction in the stability fields of staurolite and garnet to higher pressures, in comparison to those predicted by KFMASH grids.     

Phase equilibria modelling of residual migmatites and granulites: An evaluation of the melt‐reintegration approach

Suprasolidus continental crust is prone to loss and redistribution of anatectic melt to shallow crustal levels. These processes ultimately lead to differentiation of the continental crust. The majority of granulite facies rocks worldwide has experienced melt loss and the reintegration of melt is becoming an increasingly popular approach to reconstruct the prograde history of melt‐depleted rocks by means of phase equilibria modelling. It involves the stepwise down‐temperature reintegration of a certain amount of melt into the residual bulk composition along an inferred P–T path, and various ways of calculating and reintegrating melt compositions have been developed and applied. Here different melt‐reintegration approaches are tested using El Hoyazo granulitic enclaves (SE Spain), and Mt. Stafford residual migmatites (central Australia). Various sets of P–T pseudosections were constructed progressing step by step, to lower temperatures along the inferred P–T paths. Melt‐reintegration was done following one‐step and multi‐step procedures proposed in the literature. For El Hoyazo granulites, modelling was also performed reintegrating the measured melt inclusions and matrix glass compositions and considering the melt amounts inferred by mass–balance calculations. The overall topology of phase diagrams is pretty similar, suggesting that, in spite of the different methods adopted, reintegrating a certain amount of melt can be sufficient to reconstruct a plausible prograde history (i.e. melting conditions and reactions, and melt productivity) of residual migmatites and granulites. However, significant underestimations of melt productivity may occur and have to be taken into account when a melt‐reintegration approach is applied to highly residual (SiO₂ <55 wt%) rocks, or to rocks for which H₂O retention from subsolidus conditions is high (such as in the case of rapid crustal melting triggered by mafic magma underplating).     

Mineral equilibria constraints on open‐system melting in metamafic compositions

The recent development of activity–composition relations for mineral and melt phases in high‐grade metamafic rocks allows mineral equilibria tools to be used to further aid our understanding of partial melting and the mineralogical consequences of melt segregation in these rocks. We show that bulk compositional data from natural amphibolites cover a wide compositional range, with particular variability in the content and ratios of Ca, Na and K indicating that low‐grade metasomatic alteration can substantially alter the igneous protolith chemistry and potentially affect the volume and composition of melt generated. Mineral equilibria calculations for five samples that span the compositional variability in our data set indicate that melting occurs primarily via the fluid‐absent breakdown of amphibole+quartz to produce a pressure‐sensitive peritectic assemblage of augite, orthopyroxene and/or garnet. The introduction of orthopyroxene at the onset of the amphibolite‐to‐granulite‐facies transition at lower pressure results in an increased rate of melt production until quartz is typically exhausted, and this is similarly seen for the introduction of garnet at higher pressure. Calculated melt compositions are dependent on the protolith composition, but initial solidus melting and biotite breakdown produce 1–3 mol.% of K‐rich granitic melts. As hornblende melting proceeds, 15–20 vol.% of either more granodioritic‐to‐tonalitic or granodioritic‐to‐trondhjemitic melt is produced. Once quartz is exhausted, intermediate to mafic melt compositions are produced at ultrahigh‐temperature conditions. Quartz‐rich lithologies with high Ca coupled to low Na and K are the most fertile under orogenic conditions, yielding up to 25 mol.% of sub‐alkalic granitic melt by 850°C. Such rocks did not experience significant subsolidus alteration. Altered compositions with low Ca and elevated Na and K are not as fertile, yielding less than 15 mol.% of alkalic granitic melt by 850°C. These melt volumes are enough to be segregated, and can make a contribution to granite magmatism and intracrustal differentiation that should not be overlooked.     

Separating metamorphic events in the Fosdick migmatite–granite complex,West Antarctica

The Fosdick migmatite–granite complex in West Antarctica records evidence for two high‐temperature metamorphic events, the first during the Devonian–Carboniferous and the second during the Cretaceous. The conditions of each high‐temperature metamorphic event, both of which involved melting and multiple melt‐loss events, are investigated using phase equilibria modelling during successive melt‐loss events, microstructural observations and mineral chemistry. In situ SHRIMP monazite and TIMS Sm–Nd garnet ages are integrated with these results to constrain the timing of the two events. In areas that preferentially preserve the Devonian–Carboniferous (M₁) event, monazite grains in leucosomes and core domains of monazite inclusions in Cretaceous cordierite yield an age of c. 346 Ma, which is interpreted to record the timing of monazite growth during peak M₁ metamorphism (～820–870 °C, 7.5–11.5 kbar) and the formation of garnet–sillimanite–biotite–melt‐bearing assemblages. Slightly younger monazite spot ages between c. 331 and 314 Ma are identified from grains located in fractured garnet porphyroblasts, and from inclusions in plagioclase that surround relict garnet and in matrix biotite. These ages record the growth of monazite during garnet breakdown associated with cooling from peak M₁ conditions. The Cretaceous (M₂) overprint is recorded in compositionally homogeneous monazite grains and rim domains in zoned monazite grains. This monazite yields a protracted range of spot ages with a dominant population between c. 111 and 96 Ma. Rim domains of monazite inclusions in cordierite surrounding garnet and in coarse‐grained poikiloblasts of cordierite yield a weighted mean age of c. 102 Ma, interpreted to constrain the age of cordierite growth. TIMS Sm–Nd ages for garnet are similar at 102–99 Ma. Mineral equilibria modelling of the residual protolith composition after Carboniferous melt loss and removal of inert M₁ garnet constrains M₂ conditions to ～830–870 °C and ～6–7.5 kbar. The modelling results suggest that there was growth and resorption of garnet during the M₂ event, which would facilitate overprinting of M₁ compositions during the M₂ prograde metamorphism. Measured garnet compositions and Sm–Nd diffusion modelling of garnet in the migmatitic gneisses suggest resetting of major elements and the Sm–Nd system during the Cretaceous M₁ overprint. The c. 102–99 Ma garnet Sm–Nd ‘closure’ ages correspond to cooling below 700 °C during the rapid exhumation of the Fosdick migmatite–granite complex.