Calculated phase equilibria in K2O-FeO-MgO-Al2O3-SiO2-H2O for silica-undersaturated sapphirine-bearing mineral assemblages

Silica‐undersaturated, sapphirine‐bearing granulites occur in a large number of localities worldwide. Such rocks have historically been under‐utilized for estimating P–T evolution histories because of limited experimental work, and a consequent poor understanding of the topology and P–T location of silica‐undersaturated mineral equilibria. Here, a calculated P–T projection for sapphirine‐bearing, silica‐undersaturated metapelitic rock compositions is constructed using THERMOCALC for the FeO‐MgO‐Al₂O₃‐SiO₂ (FMAS) and KFMASH (+K₂O + H₂O) chemical systems, allowing quantitative analysis of silica‐undersaturated mineral assemblages. This study builds on that for KFMASH sapphirine + quartz equilibria [Kelsey et al. (2004) Journal of Metamorphic Geology, vol. 22, pp. 559–578]. FMAS equilibria are significantly displaced in P–T space from silicate melt‐bearing KFMASH equilibria. The large number of univariant silica‐undersaturated KFMASH equilibria result in a P–T projection that is topologically more complex than could be established on the basis of experiments and/or natural assemblages. Coexisting sapphirine and silicate melt (with or without corundum) occur down to c. 900 °C in KFMASH, some 100 °C lower than in silica‐saturated compositions, and from pressures of c.≤1 to ≥12 kbar. Mineral compositions and composition ranges for the calculated phases are consistent with natural examples. Bulk silica has a significant effect on the stability of sapphirine‐bearing assemblages at a given P–T, resulting in a wide variety of possible granulite facies assemblages in silica‐undersaturated metapelites. Calculated pseudosections are able to reproduce many naturally occurring silica‐undersaturated assemblages, either within a single assemblage field or as the product of a P–T trajectory crossing several fields. With an understanding of the importance of bulk composition on sapphirine stability and textural development, silica‐undersaturated assemblages may be utilized in a quantitative manner in the detailed metamorphic investigation of high‐grade terranes.     

Experimental study of phase relations involving osumilite in the system K2O-FeO-MgO-Al2O3-SiO2-H2O at high pressure and temperature

Abstract Phase relations and mineral chemistry for garnet (Grt), orthopyroxene (Opx), sapphirine (Spr), water-undersaturated cordierite (Crd), osumilite (Osu), sillimanite (Sil), K-feldspar (Kfs), quartz (Qtz) and a water-undersaturated liquid (Liq) have been determined experimentally in the system KFMASH (K₂O-FeO-MgO-Al₂O₃-SiO₂-H₂O) under low P_H2O and f_O2 conditions. Four compositions have been studied with 100 [Mg/(Mg + Fe)] ranging from 65.6 to 89.7. Based on our experimental data, a P-T grid is derived for the KFMASH system in the presence of quartz, orthopyroxene and liquid. Osumilite has been found in various mineral assemblages from 950 to 1100°C and 7.5 to 11 kbar. In the temperature range 1000-1100°C, the pair Os-Grt is stable over a pressure range of about 3kbar. The divariant reaction Os + Opx = Grt + Kfs + Qtz runs to the right with increasing pressure. Because osumilite is the most magnesian phase it is restricted to Mg-rich compositions at high pressure. The reaction defining the upper pressure stability limit of Os-Grt is located around 11 kbar with a nearly flat dP/dT slope over the temperature range 950–100°C. Over the entire temperature range investigated osumilite is not stable beyond 12 kbar. The data imply a restricted pressure range between 11 and 12 kbar for the stability of the assemblage Os-Opx-Sil-Kfs-Qtz. At 1050°C and above, osumilite occurs in various mineral assemblages together with the high-T pair Spr-Qtz. When coexisting with garnet, orthopyroxene or sapphirine, osumilite is always the most magnesian phase. At 1050 and 1100°C, liquid is invariably the most Fe-rich phase in the run product. Our data support a theoretical P-T grid for the KFMAS system in which osumilite is stable outside the field of the high-T assemblage Spr-Qtz. Moreover, our grid indicates that Os-Opx-Sil-Kfs-Qtz has a more restricted pressure and compositional stability domain than Os-Grt, in agreement with natural occurrences. Osumilite is stable over a large pressure range, such that in Mg-rich rocks, and at high temperature, it can occur at any depth in normal thickness continental crust.     

A calculated petrogenetic grid for the system K2O-FeO-MgO-Al2O3-SiO2-H2O, with particular reference to contact-metamorphosed pelites

A petrogenetic grid is presented for the system KFMASH (K₂O-FeO-MgO-Al₂O₃-SiO₂-H₂O), including biotite, muscovite, K-feldspar, chlorite, chloritoid, staurolite, cordierite, garnet, orthoamphibole, orthopyroxene, spinel, andalusite, sillimanite, kyanite, quartz and corundum with H₂O in excess, which was calculated using the computer program THERMOCALC and the Powell and Holland internally consistent thermodynamic dataset. By removing the normal constraint of having quartz in excess, both quartz-bearing and quartz-absent equilibria are shown. Quartz-absent equilibria are particularly relevant at high- T and low- P conditions, because of their common occurrence at these conditions. The calculated mineral assemblage and mineral compositional variations in terms of FeMg-1 and (Fe, Mg)SiAl_-2 exchange vectors are broadly compatible with observations on natural rocks, particularly when non-KFMASH components are taken into account.     

Calculated mineral equilibria for eclogites in CaO–Na2O–FeO–MgO–Al2O3–SiO2–H2O: application to the Pouébo Terrane, Pam Peninsula, New Caledonia

The high- P , medium- T  Pouébo terrane of the Pam Peninsula, northern New Caledonia includes barroisite- and glaucophane-bearing eclogite and variably rehydrated equivalents. The metamorphic evolution of the Pouébo terrane is inferred from calculated P–T  and P–T  – X H2O pseudosections for bulk compositions appropriate to these rocks in the model system CaO–Na₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O. The eclogites experienced a clockwise P–T  path that reached P ≈19  kbar and T  ≈600  °C. The eclogitic mineral assemblages are preserved because reaction consequent upon decompression consumed the rocks' fluid. Extensive reaction occurred only in rocks with fluid influx during decompression of the Pouébo terrane.     

H2O in metamorphism and unexpected behaviour in the preservation of metamorphic mineral assemblages

The preservation of mineral assemblages that were fluid‐present during their prograde history is primarily related to the consumption of the fluid by growth of more hydrous minerals as the retrograde history begins. The range of behaviour relating to the preservation of mineral assemblages is examined using calculated phase diagrams for fluid‐saturated conditions, contoured for the H₂O content of the mineral assemblage. At equilibrium, as a mineral assemblage crosses contours of decreasing H₂O content along a pressure–temperature path, it dehydrates, the fluid being lost from the rock. If the assemblage crosses contours of increasing H₂O content, the mineral assemblage starts to rehydrate using any fluid on its grain boundaries. When the rock has consumed its fluid, the resulting mineral assemblage is that preserved in the rock. Conditions relating to the preservation of mineral assemblages are discussed, and examples of the consequences of different pressure–temperature paths on preservation in a metapelitic and a metabasic rock composition are considered on phase diagrams calculated with thermocalc .     

Synthetic Fluid Inclusions in the Systems NaCl-H2O and NaCl-CO2-H2O: Dissolution Temperatures of Halite

Abstract. This study examined the effect of CO₂ on NaCl solubility in hydrothermal fluid, with the synthetic fluid inclusion technique. Fluid inclusions of 30–40 wt% NaCl and 5 mol % CO₂ were synthesized, and their halite dissolution temperatures, T_m(halite), were measured. The solubilities of NaCl in CO₂-bearing aqueous fluid were obtained at 160–320C under vapor-saturated pressures. The T_m(halite) value in aqueous fluid with 5 mol % CO₂ obtained in this study agrees with that of Schmidt et al. (1995), showing that 5 mol % CO₂ reduces the solubility of NaCl by about 1 wt%.
Calculation of magnetite solubility suggests that 5–10 mol % CO2 decreases magnetite solubility by 4.5–8.9 % relative to the magnetite solubility in CO2-free solution. Therefore, an increase of CO2 content in ore-forming solutions may cause deposition of iron minerals and produce ore deposits.     

The upper thermal stability of chlorite + quartz: an experimental study in the system MgO-Al2O3-SiO2-H2O

Experiments up to water pressures of 21 kbar have been undertaken to bracket the reactions chlorite + quartz = talc + kyanite + H₂O, chlorite + quartz = talc + cordierite + H₂O, and talc + kyanite + quartz = cordierite ± H₂O by reversed runs in the system MgO-Al₂O₃-SiO₂-H₂O (MASH). These reaction curves intersect at an invariant point (IP1) at PH₂O = 6.4 ± 0.2 kbar and a temperature of 624 ± 4°C. The curve of the chlorite + quartz breakdown to talc + kyanite + H₂O at water pressures above 6.4 kbar shows a negative dP/dT, with the slope decreasing with rising pressure, whereas the slope of the breakdown curve to talc + cordierite + H₂O at water pressures is clearly positive. The composition of the chlorite solid solution reacting with quartz has been estimated to be approximately Mg_4.85Al_1.15[Al_1.15Si_2.85O₁₀](OH)₈ over the entire pressure range investigated. The composition of the talc solid solution forming by the breakdown of chlorite + quartz appears to be Mg_2.94Al_0.06[Al_0.06Si_3.94O₁₀](OH)₂ at PH₂O = 2kbar. With increasing pressure, the Al content of talc decreases, reaching a value of about 0.06 atoms per formula unit at P,H₂O = 21 kbar. As a consequence of the new experimental data, the existing phase topologies of the MASH-system and K₂O-MASH-system have been revised. For example, the invariant point IP1 and the univariant reaction curve kyanite + talc + H₂O = chlorite + cordierite are stable. For this reason, the development of medium- to high-temperature metamorphic rocks compositionally approximating the MASH-system must be reconsidered. The whiteschists from Sar e Sang, Afghanistan, are treated as an example. The application of the present experimental data to metamorphic rocks of more normal composition requires the examination of the influence of further components. This leads to the conclusion that the introduction of Fe²⁺ into magnesian chlorite extends its stability field in the presence of quartz by 10°-15°C in comparison with pure Mg-chlorite.     

Modelling of mineral equilibria in ultrahigh-temperature metamorphic rocks from the Anápolis–Itauçu Complex, central Brazil

A new quantitative approach to constraining mineral equilibria in sapphirine‐bearing ultrahigh‐temperature (UHT) granulites through the use of pseudosections and compatibility diagrams is presented, using a recently published thermodynamic model for sapphirine. The approach is illustrated with an example from an UHT locality in the Anápolis–Itauçu Complex, central Brazil, where modelling of mineral equilibria indicates peak metamorphic conditions of about 9 kbar and 1000 °C. The early formed, coarse‐grained assemblage is garnet–orthopyroxene–sillimanite–quartz, which was subsequently modified following peak conditions. The retrograde pressure–temperature (P–T) path of this locality involves decompression across the FeO–MgO–Al₂O₃–SiO₂ (FMAS) univariant reaction orthopyroxene + sillimanite = garnet + sapphirine + quartz, resulting in the growth of sapphirine–quartz, followed by cooling and recrossing of this reaction. The resulting microstructures are modelled using compatibility diagrams, and pseudosections calculated for specific grain boundaries considered as chemical domains. The sequence of microstructures preserved in the rocks constrains a two‐stage isothermal decompression–isobaric cooling path. The stability of cordierite along the retrograde path is examined using a domainal approach and pseudosections for orthopyroxene–quartz and garnet–quartz grain boundaries. This analysis indicates that the presence or absence of cordierite may be explained by local variation in a_H2O. This study has important implications for thermobarometric studies of UHT granulites, mainly through showing that traditional FMAS petrogenetic grids based on experiments alone may overestimate P–T conditions. Such grids are effectively constant a_H2O sections in FMAS‐H₂O (FMASH), for which the corresponding a_H2O is commonly higher than that experienced by UHT granulites. A corollary of this dependence of mineral equilibria on a_H2O is that local variations in a_H2O may explain the formation of cordierite without significant changes in P–T conditions, particularly without marked decompression.     

Eclogites from the south Tianshan, NW China: petrological characteristic and calculated mineral equilibria in the Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O system

Eclogites from the south Tianshan, NW China are grouped into two types: glaucophane and hornblende eclogites, composed, respectively, of garnet + omphacite + glaucophane + paragonite + epidote + quartz and garnet + omphacite + hornblende (sensu lato) + paragonite + epidote + quartz, plus accessory rutile and ilmenite. These eclogites are diverse both in mineral composition and texture not only between the two types but also among the different selected samples within the glaucophane eclogite. Using thermocalc 3.1 and recent models of activity–composition relation for minerals, a P–T projection and a series of P–T pseudosections for specific samples of eclogite have been calculated in the system Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O (NCFMASH) with quartz and water taken to be in excess. On the basis of these phase diagrams, the phase relations and P–T conditions are well delineated. The three selected samples of glaucophane eclogite AK05, AK11 and AK17 are estimated to have peak P–T conditions, respectively, of 540–550 °C at c. 16 kbar, c. 560 °C at 15–17 kbar and c. 580 °C at 15–19 kbar, and two samples of hornblende eclogite AK10 and AK30 of 610–630 °C and 17–18 kbar. Together with H₂O‐content contours in the related P–T pseudosections and textural relations, both types of eclogite are inferred to show clockwise P–T paths, with the hornblende eclogite being transformed from the glaucophane eclogite assemblage dominantly through increasing temperature.     

Eclogite facies metarodingites – phase relations in the system SiO2-Al2O3-Fe2O3-FeO-MgO-CaO-CO2-H2O: an example from the Zermatt-Saas ophiolite

Eclogite facies metarodingites occur as deformed dykes in serpentinites of the Zermatt‐Saas ophiolite (Western Alps). They formed during the subduction of the Tethys oceanic lithosphere in the Early Tertiary. The metarodingites developed as a consequence of serpentinization of the oceanic mantle. Three major types of metarodingites (R1, R2 & R3) can be distinguished on the basis of their mineralogical composition. All metarodingites contain vesuvianite, chlorite and hydrogrossular in high modal amounts. In addition they contain: R1 – diopside, tremolite, clinozoisite, calcite; R2 – hydroandradite, diopside, epidote, calcite; and R3 – hydroandradite. Both garnets contain a small but persistent amount of hydrogarnet component. The different metarodingites reflect different original dyke rocks in the mantle. In each group of metarodingite, textural relations suggest that reactions adjusted the assemblages along the P–T path travelled by the ophiolite during subduction and exhumation. Reactions and phase relations derived from local textures in metarodingite can be modelled in the eight‐component system: SiO₂‐Al₂O₃‐Fe₂O₃‐FeO‐MgO‐CaO‐CO₂‐H₂O. This permits the analysis of redox reactions in the presence of andradite garnet and epidote in many of the rocks. Within this system, the phase relations in eclogite facies metarodingites have been explored in terms of T–X_CO2, T–μ(SiO₂), μ(Cal)–μ(SiO₂) and P–T sections. It was found that rodingite assemblages are characterized by low μ(SiO₂) and low X_CO2 conditions. The low SiO₂ potential is externally imposed onto the rodingites by the large volume of antigorite‐forsterite serpentinites enclosing them. Moreover, μ(SiO₂) decreases consistently from metarodingite R1 to R3. The low μ(SiO₂) enforced by the serpentinites favours the formation of hydrogarnet and vesuvianite. Rodingite formation is commonly associated with hydrothermal alteration of oceanic lithosphere at the ocean floor, in particular to ocean floor serpentinization. Our analysis, however, suggests that the metarodingite assemblages may have formed at high‐pressure conditions in the subduction zone as a result of serpentinization of oceanic mantle by subduction zone fluids.     

Low-pressure granulite facies metapelitic assemblages and corona textures from MacRobertson Land, east Antarctica: the importance of Fe2O3 and TiO2 in accounting for spinel-bearing assemblages

Low-pressure granulite facies metasedimentary gneisses exposed in MacRobertson Land, east Antarctica, include hercynitic spinel-bearing metapelitic gneisses. Peak metamorphic mineral assemblages include spinel + rutile + ilmenite + sillimanite + garnet, spinel + ilmenite + sillimanite + garnet + cordierite, ortho-pyroxene + magnetite + ilmenite + garnet, spinel + cordierite + biotite + ilmenite and orthopyroxene + cordierite + biotite, each with quartz, K-feldspar and melt. The presence of garnet + biotite- and cordierite + orthopyroxene-bearing assemblages implies crossing tie-lines in AFM projection for the K₂O-FeO-MgO-Al₂O₃-SiO₂-H₂O (KFMASH) system. This apparent contradiction, and the presence of spinel, rutile and ilmenite in the assemblages, is acounted for by using the KFMASH-TiO₂-O₂ system, i.e. AFM + TiO₂+ Fe₂O₃. We derive a petrogenetic grid for this system, applicable to low-pressure granulite facies metamorphic conditions. Retrograde assemblages are interpreted from corona textures on hercynitic spinel and Fe-Ti oxides. The relative positions of the peak and retrograde metamorphic assemblages on the petrogenetic grid suggest that corona development occurred during essentially isobaric cooling.     

FeO*-Al2O3-TiO2-Rich Rocks of the Tertiary Bana Igneous Complex, West Cameroon

FeO*‐Al₂O₃‐TiO₂‐rich rocks are found associated with transitional tholeiitic lava flows in the Tertiary Bana plutono‐volcanic complex in the continental sector of the Cameroon Line. These peculiar rocks consist principally of iron‐titanium oxides, aluminosilicates and phosphates, and occur as layers 1–3 m thick occupying the upper part of lava flows on the southwest (site 1) and northwest (site 2) sites of the complex. Mineral constituents of the rocks include magnetite, ilmenite, hematite, rutile, corundum, andalusite, sillimanite, cordierite, quartz, plagioclase, alkali feldspar, apatite, Fe‐Mn phosphate, Al phosphate, micas and fine mixtures of sericite and silica. Texturally and compositionally, the rocks can be subdivided into globular type, banded type, and Al‐rich fine‐gained massive type. The first two types consist of dark globule or band enriched in Fe‐Ti oxides and apatite and lighter colored groundmass or bands enriched in aluminosilicates and quartz, respectively. The occurrence of andalusite and sillimanite and the compositional relations of magnetite and ilmenite in the FeO*‐Al₂O₃‐TiO₂‐rich rocks suggest temperatures of crystallization in a range of 690–830°C at low pressures. The Bana FeO*‐Al₂O₃‐TiO₂‐rich rocks are characterized by low concentrations of SiO₂ (25–54.2 wt%), Na₂O + K₂O (0–1%), CaO (0–2%) and MgO (0–0.5%), and high concentrations of FeO* (total iron as FeO, 20–42%), Al₂O₃ (20–42%), TiO₂ (3–9.2%), and P₂O₅ (0.26–1.30%). TiO₂ is positively correlated with Al₂O₃ and inversely correlated with FeO*. The bulk rock compositions cannot be derived from the associated basaltic magma by crystal fractionation or by partial melting of the mantle or lower crustal materials. In ternary diagrams of (Al₂O₃)?(CaO + Na₂O + K₂O)?(FeO*+ MnO + MgO) and (SiO₂)?(FeO*)?(Al₂O₃), the compositional field of the rocks is close to that of laterite and is distinct from the common volcanic rocks, suggesting that the rocks are derived from lateritic materials by recrystallization when the materials are heated by the basaltic magmas. A hydrothermal origin is discounted because the rocks contain high‐temperature mineral assemblages and lack sulfide minerals. It is proposed that the FeO*‐Al₂O₃‐TiO₂‐rich rocks of the Bana complex were formed by pyrometamorphism of laterite by the heat of basaltic magmas.     

Singularities in NCKFMASH (Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O)

A new petrogenetic grid is presented for the system NCKFMASH (Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O), in which Ca is incorporated in garnet, and CaAlNa₋₁Si₋₁ solid solution is considered for both the plagioclase and white-mica structures. A compatibility diagram for plagioclase-bearing metapelitic assemblages within the NCKFMASH system also has been derived. A dominant feature of the NCKFMASH grid is the singularities and associated singular reactions which occur along plagioclase+margarite- and plagioclase+paragonite-bearing univariant equilibria. The singularities represent compositional coplanarities which occur in response to the CaAlNa₋₁Si₋₁ substitution occurring at different rates in plagioclase and white-mica. This is controlled by a fundamental difference in the mixing within the two mineral structures. The singularities give rise to a number of intriguing phase diagram features, including azeotropes. From the results presented here, it is predicted that the occurrence of margarite and paragonite in pelitic rocks is controlled by equilibria related to the singularities. The presence of these white-micas is strongly dependent upon bulk composition, and plagioclase-bearing, margarite/paragonite-free assemblages, typical of Barrovian-type terranes, are predicted for bulk compositions of Mg/(Mg+Fe)≈0.4 and Ca/(Ca+Na)≈0.4 at for example 5.5  kbar.     

低温平衡ZnS-PbS-FeS-H_2S四组分体系的热力学分析

本文介绍了热力学相图在浅成低温热液硫化物矿床中的应用,并以三江地区金顶铅锌矿床中的矿物含量为例进行定量分析。一方面在相同温度下,浓度与矿物(组合)之间存在对应关系,并且一些矿物(组合)对应特定的酸碱条件,例如在400K和105Pa条件下,黄铁矿与方铅矿的组合在碱性环境下稳定,而方铅矿与闪锌矿的组合在酸性环境中稳定,且酸性条件下当lg[Pb2+]≥-11.29时,才开始出现方铅矿;另一方面对比了298.15K和400K条件下矿物共生组合的及介质pH值的变化情况,并得到400K条件下形成矿物或矿物组合所需离子的浓度更高。     

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.     

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.     

Review of the systematics of CO2–H2O fluid inclusions

Aqueous solutions that contain volatile (gas) components are one of the most important types of fluid in the Earth's crust. The record that such fluids have left in the form of fluid inclusions in minerals provides a wealth of insight into the geochemical and petrologic processes in which the fluids participated. This article reviews the systematics of CO₂–H₂O fluid inclusions as a starting point for interpreting the chemically more complex systems. The phase relations of the binary are described with respect to a qualitative P–T–X model, and isoplethic–isochoric paths through this model are used to explain the equilibrium and non-equilibrium behaviour of fluid inclusions during microthermometric heating and cooling. The P–T–X framework is then used to discuss the various modes of fluid inclusion entrapment, and how the resulting assemblage textures can be used to interpret the P–T conditions, phase states, and evolution paths of the parent solutions. Finally, quantitative methods are reviewed by which bulk molar volume and composition of CO₂–H₂O fluid inclusions can be determined from microthermometric observations of phase transitions.     

Sapphirine parageneses from the Caraiba complex, Bahia, Brazil: the influence of Fe2+–Fe3+ distribution on the stability of sapphirine in natural assemblages

Abstract Sapphirine-bearing rocks occur in three conformable, metre-size lenses in intrusive quartzo-feldspathic orthogneisses in the Curaçà valley of the Archaean Caraiba complex of Brazil. In the lenses there are six different sapphirine-bearing rock types, which have the following phases (each containing phlogopite in addition): A: Sapphirine, orthopyroxene; B: Sapphirine, cordierite, orthopyroxene, spinel; C: Sapphirine, cordierite; D: Sapphirine, cordierite, orthopyroxene, quartz; E: Sapphirine, cordierite, orthopyroxene, sillimanite, quartz; F: Sapphirine, cordierite, K-feldspar, quartz. Neither sapphirine and quartz nor orthopyroxene and sillimanite have been found in contact, however. During mylonitization, introduction of silica into the three quartz-free rocks (which represent relict protolith material) gave rise to the three cordierite and quartz-bearing rocks. Stable parageneses in the more magnesian rocks were sapphirine–orthopyroxene and sapphirine–cordierite. In more iron-rich rocks, sapphirine–cordierite, sapphirine-cordierite–sillimanite, cordierite–sillimanite, sapphirine–cordierite–spinel–magnetite and quartz–cordierite–orthopyroxene were stable. The iron oxide content in sapphirine of the six rocks increases from an average of 2.0 to 10.5 wt % (total Fe as FeO) in the order: C,F–A,D–B,E. With increase in Fe there is an increase in recalculated Fe₂O₃ in sapphirine. The four rock types associated with the sapphirine-bearing lenses are: I: Orthopyroxene, cordierite, biotite, quartz, feldspar tonalitic to grandioritic gneiss; II: Biotite, quartz, feldspar gneiss; III: Orthopyroxene, clinopyroxene, hornblende, plagioclase meta-norite; IV: Biotite, orthopyroxene, quartz, feldspar, garnet, cordierite, sillimanite granulite gneiss. The stable parageneses in type IV are orthopyroxene–cordierite–quartz, garnet–sillimanite–quartz and garnet–cordierite–sillimanite. Geothermobarometry suggests that the associated host rocks equilibrated at 720–750°C and 5.5–6.5 kbar. Petrogenetic grids for the FMASH and FMAFSH (FeO–MgO–Al₂O₃–Fe₂O₃–SiO₂–H₂O) model systems indicate that sapphirine-bearing assemblages without garnet were stabilized by a high Fe³⁺ content and a high X_Mg= (Mg/ (Mg+Fe²⁺)) under these P–T conditions.     

Charnockitic alteration: evidence for CO2 infiltration in granulite facies metamorphism

Charnockitic alteration (arrested orthopyroxene formation in biotite- and amphibole-bearing rocks) occurs in high-grade terranes of all ages. Three criteria are used to show that this alteration was produced in many locations by a migrating fluid phase: (i) diffuseness of the alteration—the alteration zones are often quite unlike discrete migmatitic veins; (ii) relation to deformation—most occurrences show alteration closely associated with warping of foliation or dilation cracks; (iii) open-system alteration—whilst some occurrences represent nearly isochemical alteration, slight changes in bulk composition, often loss of mafic constituents and gain of Na and Si, are evident in detailed mass-balance analysis. Y and sometimes Rb are characteristically depleted. Partial melting sometimes accompanied volatile infiltration, as evidenced by more discrete veins and euhedral orthopyroxene. It is quite unlikely, however, that open-system alteration was produced by escape of viscous quartzo-feldspathic melts. Pervasive migration of low-T lamprophyric (mafic–alkaline, CO₂-charged) interstitial liquids is a possibility by virtue of their extreme fluidity, but CO₂ infiltration was needed to generate these liquids. Vapour-deficient dehydration melting is another feasible mechanism of orthopyroxene formation which may have operated in conjunction with CO₂ infiltration. Characteristic development of charnockitic alteration in some prograde amphibolite to granulite facies transitions, as in the Dharwar Craton of South India, suggests that the alteration is a fundamental feature of the granulite facies metamorphism, implying active and causal participation of migrating fluids. In other high-grade terranes like the Adirondack Mountains of New York, this kind of alteration is rare, and fluid action does not seem to have been important in the metamorphism. A vapour phase participating in charnockitic metamorphism was necessarily one of relatively low H₂O, therefore presumably rich in CO₂. Consideration of possible large CO₂ sources leads to the conclusion that emanations from volatile-rich basalts emplaced in the lower crust are the most probable source of charnockitizing fluids. The ultimate source would therefore be enriched subcontinental lithosphere or asthenosphere. The Rb-depleted pyroxene gneiss (charnockitic) terranes may be characteristic of zones of large-scale transcurrent or oblique-motion faults which tap such great depths.     

The formation of eclogite facies metatroctolites and a general petrogenetic grid in Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O (NCFMASH)

Eclogite facies metatroctolites from a variety of Western Alps localities (Voltri, Monviso, Lanzo, Allalin, Zermat–Saas, etc.) that preserve textural evidence of their original form as bimineralic olivine‐plagioclase rocks are considered in terms of calculated mineral equilibria in the system Na₂O‐CaO‐FeO‐MgO‐Al₂O₃‐SiO₂‐H₂O (NCFMASH). Pseudosections, based on a new petrogenetic grid for NCFMASH presented here, are used to unravel the metamorphic history of the metatroctolites, considering the rocks to consist of different composition microdomains corresponding to the original olivine and plagioclase grains. On the basis that the preservation of the mineral assemblage in each microdomain will tend to be from where on a rock's P–T path the metamorphic fluid phase is used up via rehydration reactions, P–T pseudosections contoured for water content, and P–T path‐M_H2O (amount of water) pseudosections, are used to examine fluid behaviour in each microdomain. We show that the different microdomains are likely to preserve their mineral assemblages from different places on the P–T path. For the olivine microdomain, the diagnostic mineral assemblage is chloritoid + talc (+ garnet + omphacite). The preservation of this assemblage, in the light of the closed system P–T path‐M_H2O relationships, implies that the microdomain loses its metamorphic fluid as it starts to decompress, and, in the absence of subsequent hydration, the high pressure mineral assemblage is then preserved. In the plagioclase microdomain, the diagnostic assemblage is epidote (or zoisite) + kyanite + quartz suggesting a lower pressure (of about 2 GPa) than for the olivine microdomain. In the light of P–T path‐M_H2O relationships, development of this assemblage implies breakdown of lawsonite across the lawsonite breakdown reaction, regardless of the maximum pressure reached. It is likely that the plagioclase microdomain was mainly fluid‐absent prior to lawsonite breakdown, only becoming fluid‐present across the reaction, then immediately becoming fluid‐absent again.