Cordierite as a sensor of fluid conditions in high-grade metamorphism and crustal anatexis

Cordierite H₂O and CO₂ volatile saturation surfaces derived from recent experimental studies are presented for P–T conditions relevant to high‐grade metamorphism and used to evaluate fluid conditions attending partial melting and granulite formation. The volatile saturation surfaces and saturation isopleths for both H₂O and CO₂ in cordierite are strongly pressure dependent. In contrast, the uptake of H₂O by cordierite in equilibrium with melts formed through biotite dehydration melting, controlled by the distribution of H₂O between granitic melt and cordierite, D_w[D_w = wt% H₂O (melt)/wt% H₂O(Crd)], is mainly temperature dependent. D_w = 2.5–6.0 for the H₂O contents (0.4–1.6 wt percentage) typical of cordierite formed through biotite dehydration melting at 3–7 kbar and 725–900 °C. This range in D_w causes a 15–30% relative decrease in the total wt% of melt produced from pelites. Cordierite in S‐type granites are H₂O‐rich (1.3–1.9 wt%) and close to or saturated in total volatiles, signifying equilibration with crystallizing melts that achieved saturation in H₂O. In contrast, the lower H₂O contents (0.6–1.2 wt percentage) preserved in cordierite from many granulite and contact migmatite terranes are consistent with fluid‐absent conditions during anatexis. In several cases, including the Cooma migmatites and Broken Hill granulites, the cordierite volatile compositions yield a_H2O values (0.15–0.4) and melt H₂O contents (2.2–4.4 wt%) compatible with model dehydration melting reactions. In contrast, H₂O leakage is indicated for cordierite from Prydz Bay, Antarctica that preserve H₂O contents (0.5–0.3 wt%) which are significantly less than those required (1.0–0.8 wt%) for equilibrium with melt at conditions of 6 kbar and 860 °C. The CO₂ contents of cordierite in migmatites range from negligible (< 0.1 wt%) to high (0.5–1.0 wt%), and bear no simple relationship to preserved cordierite H₂O contents and a_H2O. In most cases the cordierite volatile contents yield total calculated fluid activities (a_H2O + a_CO2) that are significantly less than those required for fluid saturation at the P–T conditions of their formation. Whether this reflects fluid absence, dilution of H₂O and CO₂ by other components, or leakage of H₂O from cordierite is an issue that must be evaluated on a case‐by‐case basis.     

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.     

Partial melting in the Inzie Head gneisses: the role of water and a petrogenetic grid in KFMASH applicable to anatectic pelitic migmatites

A sequence of prograde isograds is recognized within the Dalradian Inzie Head gneisses where pelitic compositions have undergone variable degrees of partial melting via incongruent melting reactions consuming biotite. Three leucosome types are identified. At the lowest grades, granitic leucosomes containing porphyroblasts of cordierite (CRD‐melt) are abundant. At intermediate grades, CRD‐melt mingles with garnetiferous leucosomes (GT‐melt). At the highest grades, CRD‐melt coexists with orthopyroxene‐bearing leucosomes (OPX‐melt), while garnet is conspicuously absent. The prograde metamorphic field gradient is constrained to pressures of 2–3 kbar below the CRD‐melt isograd, and no greater than 4.5 kbar at the highest grade around Inzie Head. A petrogenetic grid, calculated using thermocalc , is presented for the K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O (KFMASH) system for the phases orthopyroxene, garnet, cordierite, biotite, sillimanite, H₂O and melt with quartz and K‐feldspar in excess. For the implied field gradient, the reaction sequence predicted by the grid is consistent with the successive prograde development of each leucosome type. Compatibility diagrams suggest that, as anatexis proceeded, bulk compositions may have been displaced towards higher MgO content by the removal of (relatively) ferroan granitic leucosome. An isobaric (P = 4 kbar) T–a_H2O diagram shows that premigmatization fluids must have been water‐rich (a_H2O > 0.85) and suggests that, following the formation of small volumes of CRD‐melt, the system became fluid‐absent and melting reactions buffered a_H2O to lower values as temperatures rose. GT‐ and OPX‐melt formed by fluid‐absent melting reactions, but a maximum of 7–11% CRD‐melt fraction can be generated under fluid‐absent conditions, much less than the large volumes observed in the field. There is strong evidence that the CRD‐melt leucosomes could not have been derived by buoyantly aided upwards migration from levels beneath the migmatites. Their formation therefore required a significant influx of H₂O‐rich fluid, but in a quantity insufficient to have exhausted the buffering capacity of the solid assemblage plus melt. Fluid : rock ratios cannot have exceeded 1 : 30. The fluid was channelled through a regionally extensive shear zone network following melt‐induced failure. Such an influx of fluid at such depths has obvious consequences for localized crustal magma production and possibly for cordierite‐bearing granitoids in general.     

Reactive flow of mixed CO2–H2O fluid and progress of calc-silicate reactions in contact metamorphic aureoles: insights from two-dimensional numerical modelling

Previous models of hydrodynamics in contact metamorphic aureoles assumed flow of aqueous fluids, whereas CO₂ and other species are also common fluid components in contact metamorphic aureoles. We investigated flow of mixed CO₂–H₂O fluid and kinetically controlled progress of calc‐silicate reactions using a two‐dimensional, finite‐element model constrained by the geological relations in the Notch Peak aureole, Utah. Results show that CO₂ strongly affects fluid‐flow patterns in contact aureoles. Infiltration of magmatic water into a homogeneous aureole containing CO₂–H₂O sedimentary fluid facilitates upward, thermally driven flow in the inner aureole and causes downward flow of the relatively dense CO₂‐poor fluid in the outer aureole. Metamorphic CO₂‐rich fluid tends to promote upward flow in the inner aureole and the progress of devolatilization reactions causes local fluid expulsion at reacting fronts. We also tracked the temporal evolution of P‐T‐X_CO2conditions of calc‐silicate reactions. The progress of low‐ to medium‐grade (phlogopite‐ to diopside‐forming) reactions is mainly driven by heat as the CO₂ concentration and fluid pressure and temperature increase simultaneously. In contrast, the progress of the high‐grade wollastonite‐forming reaction is mainly driven by infiltration of chemically out‐of‐equilibrium, CO₂‐poor fluid during late‐stage heating and early cooling of the inner aureole and thus it is significantly enhanced when magmatic water is involved. CO₂‐rich fluid dominates in the inner aureole during early heating, whereas CO₂‐poor fluid prevails at or after peak temperature is reached. Low‐grade metamorphic rocks are predicted to record the presence of CO₂‐rich fluid, and high‐grade rocks reflect the presence of CO₂‐poor fluid, consistent with geological observations in many calc‐silicate aureoles. The distribution of mineral assemblages predicted by our model matches those observed in the Notch Peak aureole.     

Granulite facies metamorphism and subsolidus fluid-absent reworking, Strangways Range, Arunta Block, central Australia

Orthopyroxene‐rich quartz‐saturated granulites of the Strangways Range, Arunta Block, central Australia, record evidence of two high‐grade metamorphic events. Initial granulite facies metamorphism (M₁, at c. 1.7 Ga) involved partial melting and migmatization culminating in conditions of 8.5 kbar and 850 °C. Preservation of the peak M₁ mineral assemblages from these conditions indicates that most of the generated melt was lost from these rocks at or near peak metamorphic conditions. Subsequent reworking (M₂, at c. 1.65 Ga) is characterized by intense deformation, the absence of partial melting and the development of orthopyroxene–sillimanite ± gedrite‐bearing mineral assemblages. Gedrite is only present in cordierite‐rich lithologies where it preferentially replaces M₁ cordierite porphyroblasts. Pseudosection calculations indicate that M₂ occurred at subsolidus fluid‐absent conditions (a_H2o ～ 0.2) at 6–7.5 kbar and 670–720 °C. The mineral assemblages in the reworked rocks are consistent with closed system behaviour with respect to H₂O subsequent to M₁ melt loss. M₂ reworking was primarily driven by increased temperature from the stable geotherm reached after cooling from M₁ and deformation‐induced recrystallization and re‐equilibration, rather than rehydration from an externally derived fluid. The development of the M₂ assemblages is strongly dependent on the intensity of deformation, not only for promoting equilibration, but also for equalizing the volume changes that result from metamorphic reactions. Calculations suggest that the protoliths of the orthopyroxene‐rich granulites were cordierite–orthoamphibole gneisses, rather than pelites, and that the unusual bulk compositions of these rocks were inherited from the protoliths. Melt loss is insufficient to account for the genesis of these rocks from more typical pelitic compositions. In quartz‐rich gneisses, however, melt loss along the M₁ prograde path was able to modify the bulk rock composition sufficiently to stabilize peak metamorphic assemblages different from those that would have otherwise developed.     

Anatexis and fluid regime of the deep continental crust: New clues from melt and fluid inclusions in metapelitic migmatites from Ivrea Zone (NW Italy)

We investigate the inclusions hosted in peritectic garnet from metapelitic migmatites of the Kinzigite Formation (Ivrea Zone, NW Italy) to evaluate the starting composition of the anatectic melt and fluid regime during anatexis throughout the upper amphibolite facies, transition, and granulite facies zones. Inclusions have negative crystal shapes, sizes from 2 to 10 μm and are regularly distributed in the core of the garnet. Microstructural and micro‐Raman investigations indicate the presence of two types of inclusions: crystallized silicate melt inclusions (i.e., nanogranitoids, NI), and fluid inclusions (FI). Microstructural evidence suggests that FI and NI coexist in the same cluster and are primary (i.e., were trapped simultaneously during garnet growth). FI have similar compositions in the three zones and comprise variable proportions of CO₂, CH₄, and N₂, commonly with siderite, pyrophyllite, and kaolinite, suggesting a COHN composition of the trapped fluid. The mineral assemblage in the NI contains K‐feldspar, plagioclase, quartz, biotite, muscovite, chlorite, graphite and, rarely, calcite. Polymorphs such as kumdykolite, cristobalite, tridymite, and less commonly kokchetavite, were also found. Rehomogenized NI from the different zones show that all the melts are leucogranitic but have slightly different compositions. In samples from the upper amphibolite facies, melts are less mafic (FeO + MgO = 2.0–3.4 wt%), contain 860–1700 ppm CO₂ and reach the highest H₂O contents (6.5–10 wt%). In the transition zone melts have intermediate H₂O (4.8–8.5 wt%), CO₂ (457–1534 ppm) and maficity (FeO + MgO = 2.3–3.9 wt%). In contrast, melts at granulite facies reach highest CaO, FeO + MgO (3.2–4.7 wt%), and CO₂ (up to 2,400 ppm), with H₂O contents comparable (5.4–8.3 wt%) to the other two zones. Our results represent the first clear evidence for carbonic fluid‐present melting in the Ivrea Zone. Anatexis of metapelites occurred through muscovite and biotite breakdown melting in the presence of a COH fluid, in a situation of fluid–melt immiscibility. The fluid is assumed to have been internally derived, produced initially by devolatilization of hydrous silicates in the graphitic protolith, then as a result of oxidation of carbon by consumption of Fe³⁺‐bearing biotite during melting. Variations in the compositions of the melts are interpreted to result from higher T of melting. The H₂O contents of the melts throughout the three zones are higher than usually assumed for initial H₂O contents of anatectic melts. The CO₂ contents are highest at granulite facies, and show that carbon‐contents of crustal magmas are not negligible at high T. The activity of H₂O of the fluid dissolved in granitic melts decreases with increasing metamorphic grade. Carbonic fluid‐present melting of the deep continental crust represents, together with hydrate‐breakdown melting reactions, an important process in the origin of crustal anatectic granitoids.     

Fluid‐fluxed melting and melt loss in a syntectonic contact metamorphic aureole from the Variscan eastern Pyrenees

Open‐system behaviour through fluid influx and melt loss can produce a variety of migmatite morphologies and mineral assemblages from the same protolith composition. This is shown by different types of granulite facies migmatite from the contact aureole of the Ceret gabbro–diorite stock in the Roc de Frausa Massif (eastern Pyrenees). Patch, stromatic and schollen migmatites are identified in the inner contact aureole, whereas schollen migmatites and residual melanosomes are found as xenoliths inside the gabbro–diorite. Patch and schollen migmatites record D1 and D2 structures in folded melanosome and mostly preserve the high‐T D2 in granular or weakly foliated leucosome. Stromatic migmatites and residual melanosomes only preserve D2. The assemblage quartz–garnet–biotite–sillimanite–cordierite±K‐feldspar–plagioclase is present in patch and schollen migmatites, whereas stromatic migmatites and residual melanosomes contain a sub‐assemblage with no sillimanite and/or K‐feldspar. A decrease in X _Fe (molar Fe/(Fe + Mg)) in garnet, biotite and cordierite is observed from patch migmatites through schollen and stromatic migmatites to residual melanosomes. Whole‐rock compositions of patch, schollen and stromatic migmatites are similar to those of non‐migmatitic rocks from the surrounding area. These metasedimentary rocks are interpreted as the protoliths of the migmatites. A decrease in the silica content of migmatites from 63 to 40 wt% SiO₂ is accompanied by an increase in Al₂O₃ and MgO+FeO and by a depletion in alkalis. Thermodynamic modelling in the NCKFMASHTO system for the different types of migmatite provides peak metamorphic conditions ~7–8 kbar and 840 °C. A nearly isothermal decompression history down to 5.5 kbar was followed by isobaric cooling from 840 °C through 690 °C to lower temperatures. The preservation of granulite facies assemblages and the variation in mineral assemblages and chemical composition can be modelled by ongoing H₂O‐fluxed melting accompanied by melt loss. The fluids were probably released by the crystallizing gabbro–diorite, infiltrating the metasedimentary rocks and fluxing melting. Release of fluids and melt loss were probably favoured by coeval deformation (D2). The amount of melt remaining in the system varied considerably among the different types of migmatite. The whole‐rock compositions of the samples, the modelled compositions of melts at the solidus at 5.5 kbar and the residues show a good correlation.     

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.     

Cordierite as an indicator of thermodynamic conditions of petrogenesis

A refined thermodynamic model of H₂O and CO₂ bearing cordierite based on recent data on volatile incorporation into cordierite (Thompson et al. in Contrib Mineral Petrol 142:107–118, 2001; Harley and Carrington in J Petrol 42:1595–1620, 2001) reflects non-ideality of channel H₂O and CO₂ mixing. The dependence of cordierite H₂O and CO₂ contents on P, T and equilibrium fluid composition has been calculated for the range 600–800°C and 200–800 MPa. It has been used for establishing thermodynamic conditions of cordierite formation and the following retrograde P–T paths of cordierite rocks from many localities. Estimates of the H₂O and CO₂ activities have shown that cordierites in granites, pegmatites and high-pressure granulites were formed in fluid-saturated conditions and wide range of H₂O/CO₂ relations. Very low cordierite H₂O contents in many migmatites may be caused not only by fluid-undersaturated conditions at rock formation and H₂O leakage on retrograde P–T paths but also by the presence of additional volatile components like CH₄ and N₂. The pressure dependence of cordierite-bearing mineral equilibria on fluid H₂O/CO₂ relations has been evaluated.     

Melting and melt segregation in the aureole of the Glenmore Plug, Ardnamurchan

Contact metamorphism caused by the Glenmore plug in Ardnamurchan, a magma conduit active for 1 month, resulted in partial melting, with melt now preserved as glass. The pristine nature of much of the aureole provides a natural laboratory in which to investigate the distribution of melt. A simple thermal model, based on the first appearance of melt on quartz–feldspar grain boundaries, the first appearance of quartz paramorphs after tridymite and a plausible magma intrusion temperature, provides a time‐scale for melting. The onset of melting on quartz–feldspar grain boundaries was initially rapid, with an almost constant further increase in melt rim thickness at an average rate of 0.5–1.0 × 10^?9 cm s^?1. This rate was most probably controlled by the distribution of limited amounts of H₂O on the grain boundaries and in the melt rims. The melt in the inner parts of the aureole formed an interconnected grain‐boundary scale network, and there is evidence for only limited melt movement and segregation. Layer‐parallel segregations and cross‐cutting veins occur within 0.6 m of the contact, where the melt volume exceeded 40%. The coincidence of the first appearance of these signs of the segregation of melt in parts of the aureole that attained the temperature at which melting in the Qtz–Ab–Or system could occur, suggests that internally generated overpressure consequent to fluid‐absent melting was instrumental in the onset of melt movement.     

Silica depleted melting of pelites. Petrogenetic grid and application to the Susqueda Aureole, Spain

Metapelitic rocks in the low pressure contact metamorphic aureole around the Susqueda igneous complex, Spain show a number of features that make them an ideal testing ground for the modelling of silica‐undersaturated melting. Rocks in the aureole experienced localized depletion in silica by the segregation of quartz veins during a pre‐anatectic, regional cordierite‐andalusite grade metamorphic event. These rocks were then intruded by gabbroic to dioritic rocks of the Susqueda igneous complex that formed a migmatitic contact metamorphic aureole in the country rocks. This migmatisation event caused quartz‐saturated hornfels and restite formation in rocks that had experienced no quartz vein segregation in the previous regional metamorphic event, but silica‐undersaturated melting in those rocks that were previously depleted in silica. Silica‐undersaturated melting is investigated using a new petrogenetic P–T projection and equilibrium pseudosections calculated in the KFMASH and NCKFMASH systems, respectively. The grid considers quartz absent equilibria and a range of phases that form typically in silica‐undersaturated bulk compositions, for example corundum. It is shown that the quartz‐rich precursors in the Susqueda contact aureole produced about 10% melt during contact metamorphism. However, most of this melt was extracted leaving behind rocks with restitic bulk compositions and minor leucosome segregation. It is suggested that the melt mixed with the host igneous rocks causing an apparent magmatic zoning from diorite in the centre of the complex to tonalite at the margins. In contrast, the quartz‐poor precursors (from which the quartz veins segregated) melted in the silica‐undersaturated field producing a range of assemblages including peritectic corundum and spinel. Melting of the silica‐undersaturated rocks produced only negligible melt and no subsequent melt loss.     

Phase equilibria for graphitic metapelite including solution of CO2 in melt and cordierite: implications for dehydration,partial melting and graphite precipitation

When graphite is present, carbon‐bearing species dissolve in the C‐O‐H fluid and lower the activity of water (). Accordingly, metamorphic reactions that involve water, namely dehydration and partial melting reactions, adjust their P–T positions to accommodate the change of . In this modelling study, pseudosections are calculated for graphite‐bearing systems that are either closed or that progressively lose fluid and/or melt. The diagrams incorporate a new model of CO₂ solubility in felsic melts that we derived to be compatible with a recently published melt model. As the result of the lowered in the carbon‐bearing systems, the temperature displacements of the solidus can be as large as 50 °C at low pressures in cordierite‐bearing zones (<4 kbar), but are smaller than 15 °C at mid‐pressure P–T conditions (4–9 kbar). In the supersolidus region, the phase relations among silicate minerals + melt are very close to those in carbon‐free systems. The fluid CO₂ content increases as temperature increases in the supersolidus assemblages. The CO₂‐rich fluid can be stable in granulite facies conditions in an oxidized system. In graphitic systems, melt and/or cordierite dominate the CO₂ budget of high‐grade rocks. During cooling, the fluid that exsolves from such crystalizing melt is CO₂‐rich. In addition to the phase relations, the pseudosections presented in this study enable researchers to quantitatively investigate the evolution of phase modes, including graphite, along specific metamorphic P–T paths. At low pressures in the cordierite stability field, graphite is predicted to precipitate as the pressure increases or temperature decreases in the subsolidus assemblages, or temperature increases in the region of melt + fluid coexistence. On the other hand, the graphite abundance remains nearly constant along the mid‐pressure P–T series, but the graphite mode in the supersolidus region may increase due to residual enrichment if the melt is extracted. The modelling results show that metamorphic processes in closed systems lead to only small changes in graphite mode (a few tenths of a per cent). This strongly suggests that open‐system behaviours are required for large amounts of graphite deposition, including fluid infiltration and mixing or residual enrichment processes in high‐grade rocks. In addition to P–T pseudosections, P/T–X_O diagrams (X_O = O/(H + O) in the fluid) illustrate the thermodynamic features of internal buffering from another perspective, and explore the dependence of phase relations on the externally imposed redox state. If the system is equilibrated with CO₂ or CH₄‐rich infiltrating fluid, the temperature displacements of metamorphic reactions can be larger than 50 °C, compared with carbon‐free systems.     

Textural evolution and partial melting of arkose in a contact aureole: a case study and implications

Recognition of partial melting in metamorphic rocks is a difficult task, as leucosomes can have a variety of origins. By comparing the observed values of the solid-solid dihedral angles with the known equilibrium values, and close examination of the shapes and compositions of feldspar grains, it is possible to unequivocally identify melt textures. Textural relations in a series of meta-arkose samples from the contact aureole of the Ballachulish Igneous Complex in the Scottish Highlands demonstrate that, when former melt pockets are not highly deformed, their presence can be recognized petrographically, by detailed examination of textures on the grain scale. Identification of melt textures and their distribution in the Ballachulish aureole has led to appreciation of the fundamental role of magmatically derived H₂O in producing the partial melting. It has also allowed calculation of the H₂O flux involved, and recognition that fractures were the major fluid pathways during metamorphism.     

Role of fluids in migmatites: CO2-H2O fluid inclusions in leucosomes from the Deep Freeze Range migmatites (Terra Nova Bay, Antarctica)

ABSTRACT The metasedimentary sequence of the Deep Freeze Range (northern Victoria Land, Antarctica) experienced high-T/low-F metamorphism during the Cambro-Ordovician Ross orogeny. The reaction Bt + Sil + Qtz = Grt + Crd + Kfs + melt was responsible for the formation of migmatites. Peak conditions were c. 700–750° C, c. 3.5–5 kbar and x_H2Oc. 0.5). Distribution of fluid inclusions is controlled by host rock type: (1) CO₂-H₂O fluid inclusions occur only in graphite-free leucosomes; (2) CO₂–CH₄± H₂O fluid inclusions are the most common type in leucosomes, and in graphite-bearing mesosomes and gneiss; and (3) CO₂–N₂–CH₄ fluid inclusions are observed only in the gneiss, and subordinately in mesosomes. CO₂–H₂O mixtures (41% CO₂, 58% H₂O, 1% Nad mol.%) are interpreted as remnants of a synmig-matization fluid; their composition and density are compatible P–T–a_H2O conditions of migmatization (c. 750° C, c. 4 kbar, x_H2Oc. 0.5). CO₂-H₂O fluid in graphite-free leucosomes cannot originate via partial melting of graphite-bearing mesosomes in a closed system; this would have produced a mixed CO₂–CH₄ fluid in the leucosomes by a reaction such as Bt + Sil + Qtz + C ± H₂O = Grt + Crd + Kfs + L + CO₂+ CH₄. We conclude that an externally derived oxidizing CO₂-H₂O fluid was present in the middle crust and initiated anatexis. High-density CO₂-rich fluid with traces of CH₄ characterizes the retrograde evolution of these rocks at high temperatures and support isobaric cooling (P–T anticlockwise path). In unmigmatized gneiss, mixed CO₂–N₂–CH₄ fluid yields isochores compatible with peak metamorphic conditions (c. 700–750° C, c. 4–4.5 kbar); they may represent a peak metamorphic fluid that pre-dated the migmatization.     

High to ultrahigh temperature contact metamorphism and dry partial melting of the Tasiuyak paragneiss,Northern Labrador

Contact aureoles of the anorthositic to granitic plutons of the Mesoproterozoic Nain Plutonic Suite (NPS), Labrador, are particularly well developed in the Palaeoproterozoic granulite facies, metasedimentary, Tasiuyak gneiss. Granulite facies regional metamorphism (M_R), c. 1860 Ma, led to biotite dehydration melting of the paragneiss and melt migration, leaving behind biotite‐poor, garnet–sillimanite‐bearing quartzofeldspathic rocks. Subsequently, Tasiuyak gneiss within a c. 1320 Ma contact aureole of the NPS was statically subjected to lower pressure, but higher temperature conditions (M_C), leading to a second partial melting event, and the generation of complex mineral assemblages and microstructures, which were controlled to a large extent by the textures of the M_R assemblage. This control is clearly seen in scanning electron microscopic images of thin sections and is further supported by phase equilibria modelling. Samples collected within the contact aureole near Anaktalik Brook, west of Nain, Labrador, mainly consist of spinel–cordierite and orthopyroxene–cordierite (or plagioclase) pseudomorphs after M_R sillimanite and garnet, respectively, within a quartzofeldspathic matrix. In addition, some samples contain fine‐grained intergrowths of K‐feldspar–quartz–cordierite–orthopyroxene inferred to be pseudomorphs after osumulite. Microstructural evidence of the former melt includes (i) coarse‐grained K‐feldspar–quartz–cordierite–orthopyroxene domains that locally cut the rock fabric and are inferred to represent neosome; (ii) very fine‐ to medium‐grained cordierite–quartz intergrowths interpreted to have formed by a reaction involving dissolution of biotite and feldspar in melt; and (iii) fine‐scale interstitial pools or micro‐cracks filled by feldspar interpreted to have crystallized from melt. Ultrahigh temperature (UHT) conditions during contact metamorphism are supported by (i) solidus temperatures >900 °C estimated for all samples, coupled with extensive textural evidence for contact‐related partial melting; (ii) the inferred (former) presence of osumilite; and (iii) titanium‐in‐quartz thermometry indicating temperatures within error of 900 °C. The UHT environment in which these unusual textures and minerals were developed was likely a consequence of the superposition of more than one contact metamorphic event upon the already relatively anhydrous Tasiuyak gneiss.     

The metamorphic evolution of metapelitic granulites from Radok Lake, northern Prince Charles Mountains, east Antarctica; evidence for an anticlockwise P–T path

Mineral textures in metapelitic granulites from the northern Prince Charles Mountains, coupled with thermodynamic modelling in the K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃ (KFMASHTO) model system, point to pressure increasing with increasing temperature on the prograde metamorphic path, followed by retrograde cooling (i.e. an anticlockwise P–T path). Textural evidence for the increasing temperature part of the path is given by the breakdown of garnet and biotite to form orthopyroxene and cordierite in sillimanite‐absent rocks, and through the break‐down of biotite and sillimanite to form spinel, cordierite and garnet in more aluminous assemblages. This is equated to the advective addition of heat from the regional emplacement of granitic and charnockitic magmas dated at c. 980 Ma. A subsequent increase in pressure, inferred from the break‐down of spinel and quartz to sillimanite, cordierite and garnet in aluminous rocks, is attributed to crustal thickening related to upright folding dated at 940–910 Ma. The terrane attained peak metamorphic temperatures of c. 880 °C at pressures of c. 6.0–6.5 kbar during this event. Subsequent cooling is inferred from the localised breakdown of cordierite and garnet to form biotite and sillimanite that developed in the latter stages of the same event. The textural observations described are interpreted via the application of P–T and P–T–X pseudosections. The latter show that most rock compositions preserve only fragments of the overall P–T path; a result of different rock compositions undergoing mineral assemblage changes, or changes in mineral modal abundance, on different sections of the P–T path. The results also suggest that partial melting during granulite facies metamorphism, coupled with melt loss and dehydration, initiated a switch from pervasive ductile, to discrete ductile/brittle deformation, during retrograde cooling.     

A stable isotope study of the migmatitic rocks in the Ballachulish contact aureole, Scotland

The highest grade pelitic and semipelitic rocks of the Ballachulish aureole are dominantly potash feldspar + cordierite + biotite hornfelses with widely variable amounts of quartz, plagioclase, andalusite, sillimanite and corundum (together with accessory phases). On a microscopic scale these hornfelses show textural evidence of the presence of melt, whilst on a mesoscopic scale they contain a variety of leucosomes. Oxygen isotope studies have been carried out on both whole rocks and mineral separates in order to: (1) assess the sources of molten and volatile constituents and (2) determine the extents of isotopic homogenization and equilibration. Data from localities with both restricted and extensive evidence of leucosomes and melt development are compared, as well as one locality with petrographic evidence of melt incursion from the igneous complex. The whole-rock δ¹⁸O values of the leucosomes (10.5–14.9%.) are in general similar to the immediately adjacent mesosomes (9.9–14.5%.) which are typically cordierite- and feldspar-rich hornfelses. Isotopic evidence is thus consistent with an in-situ partial melt origin for the leucosomes, without the substantial addition of externally derived components. In the area of extensive melt development, the ‘chaotic zone’, it is possible there was addition of an H₂O-rich fluid phase (6-13 wt%) from the igneous complex which resulted in a slight lowering of δ¹⁸O values by 0.5–1.0%. Quartz mineral separates were used to assess the degree of local isotopic homogenization. In the extensively molten area (chaotic zone) there is extensive homogenization between rock layers (quartz δ¹⁸O usually within 1.0%), whilst in less molten areas δ¹⁸O quartz has a range of c. 3.0%. The greater homogenization in the chaotic zone is attributed to the increased degree of melting and infiltration of H₂O-rich fluid from the igneous complex.     

Melt inclusion constraints on volatile systematics and degassing history of the 2014–2015 Holuhraun eruption,Iceland

The mass of volatiles emitted during volcanic eruptions is often estimated by comparing the volatile contents of undegassed melt inclusions, trapped in crystals at an early stage of magmatic evolution, with that of the degassed matrix glass. Here we present detailed characterisation of magmatic volatiles (H₂O, CO₂, S, Fl and Cl) of crystal-hosted melt and fluid inclusions from the 2014–2015 Holuhraun eruption of the Bárðarbunga volcanic system, Iceland. Based on the ratios of magmatic volatiles to similarly incompatible trace elements, the undegassed primary volatile contents of the Holuhraun parental melt are estimated at 1500–1700 ppm CO₂, 0.13–0.16 wt% H₂O, 60–80 ppm Cl, 130–240 ppm F and 500–800 ppm S. High-density fluid inclusions indicate onset of crystallisation at pressures?≥?0.4 GPa (~?12 km depth) promoting deep degassing of CO₂. Prior to the onset of degassing, the melt CO₂ content may have reached 3000–4000 ppm, with the total magmatic CO₂ budget estimated at  23–55 Mt. SO₂ release commenced at 0.12 GPa (~?3.6 km depth), eventually leading to entrapment of SO₂ vapour in low-density fluid inclusions. We calculate the syn-eruptive volatile release as 22.2 Mt of magmatic H₂O, 5.9–7.7 Mt CO₂, and 11.3 Mt of SO₂ over the course of the eruption; F and Cl release were insignificant. Melt inclusion constraints on syn-eruptive volatile release are similar to estimates made during in situ field monitoring, with the exception of H₂O, where field measurements may be heavily biased by the incorporation of meteoric water.     

Properties of fluids attending variable recrystallization of quartzite during contact metamorphism in the White‐Inyo Range,California

Fluid inclusions in the metamorphic aureole of the Eureka Valley‐Joshua Flat‐Beer Creek (EJB) pluton in the White‐Inyo Range, California, reveal the compositions and origin of fluids that were present during variable recrystallization of quartzite with sedimentary grain shapes to metaquartzite with granoblastic texture. Metamorphosed sedimentary formations, including quartzites, marbles, calcsilicates and schists, became ductile and strongly attenuated in the aureole during growth of the magma chamber. The microstructures of quartzites have an unusual distribution in that within ~250 m from the pluton, where temperatures exceeded 650 °C, they exhibit relict sedimentary grain shapes, only small amount of grain boundary migration (GBM), and crystallographic preferred orientations (CPOs) dominated by <a> slip. At distances >250 m, quartzites were completely recrystallized by GBM and CPOs are indicative of prism [c] slip, characteristics that are typically associated with H₂O‐assisted, high‐T recrystallization. The lack of extensive GBM in the inner aureole can be attributed to rapid replacement of H₂O by CO₂ produced by reaction of quartz grains with calcite cement that also produced interstitial wollastonite. Fluid inclusions in the inner aureole generally occur in margins of quartz grains and are either wholly aqueous (Type 1) or also contain H₂S, CO₂ and CH₄ (Type 2). Type 2 inclusions occur only in some stratigraphic layers. In both inclusion types, NaCl and CaCl₂, in variable proportions, dominate the solutes in the aqueous phase, whereas FeCl₂ and KCl are less abundant solutes. The solutes indicate attainment of a degree of equilibrium with carbonates and schists that are interbedded with the quartzites. Some Types 1 and 2 inclusions in the inner aureole show evidence of decrepitation due to high amounts of strain and/or heating suffered by the host rocks, which suggests that they represent pore fluids that existed in the rocks prior to contact metamorphism. In addition to Type 1 inclusions, outer aureole quartzites also contain inclusions that contain CO₂ vapour bubbles in addition to aqueous phase (Type 3). These inclusions only occur in interiors of granoblastic quartz that was produced by large amounts of GBM. The aqueous phase has identical ranges of first melting and final ice melting temperatures as Type 1 inclusions, suggesting that they have the same solute compositions. These inclusions are thought to represent the interstitial pore H₂O that promoted recrystallization of quartz and reacted with graphite to produce CO₂. Absence of significant amounts of CH₄ in Type 3 inclusions is attributed to elevated fO₂ that was buffered by mineral assemblages in interbedded schists. As opposed to the large amount of CO₂ that was produced by the wollastonite‐forming reaction in the inner aureole to inhibit GBM, the amount of CO₂ produced in the outer aureole by reaction between H₂O and graphite was apparently insufficient to inhibit recrystallization of quartz.     

Heterogeneously entrapped,vapor-rich melt inclusions record pre-eruptive magmatic volatile contents

Silicate melt inclusions (MI) commonly provide the best record of pre-eruptive H₂O and CO₂ contents of subvolcanic melts, but the concentrations of CO₂ and H₂O in the melt (glass) phase within MI can be modified by partitioning into a vapor bubble after trapping. Melt inclusions may also enclose vapor bubbles together with the melt (i.e., heterogeneous entrapment), affecting the bulk volatile composition of the MI, and its post-entrapment evolution. In this study, we use numerical modeling to examine the systematics of post-entrapment volatile evolution within MI containing various proportions of trapped vapor from zero to 95 volume percent. Modeling indicates that inclusions that trap only a vapor-saturated melt exhibit significant decrease in CO₂ and moderate increase in H₂O concentrations in the melt upon nucleation and growth of a vapor bubble. In contrast, inclusions that trap melt plus vapor exhibit subdued CO₂ depletion at equivalent conditions. In the extreme case of inclusions that trap mostly the vapor phase (i.e., CO₂–H₂O fluid inclusions containing trapped melt), degassing of CO₂ from the melt is negligible. In the latter scenario, the large fraction of vapor enclosed in the MI during trapping essentially serves as a buffer, preventing post-entrapment modification of volatile concentrations in the melt. Hence, the glass phase within such heterogeneously entrapped, vapor-rich MI records the volatile concentrations of the melt at the time of trapping. These numerical modeling results suggest that heterogeneously entrapped MI containing large vapor bubbles represent amenable samples for constraining pre-eruptive volatile concentrations of subvolcanic melts.