New data on the kinetics of dehydration of muscovite + quartz suggest the necessity for a careful treatment of both surface kinetics and diffusion processes in metamorphic reactions. A new model is proposed that illustrates the relative role of diffusion and surface reactions in the overall metamorphic process. The rate law for the reaction at mineral surfaces derived from the experimental data is shown to be probably non-linear and similar to rate laws derived from Monte Carlo calculations. The experimental rate data is then used in a heat flow calculation to model the evolution of the muscovite isograd in the field. The position of the isograd, the temperature oversteps above equilibrium, and the width of ‘reaction zones’ are then analysed as a function of intrusion size and kinetic parameters.

A proportion of the heat added to a body of rock during prograde metamorphism will be absorbed in the chemical work of metamorphic recrystallization. When and where heat is so absorbed will affect the exact thermal histories of the rocks, and hence the metamorphic textures. This paper reports the results of modelling of the inter-relations between reaction progress and thermal histories in a rock column. The results suggest that volumes of rock undergoing reaction at any moment act as heat sinks and absorb heat from the surrounding rock, that reaction generally takes place close to the temperature at which nucleation took place, and that steady heating of a rock pile can give rise to a reaction history in which spurts of reaction are separated by ‘quiet’, non-reactive intervals.

Transmission electron microscopy and analytical electron microscopy have been used to study the breakdown reaction of muscovite during pyrometa-morphism. The transformation has been shown to be topotactic in nature, with the orientations of the product biotite and alkali feldspar being strongly controlled by the precursor phase. Microprobe investigations indicate that the reaction is probably isochemical with no detectable interaction with adjacent phases. Chemical analyses of the products carried out by AEM have enabled a possible balanced reaction to be calculated. It is proposed that the spatial distribution of the product minerals can be interpreted in terms of diffusion of species from one domain in the crystal to another over distances of 5 to 10 µm as a result of chemical potential gradients which develop during the reaction. The reaction probably occurred under conditions of declining temperature between 900 and 750 °C over a period of 4–5 days. This time period was insufficient to enable the reaction to reach completion as indicated by the presence of relics of muscovite coexisting with K-feldspar, corundum, biotite, hercynite, and mullite.

The problems of characterizing inter-granular regions and of estimating rates of intergranular diffusion in metamorphic rocks are discussed. Inter-granular regions can be anhydrous, hydrated but under-saturated with H2O, or saturated with H2O, but only in the latter case can a free aqueous fluid phase be present. Estimates of intergranular diffusion coefficients (DIGR) at 550°C derived from a variety of published experimental work, vary from ∼ 10−8 m2 s−1 for diffusion of species through an intergranular fluid film to ⩽ 4 × 10−24 m2 s−1 for diffusion of SiO2 or O in anhydrous grain boundaries in quartzite. Estimates of DIGR for hydrated grain boundaries vary from ∼ 10−13 m2 s−1 to ∼ 10−21 m2 s−1; the concentration of H2O in the grain boundaries and the identity of the diffusing species (generally unknown) may be important controlling factors, and there exists the possibility of a spectrum of values between these two extremes.

Using available kinetic data it is shown that a free aqueous fluid could never have been present in parts of the basement terrane of the Sesia Zone (Western Alps) during uplift from the eclogite facies, except possibly late in the cooling history. The breakdown of sodic pyroxene + quartz occurred in response to the localized infiltration of catalytic aqueous fluid, possibly over a time interval as short as 6–6000 a, and possibly under conditions remote from equilibrium. H2O-present conditions during a dehydration reaction in metapelites of the Adula nappe (central Alps) could also have been of short duration. These examples are consistent with a model in which basement rocks at deep crustal levels are dry for long periods of time and in which the development of equilibrium mineral assemblages and microstructures generally occurs over relatively short periods of time under transitory fluid-present conditions (caused by devolatilization and/or infiltration).

Gabbros and dolerites in the Western Gneiss Region of Norway have been subjected to a high P-T regime and preserve evidence of the existence of several stages in the consequent reaction sequence. Incomplete reaction stages are characterized by corona structures between relict igneous phases and by frequent pseudo-morphs after igneous olivine, plagioclase and augite. The increasing degree of reaction is recorded by successive increases of modal garnet, omphacite and phlogopite (±orthopyroxene) to produce eclogite, often with excellent pseudomorphic preservation of the igneous fabric.

Pseudomorphic replacement of olivine by orthopyroxene (in coronas and aggregates) and of plagioclase by local assemblages of garnet, spinel, and sodic plagioclase, is interpreted as a transient reaction stage with restricted and selective diffusion between the original mafic and felsic domains. Complete eclogitization is compatible with more extensive diffusion, especially of Na and Al (on a mm scale) leading to omphacite production by replacement of olivine, augite, and orthopyroxene. Concomitant reactions in the felsic domains lead to total replacement of the transient phases by garnet, with or without inclusions of minute omphacite grains.

Strong Ca zoning of garnet in the coronites is inter-preted as a relict growth zoning, attributed to local controls by diffusion and subreactions in the plagioclase host and to local garnet + plagioclase + spinel equilibria. In contrast, complete eclogitization is associated with diffusional homogenization of garnet by (Mg, Fe)Ca−1 and MgFe−1 exchange with omphacite ± phlogopite.

Textures produced by reactions involving garnet in a sillimanite-staurolite schist have been investigated using an irreversible thermodynamic model. The model predicts that the local production or consumption of garnet is strongly influenced by the proximity of garnet to growing sillimanite and dissolving staurolite. Garnets within sillimanite segregations should dissolve near the sillimanite-bearing centre of the segregation while garnets within or adjacent to staurolite poikilo-blasts should grow as the staurolite is replaced by a muscovite-rich pseudomorph. Garnets located in the matrix may grow, not react at all, or dissolve depending on the local configuration of nearby sillimanite, staurolite, and garnet. Textures predicted by the model are similar to those observed in thin section: many garnets are truncated within sillimanite segregations; garnets located in pseudo-morphs after staurolite are equant and have thick unpoikilitic rims that suggest growth; most matrix garnets also have thick inclusion-free rims that suggest growth but a few have thin rims, indicating little growth, or are irregularly shaped, suggesting dissolution.

Coronas of symplectic pargasite [XMg = 68, XCa = 69, XSi = 68] + spinel [SP45] and orthopyroxene [EN70] separate cumulus plagioclase [AN64] and olivine [FO64] in troctolitic gabbro from Risör, Norway. Coronas with a primary microstructure characterized by low-angle grain boundaries have the mineral assemblage layer sequence,

PLAGIOCLASE : PARGASITE + SPINEL : ORTHOPYROXENE + SPINEL : ORTHOPYROXENE : OLIVINE, whereas those with an annealed microstructure have the layer sequence,

PLAGIOCLASE : PARGASITE + SPINEL : PARGASITE : ORTHOPYROXENE : OLIVINE.

Primary symplectite consists of fan-shaped grains of pargasite that open toward plagioclase and are ribbed by rods of spinel. On annealing to a single grain, low-angle grain boundaries disappear and spinel rods rotate into parallel positions. Primary orthopyroxene, initially radial to layer contacts, anneals to a single grain, rimming olivine. Irregular discontinuous layers and plumes of symplectic orthopyroxene+spinel disappear on annealing and a monomineralic layer of pargasite forms between orthopyroxene and the amphibole symplectite.

The identity of composition of intercumulus pargasite and orthopyroxene with the same phases in primary coronas, the occurrence of primary and annealed coronas rimming cumulus ilmenite and the occurrence of radial orthopyroxene separating grains of cumulus olivine and separating cumulus olivine and plagioclase argue for the origin of primary coronas by fractional crystallization of spinel-saturated troctolitic magma at a pressure greater than 5 kbar.

Irreversible thermodynamic calculations show that the mineral assemblage layer sequence of the primary coronas is diffusionally unstable and that this instability provides the driving force for their spontaneous transformation to the stable mineral assemblage layer sequence of the annealed coronas.

The data of Joesten (1986) are re-interpreted. The petrography of the coronas is not consistent with magrnatic origin. Both microstructural types described by Joesten (1986), here re-named ‘columnar’ and ‘tabular’, formed by solid-state replacement of plagioclase and of adjacent olivine or ilmenite. Tabular microstructures are not annealed, but result from overgrowth or epitaxy of amphibole and pyroxene on pre-existing grains. Since the diffusion-controlled models of Joesten (1986) can account for major aspects of the coronas, it seems possible that a slightly modified, less simplified theory might explain them fully. Open-system behaviour must be admitted, with some constraints provided by symplectites. It may also be necessary to develop the theory in more than one dimension, and to allow for departures from local equilibrium at layer boundaries.

Permian basic/ultrabasic lavas from south-west England may be divided into a ‘basaltic’ and a K-rich group. Both groups have enrichment of large-ion lithophile (LIL) elements relative to high field strength (HFS) elements, and the K-rich group show large degrees of LIL enrichment (c.50–500 times primordial mantle) in association with varied transition element concentrations. Samples from both groups 87Sr/86Sri = 0.704–0.705 and 143Nd/144Ndi = 0.5123–0.5127 and plot close to the mantle array on an ɛSr−ɛNd diagram. These data are interpreted in terms of derivation of the lavas from magmas resulting from partial melting of mantle which had experienced less (for the basaltic group) or more (for the K-rich group) enrichment in LIL elements as a result of migration of mantle melts. Such enrichment accompanied or followed subduction of oceanic lithosphere below south-west England. The resultant magmas experienced fractional crystallization of olivine and pyroxene prior to eruption.

Chemically complex pyroxenes which occur in early Proterozoic tholeiitic dolerite dykes in southern West Greenland have been investigated using back-scattered electron (BSE) imagery, X-ray mapping and electron microprobe analysis. A wide variety of compositions occur within individual pyroxene grains in these rocks. They can be explained by simultaneous nucleation of different pyroxenes, the evolution of domains around these nucleii as a response to differential chemical gradients and the sequential precipitation of different pyroxenes at progressively lower temperatures. As an example, the individual grains in one dyke sample contain domains of bronzite, hypersthene, magnesium pigeonite, augite, and subcalcic augite. Olivine in this sample varies in composition from Fo70 to Fo33, although individual grains are only weakly zoned. The wide variation in pyroxene and olivine compositions suggests ranges of crystallization temperatures from c.1250° to as low as 825°C. Such compositionally variable pyroxenes are possibly characteristic of hypabyssal tholeiitic rocks.

Rare earth minerals in ankeritic ferrocar-bonatite and associated magnetite ore, as well as in hematite-calcite-(dolomite) carbonatite (rødberg) derived from the ferrocarbonatite by post-magmatic alteration, have been studied by electron microprobe. The minerals found are monazite, parisite, and bastnäsite (identifications confirmed by X-ray diffraction) as well as an aluminous silicate with allanite composition, and possibly, synchysite. The rare earth element (REE) distribution patterns of the minerals change from light rare earth (LREE)-enriched in magnetite ore and ferrocarbonatite to less LREE-enriched, or middle REE-enriched in the most strongly re-equilibrated carbonatites. Two distinct mineral varieties, monazite-(Ce,Nd) and a Nd-fluorocarbonate, have been found in rødberg. The LREE were leached from their host minerals during re-equilibration of the carbonatite, most likely because of the influence of fluoride-bearing hydrothermal solutions.

Two compounds with the chemical composition Ca2.32Mn0.68Si2.00O7 were synthesized from a molten carbonating silicate with the melilite composition. The synthetic samples were subsequently characterized by X-ray powder diffraction, IR absorption and EPMA, and they proved to be the anhydrous phases isomorphous with kilchoanite Ca3Si2O7 and åkermanite Ca2MgSi2O7 respectively, and to be polymorphous with each other. Their crystallochemical properties suggest that Mn-åkermanite is a high-temperature structure type of Mn-kilchoanite. Substitution of Mn2+ with an intermediate ionic radius between those of Mg2+ and Ca2+ cations establishes the polymorphic relationship between åkermanite Ca2MgSi2O7 and kilchoanite Ca3Si2O7.

Ganophyllite has been shown to have alkali cation exchange capability. Partial cesium exchange for K + Na in large (> 0·3 mm) grains shows that the exchangeable cations migrate parallel to X, the crystallographic direction for the ‘interlayer’ tunnels. Such exchange capability supports the suggestion that the alkali elements are located in zeolite-like sites attached to the sides of the tunnels. Exchange experiments show that complete sodium substitution for potassium is possible also. Eggletonite, the Na analogue of ganophyllite, is shown to have an identical superlattice to ganophyllite, indicating that eggletonite differs from ganophyllite only by the exchangeable cation.

The thermal decomposition of caledonite has been examined by simultaneous differential thermal analysis, thermogravimetry and mass spectrometry. Structural H2O and CO2 are liberated endothermically between 300 and 400°C leaving a residue of lead sulphate, oxysulphate, and Cu(I) and Cu(II) oxides. A series of sharp endothermic peaks between 850 and 950°C correspond to phase transition and melting reactions of the PbO-PbSO4 mixture. The sulphate anion breaks down above 880 °C. Mass spectra of the gaseous decomposition products show SO2, SO, and O2, although SO is an artefact arising from ion fragmentation of the SO2 within the mass spectrometer. The residue at 1060 °C is composed predominantly of 2PbO · PbSO4 and Cu(I) and Cu(II) oxides.

Pyrosmalite [(Mn,Fe)8(OH,Cl)10Si6O15] has been identified by X-ray diffraction from the Pegmont lead-zinc deposit, north-west Queensland. Microprobe analyses indicate that it is the first reported occurrence of an extremely iron-rich member of the series. The characteristically high chlorine content of pyrosmalite in Pegmont and other similar base metal deposits may provide some evidence concerning the depositional environment of these stratiform Pb-Zn ores.