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The distribution of metapelitic mineral assemblages in the Nelson aureole, British Columbia, generally conforms to what is predicted from phase equilibria. However, in detail, the sequence and spacing of isograds, mineral textures and mineral compositions and mineral chemical zoning do not. Two of the main disequilibrium features in the aureole are: (i) delay in the onset and progress of several reactions, i.e. overstepping in temperature; and (ii) unreactivity of staurolite and especially garnet porphyroblasts when they are reactants in prograde reactions. The thermal overstepping is ascribed to difficulty of nucleation of the product porphyroblasts and sluggishness of dissolution of porphyroblasts when they are reactants. The extent to which these kinetic barriers delay the onset of reaction is related to the reaction affinity of each reaction, defined herein as the Gibbs free-energy difference between the thermodynamically stable, but not-yet-crystallized, products and the metastable reactants. For oversteps in temperature (DT), reaction affinity is, in turn, related to the difference in entropy (DS) between these two states through the relation A = DT * DS. Mineral reactions which release large quantities of H 2 O, such as chlorite-consuming reactions, have a higher entropy change per unit of temperature overstep, and therefore a higher reaction affinity, than those which release little or no H 2 O, such as the chloritefree staurolite-consuming reaction. Thermal overstepping is consequently expected to be less for the former than for the latter, as was estimated in the aureole where 0 to 30°C overstepping was required for garnet, staurolite and andalusite growth from a muscovite + chlorite-bearing precursor rock and 70°C overstepping was required for the growth of Al 2 SiO 5 from a staurolite-bearing, chlorite-free precursor. In all cases, reaction progress was strongly influenced by the presence or absence of fluid, with presence of fluid lowering kinetic barriers to nucleation and growth and therefore the degree of thermal overstepping. Textural features of rocks from the nearly coincident garnet, staurolite and andalusite isograds are suggestive of a fluid-catalysed Ôcascade effectÕ in which reaction took place in a narrow temperature interval; several competing muscovite + chlorite-consuming reactions, some metastable, appear to have occurred in parallel. Metamorphic reaction, fluid release and possibly fluid presence in general in the aureole were episodic rather than continuous, and in several cases well removed from equilibrium conditions. The extent to which these findings apply to regional metamorphism depends on several factors, a major one being enhanced deformation, which is expected to lower kinetic barriers to nucleation and growth.

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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.

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The extent to which kinetic barriers to nucleation and growth delay the onset of prograde metamorphic reaction, commonly known as overstepping, is related to the macroscopic driving force for reaction, termed reaction affinity. Reaction affinity is defined in the context of overstepping as the Gibbs freeenergy difference between the thermodynamically stable, but not-yet-crystallized, products and the metastable reactants. Mineral reactions which release large quantities of H 2 O, such as chloriteconsuming reactions, have a higher entropy ⁄ volume change, and therefore a higher reaction affinity per unit of temperature ⁄ pressure overstep, than those which release little or no H 2 O. The former are expected to be overstepped in temperature or pressure less than the latter. Different methods of calculating reaction affinity are discussed. Reaction affinity ÔmapsÕ are calculated that graphically portray variations in reaction affinity on equilibrium phase diagrams, allowing predictions to be made about expected degrees of overstepping. Petrological consequences of variations in reaction affinity include: (i) metamorphic reaction intervals may be discrete rather than continuous, especially in broad multivariant domains across which reaction affinity builds slowly; (ii) reaction intervals may not correspond in a simple way to reaction boundaries and domains in an equilibrium phase diagram, and may involve metastable reactions; (iii) overstepping can lead to a Ôcascade effectÕ, in which several stable and metastable reactions involving the same reactant phases proceed simultaneously; (iv) fluid generation, and possibly fluid presence in general, may be episodic rather than continuous, corresponding to discrete intervals of reaction; (v) overstepping related to slowly building reaction affinity in multivariant reaction intervals may account for the commonly abrupt development in the field of certain index mineral isograds; and (vi) P-T estimation based on combined use of phase diagram sections and mineral modes ⁄ compositions on the one hand, and classical thermobarometry methods on the other, may not agree even if the same thermodynamic data are used. Natural examples of the above, both contact and regional, are provided. The success of the metamorphic facies principle suggests that these kinetic effects are second-order features that operate within a broadly equilibrium approach to metamorphism. However, it may be that the close approach to equilibrium occurs primarily at the boundaries between the metamorphic facies, corresponding to discrete intervals of high entropy, dehydration reaction involving consumption of hydrous phases like chlorite (greenschist-amphibolite facies boundary) and mica (amphibolite-granulite facies boundary), and less so within the facies themselves. The results of this study suggest that it is important to consider the possibility of reactions removed from equilibrium when inferring the P-T-t evolution of metamorphic rocks.

A B S TR A CT Migmatitic, granulite-grade mafic gneisses make up a significant part of the Kapuskasing Structural Zone (KSZ), Ontario. Although they contain a common mineral assemblage [hornblende (Hbl)+plagioclase (Pl )+diopside (Di)±garnet (Grt)+quartz (Qtz)±titanite (Ttn)], the mafic gneisses show wide variations in modal mineralogy from hornblende-rich to diopside+garnet-rich varieties and all gradations between. Up to 25 vol.% segregated plagioclase+quartz-rich (trondhjemitic) leucosome (Tdh) is intimately associated with the mafic gneiss, occurring in a continuum of patches, veins and transecting dykes at scales ranging from decimetres to micrometres. The texture and composition of the leucosome, combined with P-T estimates for the host rocks above the solidus, suggest it represents crystallized trondhjemitic melt. Quartz is mainly restricted to the segregated leucosomes but more rarely occurs in a variety of interstitial textures in the mafic gneiss, suggesting that it crystallized from a melt phase rather than having been present as a solid phase at peak metamorphic conditions. Modal and textural data indicate a reaction relationship of the form: Hbl+Pl(+Qtz?)=Grt+Di+Ttn+leucosome (Tdh), implying that the granuliteforming process involved dehydration melting of an amphibolite protolith. Pressure-temperature estimates from Grt+Di+Pl+Qtz geothermobarometry are 9 kbar and 685-735°C; however, based on experimental studies of dehydration melting of amphibolite, we estimate that peak conditions were closer to 11 kbar, 850°C. Mass balance analysis, using the technique of singular value decomposition, and reaction space analysis were used to quantify the reaction and to determine the controls on reaction progress. The following mass balance provides a model for the natural reaction:1.00 Hbl+0.92 Pl+3.76 Qtz=1.14 Grt+1.54 Di+0.21 Ttn+1.49 Tdh+0.14 'pg'+0.39 Fe −1 Mg +0.33 NaSiCa −1 Al −1 where 'pg' is a pargasite-like exchange. In all model mass balances tested, quartz is a reactant with a large coefficient. We argue that the abundance of quartz in the amphibolite protolith was the primary control on the differing extents of reaction observed. Mineral compositional variation exerted a secondary control on reaction progress, with Fe-richer layers containing An-richer plagioclase and more actinolitic amphibole reacting earliest (i.e. at lowest temperatures). Comparison of the calculated amount of melt produced in the gneisses with that now observed implies expulsion of 5-30% of the melt. These volumes are similar to those predicted from REE modelling of Archaean tonalities and trondhjemites from a garnet amphibolite source, suggesting that the KSZ mafic gneisses may be representative of partially depleted source rocks for trondhjemite-tonalite generation.