Pressure and equilibrium in deforming rocks

It is widely proposed that tectonic pressure (the difference between the mean stress and the pressure arising from a lithostatic load) is large, and has a significant influence on mineral phase equilibria in deforming metamorphic rocks. The implication/assertion is that the mean stress is equivalent to the thermodynamic pressure which characterizes mineral phase equilibria and is a measure of how the energy changes as the volume changes. We distinguish two useful thermodynamic pressures. The first is an equilibrium thermodynamic pressure, characteristic of non‐dissipative systems and related directly to equilibrium values of the chemical potentials that define stable, equilibrium phase assemblages. The second is a non‐equilibrium thermodynamic pressure characteristic of dissipative systems with zero net entropy production and related to non‐equilibrium chemical potentials that define stable non‐equilibrium phase assemblages. In many dissipative metamorphic systems discussed in the literature, the concepts of thermodynamic pressure and chemical potential are not usefully defined because the system is not at equilibrium and/or no volume change is involved in the deformation. The conclusion of this note is that the influence of tectonic pressure on phase equilibria is minor. The role of tectonic pressure is an important issue but is only relevant to phase equilibrium when an equilibrium thermodynamic pressure can be defined; in such cases, the influence of tectonic pressure is small compared to many proposals in the literature. Except for elastic deformations, the mean stress is not useful in discussing mineral phase equilibrium.     

An analysis of uncertainty in non-equilibrium and equilibrium geothermobarometry

In statistically optimised P–T estimation, the contributions to overall uncertainty from different sources are represented by ellipses. One source, for a diffusion‐controlled reaction at non‐equilibrium, is diffusion modelling of the reaction texture. This modelling is used to estimate ratios, Q, between free‐energy differences, ΔG, of reactions among mineral end‐members, to replace the equilibrium condition ΔG = 0. The associated uncertainty is compared with those already inherent in the equilibrium case (from end‐member data, activity models and mineral compositions). A compact matrix formulation is introduced for activity coefficients, and their partial derivatives governing error propagation. The non‐equilibrium example studied is a corona reaction with the assemblage Grt–Opx–Cpx–Pl–Qtz. Two garnet compositions are used, from opposite sides of the corona. In one of them, affected by post‐reaction Fe, Mg exchange with pyroxene, the problem of reconstructing the original composition is overcome by direct use of ratios between chemical‐potential differences, given by the diffusion modelling. The number of geothermobarometers in the optimisation is limited by near‐degeneracies. Their weightings are affected by strong correlations among Q ratios. Uncertainty from diffusion modelling is not large in comparison with other sources. Overall precision is limited mainly by uncertainties in activity models. Hypothetical equilibrium P–T are also estimated for both garnet compositions. By this approach, departure from equilibrium can be measured, with statistical uncertainties. For the example, the result for difference from equilibrium pressure is 1.2 ± 0.7 kbar.     

Challenges in high-pressure granulite metamorphism in the era of pseudosections: reaction textures, compositional zoning and tectonic interpretation with examples from the Bohemian Massif

High‐pressure granulites are an important record of geodynamic processes in overthickened or subducted continental crust. Orthopyroxene‐free assemblages in granitic (ternary feldspar(s) + quartz + garnet + kyanite + rutile), intermediate (ternary feldspar(s) + quartz + garnet + clinopyroxene ± kyanite ±rutile ± titanite) and basic (garnet + clinopyroxene + plagioclase ± quartz + rutile) compositions indicate formation conditions at mantle depths. Clinopyroxene compositions in Variscan high‐pressure granulites are unusual in that they include omphacite (in plagioclase‐bearing rocks thus not eclogite) and Al‐rich diopside (i.e. indicating high Ca‐Tschermak content), with both yielding temperatures above 900 °C. Problems such as compositional zoning, multiple generations of key phases in reaction domains and unmixing of high‐temperature solid‐solution phases during cooling (ternary feldspars, omphacite) clearly indicate disequilibrium and require very careful interpretation as to which phases and compositions possibly represent a former equilibrium association. Pressure–temperature (P–T) determination by the pseudosection method, although allowing prediction of mineral assemblages, compositions and molar proportions for a fixed bulk composition for modelled P–T conditions, still requires reliable activity–composition information for the key phases feldspar and clinopyroxene as well as an interpretation of former equilibrium compositions in the investigated samples, i.e. the same restrictions applying to conventional thermobarometry. The interpretations of some recently determined pseudosections for the composition of Variscan clinopyroxene‐bearing high‐pressure granulites contradict numerous published P–T paths. However, quantitative information from thermobarometry or pseudosections must be integrated with key petrographic observations. In the case of the Variscan example, it is argued that petrographic observations and published P–T paths are consistent with mineral assemblages predicted in pseudosections and support existing tectonometamorphic models.     

The lawsonite paradox: a comparison of field evidence and mineral equilibria modelling

Lawsonite equilibria are predicted to occur over a broad P–T spectrum developed during subduction, yet lawsonite‐bearing assemblages are rare. In the context of mafic mineral equilibria modelled for the range of common crustal metamorphism (4–23 kbar, 400–750 °C) using the system Na₂O‐CaO‐K₂O‐FeO‐MgO‐Al₂O₃‐SiO₂‐H₂O and the software thermocalc , unusually high water contents are demanded by lawsonite assemblages. As a consequence, lawsonite assemblages are predicted to have difficulty forming and lawsonite equilibria to be uncommon. Metabasalt undergoing cooler subduction may experience substantial periods involving the metastable persistence of mineral assemblages because of water under‐saturation with non‐occurrence of recrystallization. If formed, lawsonite‐bearing assemblages are observed to be highly unstable; their preservation requires that exhumation be accompanied by substantial cooling. The amount of structurally bound H₂O in minerals plays a critical role in the formation and preservation of mineral assemblages, controlling key changes in rocks undergoing subduction.     

The truth and beauty of chemical potentials

This essay in honour of Mike Brown addresses aspects of chemical equilibrium and equilibration in rocks, with a focus on the role that chemical potentials play. Chemical equilibrium is achieved by diffusive flattening of chemical potential gradients. The idea of equilibration volume is developed, and the way equilibration volumes may evolve along a pressure–temperature path is discussed. The effect of the environment of an equilibration volume is key to understanding the evolution of the equilibration volume with changing conditions. The likely behaviour of equilibration volumes is used to suggest why preservation of equilibrium mineral assemblages and mineral compositions from metamorphism tends to occur. This line of logic then provides the conceptual support to conventional equilibrium thermodynamic approaches to studying rocks, using, for example, thermobarometry and pseudosections.     

Orthopyroxene–sillimanite–quartz assemblages: distribution, petrology, quantitative P–T–X constraints and P–T paths

Granulite facies magnesian metapelites commonly preserve a wide array of mineral assemblages and reaction textures that are useful for deciphering the metamorphic evolution of a terrane. Quantitative pressure, temperature and bulk composition constraints on the development and preservation of characteristic peak granulite facies mineral assemblages such as orthopyroxene + sillimanite + quartz are assessed with reference to calculated phase diagrams. In NCKFMASH and its chemical subsystems, peak assemblages form mainly in high‐variance fields, and most mineral assemblage changes reflect multivariant equilibria. The rarity of orthopyroxene–sillimanite–quartz‐bearing assemblages in granulite facies rocks reflects the need for bulk rock X_Mg of greater than approximately 0.60–0.65, with pressures and temperatures exceeding c. 8 kbar and 850 °C, respectively. Cordierite coronas mantling peak minerals such as orthopyroxene, sillimanite and quartz have historically been used to infer isothermal decompression P–T paths in ultrahigh‐temperature granulite facies terranes. However, a potentially wide range of P–T paths from a given peak metamorphic condition facilitate retrograde cordierite growth after orthopyroxene + sillimanite + quartz, indicating that an individual mineral reaction texture is unable to uniquely define a P–T vector. Therefore, the interpretation of P–T paths in high‐grade rocks as isothermal decompression or isobaric cooling may be overly simplistic. Integration of quantitative data from different mineral reaction textures in rocks with varying bulk composition will provide the strongest constraints on a P–T path, and in turn on tectonic models derived from these paths.     

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 .     

Palaeoclimate indicators (clay minerals,calcareous nannofossils,stable isotopes) compared from two successions in the late Jurassic of the Volga Basin (SE Russia)

A study of clay mineral and calcareous nannofossil abundances in late Jurassic–early Cretaceous sediments from the Volga Basin, SE Russia, is presented. From these results, we are able to compare some general patterns of mineralogical and palaeontological change for the Volga Basin to the palaeoclimate models developed for northern Europe and beyond. The two successions examined comprise calcareous mudstones with black organic‐rich shale horizons, overlain by a series of phosphatic silty sands. Clay mineralogical results show a progressive decrease in kaolinite and the concomitant increase of smectite and illite through the middle Volgian, followed by an abrupt increase in kaolinite in the late Volgian. The clay mineral evidence suggests increasing aridity at the end of the Jurassic, similar, in part, to many western European successions. Because of differential settling of clay minerals, superimposed upon this possible climatic signature is likely to be the effect of relative sea‐level change. Calcareous nannofossil analysis from a single section reveals a shift through the middle Volgian from low nutrient, warm water assemblages dominated by Watznaueria to cooler surface water and high nutrient assemblages dominated by Biscutum constans. These observations suggest that increased aridity is also associated with climatic cooling. Black shales are associated with increased productivity, higher sea levels and increases in smectite content. Hence, periods of low (chemical) hinterland weathering during semi‐arid conditions are paradoxically associated with relatively nutrient‐rich waters, and organic‐rich shales. Comparison of published carbon and oxygen stable isotope results from this and other sections to the clay mineral and nannofossil data confirms the palaeoclimatic interpretation. This study significantly improves the published biostratigraphically constrained clay mineral database for this time period, because other European and North American successions are either non‐marine (and thus poorly dated), absent (through penecontemporaneous erosion) or condensed. Copyright © 2002 John Wiley & Sons, Ltd.     

Delamerian‐aged metamorphism in the southern Curnamona Province,Australia: implications for the evolution of the Mesoproterozoic Olarian Orogeny

Monazite electron microprobe U–Th–Pb and garnet Sm–Nd isotopic data from metapelitic assemblages in the Willyama Supergroup in the southern Curnamona Province, south‐central Australia, indicate that the terrain underwent regional greenschist to amphibolite‐grade metamorphism during the c. 500 Ma Delamerian Orogeny. The Delamerian‐aged mineral assemblages include prograde garnet–staurolite and kyanite‐bearing associations that overprint andalusite‐ and sillimanite‐bearing assemblages that are interpreted to have developed during the c. 1600 Ma Olarian Orogeny. Importantly, the development of secondary kyanite‐bearing assemblages in the southern Curnamona Province has been used previously to suggest that the Olarian Orogeny followed an anticlockwise P–T evolution. If such assemblages are the product of c. 500 Ma metamorphism, then the anticlockwise P–T path is an apparent path, due to the overprint of a distinct metamorphic cycle c. 1100 Ma later. Making such distinctions is therefore extremely important when using the textural and metamorphic evolution of polycyclic terrains to model the thermal behaviour of the crust during orogeny. This study highlights the utility of in situ geochronology, linking age data to petrologically important phases and assemblages.     

Petrogenetic significance of orthopyroxene-free garnet + clinopyroxene + plagioclase ± quartz-bearing metabasites with respect to the amphibolite and granulite facies

Orthopyroxene‐free garnet + clinopyroxene + plagioclase ± quartz‐bearing mineral assemblages represent the paragenetic link between plagioclase‐free eclogite facies metabasites and orthopyroxene‐bearing granulite facies metabasites. Although these assemblages are most commonly developed under P–T conditions consistent with high pressure granulite facies, they sometimes occur at lower grade in the amphibolite facies. Thus, these assemblages are characteristic but not definitive of high pressure granulite facies. Compositional factors favouring their development at amphibolite grade include Fe‐rich mineral compositions, Ca‐rich garnet and plagioclase, and Ti‐poor hornblende. The generalized reaction that accounts for the prograde development of garnet + clinopyroxene + plagioclase ± quartz from a hornblende + plagioclase + quartz‐bearing (amphibolite) precursor is Hbl + Pl + Qtz=Grt + Cpx + liquid or vapour, depending on whether the reaction occurs above or below the solidus. There are significant discrepancies between experimental and natural constraints on the P–T conditions of orthopyroxene‐free garnet + clinopyroxene + plagioclase ± quartz‐bearing mineral assemblages and therefore on the P–T position of this reaction. Semi‐quantitative thermodynamic modelling of this reaction is hampered by the lack of a melt model and gives results that are only moderately successful in rationalizing the natural and experimental data.     

Fractionation of bulk rock composition due to porphyroblast growth: effects on eclogite facies mineral equilibria, Pam Peninsula, New Caledonia

Chemically zoned porphyroblasts in metamorphic rocks indicate that diffusional processes could not maintain equilibrium conditions on a grain scale during porphyroblast growth or establish it afterwards. An effect of this inability to maintain equilibrium is the progressive removal of elements forming garnet cores from any metamorphic reaction that occurs at the porphyroblast boundaries or in the matrix of the rock. To examine this effect on mineral assemblages, the Bence–Albee matrix correction was applied to X‐ray intensity maps collected using eclogite samples from northern New Caledonia in order to determine the chemical composition of all parts of the sample. The manipulation of these element maps allows a quantitative analysis of the fractionation of the bulk rock composition between garnet cores and the matrix. A series of calculated equilibrium‐volume compositions represents the change in matrix chemistry with progressive elemental fractionation as a consequence of prograde garnet growth under high‐P conditions. Pressure–temperature pseudosections are calculated for these compositions, in the CaO–Na₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O system. Assemblages, modal proportions and mineral textures observed in the New Caledonian eclogites can be closely modelled by progressively ‘removing’ elements forming garnet cores from the bulk rock composition. The pseudosections demonstrate how chemical fractionation effects the peak metamorphic assemblage, prograde textures and the development of retrograde assemblages.     

Calculated phase equilibria for low- and medium-pressure metapelites in the KFMASH and KMnFMASH systems

Petrogenetic grids in the KFMASH and KMnFMASH model systems calculated with the software thermocalc 3.1 are presented for the P–T range 0.5–12 kbar and 450–900 °C, for assemblages involving garnet, muscovite, chloritoid, biotite, chlorite, staurolite, cordierite, spinel, orthopyroxene, K‐feldspar, Al₂SiO₅ phases, quartz, water and melt. Based on calculated compatibility diagrams and P–T and T–M_Mn [Mn/(Mg + Fe + Mn)] pseudosections for different metapelitic bulk compositions, the principal conclusions are that the addition of Mn to the KFMASH system: (i) enhances the stability of garnet, and, to a lesser extent, aluminosilicates; (ii) reduces the stability of staurolite, cordierite and, to a lesser extent, chlorite; and (iii) extends the medium pressure stability of muscovite and the low‐P stability field of K‐feldspar. The influence of Mn on individual mineral stabilities is strongly related to rock composition, in particular, to the relative contents of Al₂O₃ and K₂O. For metapelites of a range of compositions and M_Mn values, P–T pseudosections in the KFMASH system, in most cases, do not adequately predict the mineral assemblages observed in natural assemblages under medium and low‐pressure conditions. In contrast, the P–T pseudosections in the KMnFMASH system generally provide more satisfactory results, suggesting that MnO is one of the non‐KFMASH components that should not be neglected in documenting the phase equilibria of medium‐ and low‐P metapelites.     

The metamorphic history of rocks buried,accreted and exhumed in an accretionary prism: an example from the Otago Schist,New Zealand

Although subgreenschist facies metamorphic rocks are widespread in the upper crust, mineralogical processes affecting these rocks are poorly understood. Subgreenschist mineralogical transitions have been invoked as critical controls on the mechanical behaviour of rocks within the crustal seismogenic zone, calling for further study of very low‐grade metamorphic assemblages. In this study a multi‐technique thermobarometric study of the Chrystalls Beach Complex mélange, which is located within the Otago Schist accretion‐collision assemblage of the South Island of New Zealand, is presented. The Chrystalls Beach Complex comprises highly sheared trench‐fill sedimentary rocks and scattered pillow basalts, and is inferred to have formed during Jurassic subduction under the paleo‐Pacific Gondwana margin. Equilibrium mineral assemblages indicate peak P–T conditions in the range 400–550 MPa and 250–300 °C, which is supported by chlorite thermometry. Relatively high pressures of burial and accretion during foliation development are inferred from phengite content and b₀ spacing analyses of white mica. Rare lawsonite occurs in a post‐foliation vein, and illite ‘crystallinity’ measurements indicate a thermal overprint during exhumation. These P–T estimates and their relative chronology indicate that the mineral assemblages developed along a clockwise P–T path. Based on variability in P–T estimates from different techniques, mineral assemblages developed during burial are largely overprinted during exhumation at similar or higher‐T than experienced along the prograde path. Observed subduction‐related subgreenschist assemblages are therefore likely to indicate lower‐P than experienced during subduction, as higher‐P mineral compositions re‐equilibrate during exhumation. The P–T path inferred in this study is similar in shape to P–T paths for higher grade parts of the Otago Schist, and other exhumed accretionary prisms around the world, and is therefore probably common for rocks buried, accreted and exhumed in accretionary prisms.     

Kinetic control of staurolite–Al2SiO5 mineral assemblages: Implications for Barrovian and Buchan metamorphism

The distribution and textural features of staurolite–Al₂SiO₅ mineral assemblages do not agree with predictions of current equilibrium phase diagrams. In contrast to abundant examples of Barrovian staurolite–kyanite–sillimanite sequences and Buchan‐type staurolite–andalusite–sillimanite sequences, there are few examples of staurolite–sillimanite sequences with neither kyanite nor andalusite anywhere in the sequence, despite the wide (~2.5 kbar) pressure interval in which they are predicted. Textural features of staurolite–kyanite or staurolite–andalusite mineral assemblages commonly imply no reaction relationship between the two minerals, at odds with the predicted first development (in a prograde sense) of kyanite or andalusite at the expense of staurolite in current phase diagrams. In a number of prograde sequences, the incoming of staurolite and either kyanite, in Barrovian sequences, or andalusite, in Buchan‐type sequences, is coincident or nearly so, rather than kyanite or andalusite developing upgrade of a significant staurolite zone as predicted. The width of zones of coexisting staurolite and either kyanite, in Barrovian sequences, or andalusite, in Buchan‐type sequences, is much wider than predicted in equilibrium phase diagrams, and staurolite commonly persists upgrade until its demise in the sillimanite zone. We argue that disequilibrium processes provide the best explanation for these mismatches. We suggest that kyanite (or andalusite) may develop independently and approximately contemporaneously with staurolite by metastable chlorite‐consuming reactions that occur at lower P–T conditions than the thermodynamically predicted staurolite‐to‐kyanite/andalusite reaction, a process that involves only modest overstepping (<15°C) of the stable chlorite‐to‐staurolite reaction and which is favoured, in the case of kyanite, by advantageous nucleation kinetics. If so, the pressure difference between Barrovian kyanite‐bearing sequences and Buchan andalusite‐bearing sequences could be ~1 kbar or less, in better agreement with the natural record. The unusual width of coexistence of staurolite and Al₂SiO₅ minerals, in particular kyanite and andalusite, can be accounted for by a combination of lack of thermodynamic driving force for conversion of staurolite to kyanite or andalusite, sluggish dissolution of staurolite, and possibly the absence of a fluid phase to catalyse reaction. This study represents an example of how kinetic controls on metamorphic mineral assemblage development have to be considered in regional as well as contact metamorphism.     

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.     

Chloritoid–glaucophane schist in the north Qilian orogen, NW China: phase equilibria and P–T path from garnet zonation

Chloritoid–glaucophane‐bearing rocks are widespread in the high‐pressure belt of the north Qilian orogen, NW China. They are interbedded and cofacial with felsic schists originated from greywackes, mafic garnet blueschists and low‐T eclogites. Two representative chloritoid–glaucophane‐bearing assemblages are chloritoid + glaucophane + garnet + talc + quartz (sample Q5‐49) and chloritoid + glaucophane + garnet + phengite + epidote + quartz (sample Q5‐12). Garnet in sample Q5‐49 is coarse‐, medium‐ and fine‐grained and shows two types of zonation patterns. In pattern I, X_grs is constant as X_py rises, and in pattern II X_grs decreases as X_py rises. Phase equilibrium modelling in the NC(K)MnFMASH system with Thermocalc 3.25 indicates that pattern I can be formed during progressive metamorphism in lawsonite‐stable assemblages, while pattern II zonation can be formed with further heating after lawsonite has been consumed. Garnet growth in Q5‐49 is consistent with a continuous progressive metamorphic process from ～14.5 kbar at 470 °C to ～22.5 kbar at 560 °C. Garnet in sample Q5‐12 develops with pattern I zonation, which is consistent with a progressive metamorphic process from ～21 kbar at 540 °C to ～23.5 kbar at 580 °C with lawsonite present in the whole garnet growth. The latter sample shows the highest P–T conditions of the reported chloritoid–glaucophane‐bearing assemblages. Phase equilibrium calculation in the NCKFMASH system with a recent mixing model of amphibole indicates that chloritoid + glaucophane paragenesis does not have a low‐pressure limit of 18–19 kbar as previously suggested, but has a much larger pressure range from 7–8 to 27–30 kbar, with the low‐pressure part being within the stability field of albite.     

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.     

Isobaric cooling and anti-clockwise P–T paths in the Variscan Odenwald Crystalline Complex, Germany

Mineral assemblages in Al₂O₃‐rich, SiO₂‐ and K₂O‐poor metapelitic rocks from the western Odenwald Crystalline Complex (Variscan Mid‐German Crystalline Rise, southern Germany) include corundum, spinel, cordierite, sillimanite, garnet and staurolite. Quartz is absent from almost all samples. Therefore, the applicability of conventional geothermobarometry is very limited or even impossible. Detailed petrographic investigation on selected samples permits inference of the sequence of appearance and disappearance of several mineral assemblages. The recognition of such partial re‐equilibration stages and their associated mineral assemblages, together with mineral stabilities predicted from KFMASH pseudosections, enables the determination of the pressure‐temperature (P–T) trajectories experienced by these rocks during the Variscan metamorphism. The rocks were metamorphosed under low‐P/high‐T conditions and underwent an anti‐clockwise P–T evolution. A pressure increase from about 2 kbar to 4 ± 0.5 kbar was accompanied by heating. Peak metamorphic conditions were reached at pressures of 4 ± 0.5 kbar and temperatures of at least 640 °C, probably even higher. The retrograde evolution is characterised by near‐isobaric cooling from ≥ 640 °C to approximately 550 °C. The rocks underwent the anti‐clockwise evolution in a subduction‐related magmatic arc setting. The close spatial association of the low‐P/high‐T rocks with recently discovered metabasic eclogites in the eastern part of the Odenwald Crystalline Complex may indicate a fossil paired metamorphic belt in the Central European Variscides.     

Matrix analysis of metamorphic mineral assemblages and reactions

Assemblage diagrams are widely used in interpreting metamorphic mineral assemblages. In simple systems, they can help to identify assemblages which may represent equilibrium states; to determine whether differences between assemblages reflect changes in metamorphic grade or variations in bulk composition; and to characterize isograd reactions. In multicomponent assemblages these questions can be approached by investigating the rank, composition space (range) and reaction space (null-space) of a matrix representing the compositions of the phases involved. Singular value decomposition (SVD) provides an elegant way of (1) finding the rank of a matrix and detemining orthonormal bases for both the composition space and the reaction space needed to represent an assemblage or pair of assemblages; and (2) finding a model matrix of specified rank which is closest in a least squares sense to an observed assemblage. Although closely related to least squares techniques, the SVD approach has the advantages that it tolerates errors in all observations and is computationally simpler and more stable than non-linear least squares algorithms. Models of this sort can be used to interpret multicomponent mineral assemblages by straightforward generalizations of the methods used to interpret assemblage diagrams in simpler systems. SVD analysis of mineral assemblages described by Lang and Rice (1985) demonstrates the utility of the approach.     

Up-temperature flow of surface-derived fluids in the mid-crust: the role of pre-orogenic burial of hydrated fault rocks

The Walter‐Outalpa shear zone in the southern Curnamona Province of NE South Australia is an example of a shear zone that has undergone intensely focused fluid flow and alteration at mid‐crustal depths. Results from this study have demonstrated that the intense deformation and ductile shear zone reactivation, at amphibolite facies conditions of 534 ± 20 °C and 500 ± 82 MPa, that overprint the Proterozoic Willyama Supergroup occurred during the Delamerian Orogeny (c. 500 Ma) (EPMA monazite ages of 501 ± 16 and 491 ± 19 Ma). This is in contrast to the general belief that the majority of basement deformation and alteration in the southern Curnamona Province occurred during the waning stages of the Olarian Orogeny (c. 1610–1580 Ma). These shear zones contain hydrous mineral assemblages that cut wall rocks that have experienced amphibolite facies metamorphism during the Olarian Orogeny. The shear zone rock volumes have much lower δ¹⁸O values (as low as 1‰) than their unsheared counterparts (7–9‰), and calculated fluid δ¹⁸O values (5–8‰) consistent with a surface‐derived fluid source. Hydrous minerals show a decrease in δD_(H2O) from ?14 to ?22‰, for minerals outside the shear zones, to ?28 to ?40‰, for minerals within the shear zones consistent with a contribution from a meteoric source. It is unclear how near‐surface fluids initially under hydrostatic pressure penetrate into the middle crust where fluid pressures approach lithostatic, and where fluid flow is expected to be dominantly upward because of pressure gradients. We propose a mechanism whereby faulting during basin formation associated with the Adelaidean Rift Complex (c. 700 Ma) created broad hydrous zones containing mineral assemblages in equilibrium with surface waters. These panels of fault rock were subsequently buried to depths where the onset of metamorphism begins to dehydrate the fault rock volumes evolving a low δ¹⁸O fluid that is channelled through shear zones related to Delamerian Orogenic activity.