Interplay between equilibrium and kinetics in prograde metamorphism of pelites: an example from the Nelson aureole, British Columbia

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 (ΔT), reaction affinity is, in turn, related to the difference in entropy (ΔS) between these two states through the relation A = ΔT * ΔS. Mineral reactions which release large quantities of H₂O, 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 H₂O, such as the chlorite‐free 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 Al₂SiO₅ 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 ‘cascade effect’ 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.     

基岩地区高速滑坡的多级冲程与超前溅泥气浪

本文通过对陕南基岩滑坡—石家坡高速滑坡的研究,提出了高速基岩滑坡的多级冲程和超前溅泥气浪问题。文中着重讨论了陕南基岩滑坡的形成条件与因素以及高速滑坡多级冲程和超前溅泥气浪的形成机制等问题。     

Towards a Better Understanding of the Fibrolite Problem: the Effect of Reaction Overstepping and Surface Energy Anisotropy

Trachytes from the Euganean Hills District (Italy) contain metapeliticxenoliths that have been pyrometamorphosed during incorporationin the melt. In xenoliths containing sillimanite crystallizedduring a previous regional HT/LP metamorphism, fibrolite systematicallynucleates at the grain boundaries of sillimanite prisms andwithin plagioclase crystals. Ternary feldspar thermometry showsthat plagioclase in contact with sillimanite plots along the750°C solvus that reflects near-equilibrium conditions ofregional metamorphism. Plagioclase containing fibrolite plotscloser towards the 950°C solvus, reflecting the tendencyof plagioclase to re-equilibrate at high temperature duringpyrometamorphism by a fibrolite-forming reaction:     

Assessing the extent of disequilibrium and overstepping of prograde metamorphic reactions in metapelites from the Bushveld Complex aureole, South Africa

Andalusite–staurolite–biotite hornfels metamorphosed beneath the mafic layered rocks of the Bushveld Complex, South Africa, preserves a detailed record of the relative timing of porphyroblast growth and metamorphic reactions. The sequence inferred from microstructures shows considerable overlap of the period of growth of porphyroblasts of staurolite, cordierite, biotite and andalusite, and the persistence over a similar interval of the reactant porphyroblastic phase chloritoid. This is inconsistent with calculations of equilibrium phase relations, and implies that disequilibrium processes controlled the prograde reaction sequence, despite the slow heating rates involved (1 °C per 10 000 yr). The early appearance of cordierite by a metastable reaction and its subsequent disappearance indicates that delayed nucleation of porphyroblastic phases, rather than simply sluggish reaction, is required to account for the sequence of growth. The predicted reactions for the first appearance of andalusite and staurolite have low entropy of reaction, and do not occur until they have been overtaken in terms of reaction affinity by high‐entropy devolatilisation reactions involving the breakdown of chlorite. Once the porphyroblasts have nucleated, metastable chloritoid‐breakdown reactions also contribute to their growth. The implied magnitude of the critical overstepping for andalusite nucleation is around 5 kJ mole^?1 (equivalent to 40 °C for the chlorite‐breakdown reaction), and that for other phases is expected to decrease in the order andalusite>staurolite>cordierite. Coupling between nucleation rate, crystal growth rates and the resulting grain size distribution suggests that the rate constants of natural reactions are at least an order of magnitude lower than those measured in the laboratory. Pseudomorphs after chloritoid and cordierite conserve volume but not Al or other species of low mobility, suggesting a breakdown mechanism controlled by an interface process such as the slow dissolution of the refractory porphyroblast phase, rather than by a transport step.     

Metastable growth of corundum adjacent to quartz in a spinel-bearing quartzite from the Archaean Napier Complex, Antarctica

In a granulite-facies spinel-bearing quartzite, corundum, orthopyroxene and sapphirine (and rarely cordierite and sillimanite) form partial rims separating spinel from quartz. Textures indicate the reactions:
spinel + quartz = orthopyroxene + corundum, and
spinel + quartz = orthopyroxene + sapphirine.
Thus, corundum and sapphirine are produced by reactions involving quartz. The low Al-content of the orthopyroxene (0.5–2.8 wt %) and low values for Mg–Fe distribution coefficient for spinel–sapphirine and spinel–orthopyroxene reflect low-temperature conditions during formation of the reaction products. Absence of zoning in spinel and a constant Mg–Fe distribution coefficient for spinel–sapphirine and spinel–orthopyroxene, over a compositional range, indicate Mg–Fe equilibration. It is suggested that stable reactions such as spinel + quartz = cordierite or spinel + quartz = garnet + sillimanite were over-stepped and that metastable reactions give rise to the anomalous juxtaposition of corundum + quartz.     

Petrological consequences of variations in metamorphic reaction affinity

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 free‐energy difference between the thermodynamically stable, but not‐yet‐crystallized, products and the metastable reactants. Mineral reactions which release large quantities of H₂O, such as chlorite‐consuming 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 H₂O. 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 ‘maps’ 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 ‘cascade effect’, 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.     

Formation and preservation of an overstepped segmented lagoon complex on a high‐energy continental shelf

The duration of shoreline occupation at a given sea‐level, coastal response to sea‐level change and the controls on preservation of various shoreline elements can be recognized by detailed examination of submerged shorelines on the continental shelf. Using bathymetric and seismic observations, this article documents the evolution and preservation of an incised valley and lithified barrier complex between ?65 m and ?50 m mean sea‐level on a wave‐dominated continental shelf. The barrier complex is preserved as a series of aeolianite or beachrock ridges backed by laterally extensive back‐barrier sediments. The ridges include prograded cuspate lagoonal shoreline features similar to those found in contemporary lagoons. The incised valley trends shore‐parallel behind the barrier complex and records an early phase of valley filling, followed by a phase of extensive lagoonal sedimentation beyond the margins of the incised bedrock valley. Sea‐level stability at the outer barrier position (ca ?65 m) enabled accumulation of a substantial coastal barrier that remained intact during a phase of subsequent slow sea‐level rise to ?58 m when the lagoon formed. These lagoonal sediments are stripped seawards by bay ravinement processes which caused the formation of several prograded marginal cuspate features. An abrupt rise in sea‐level to ?40 m, correlated with melt‐water pulse 1B, enabled the preservation of thick lagoonal sediments at the top of the incised valley fill and preservation on the sea bed of the cemented core of the barriers. This situation is unique to subtropical coastlines where early diagenesis is possible. The overlying sandy sediment from the uncemented upper portion of the barriers is dispersed by ravinement, partly burying the ridges and protecting the underlying sediments. The high degree of barrier or shoreline preservation is attributed to rapid overstepping of the shoreline, early cementation in favourable climatic conditions and the protection of the barrier cores by sand sheet draping.     

Reaction overstepping and re-evaluation of peak P‒T conditions of the blueschist unit Sifnos,Greece: implications for the Cyclades subduction zone

ABSTRACT

Equilibrium thermodynamic modelling, quartz in garnet (QuiG) Raman geobarometry, and modelling of garnet nucleation at overstepped conditions were applied to three garnet-bearing blueschists from a 1.5 km-long transect across the eclogite-blueschist unit in Sifnos, Greece, in order to evaluate the accuracy of P?T conditions calculated via equilibrium thermodynamics. QuiG barometry uses the Raman shift of quartz inclusions in garnet to estimate the pressure of garnet nucleation and is independent of chemical equilibrium. Garnet nucleation temperatures were estimated by determining the stability field of the palaeo-assemblage inferred from garnet inclusion suites on mineral assemblage diagrams calculated in the MnNCKFMASH system and on temperatures obtained from Zr in rutile thermometry. These conditions were then compared to P?T conditions calculated at the equilibrium garnet isograd, and the method of intersecting isopleths. The P?T conditions calculated with intersecting garnet isopleths over- and underestimated the temperature of nucleation in samples SPH99-1a and SPH99-7, respectively, whereas they significantly underestimated nucleation pressure in SPH99-5. Nucleation of garnet in SPH99-1a at 12 kbar and ~484°C requires overstepping of ~6 kbar and a reaction affinity of 2.2 kJ mol^?1 O. SPH99-5 requires overstepping of ~8 kbar with garnet reaction affinities of at least 2.0 kJ mol^?1 O at 15 kbar and ~520°C. SPH99-7 requires overstepping of approximately 15 kbar and affinities of about 2.0–2.4 kJ mol^?1 O at ~23 kbar and ~530°C. The geotherms calculated from SPH99-7 (~6.7°C km^?1) and SPH99-5 (9.8°C km^?1) are in accordance with previous studies. The geotherm calculated from SPH99-1a, however, is warmer (11.3°C km^?1), and could reflect changes in the rate of subduction or differences in structural position within the down-going slab. The 10 kbar pressure difference between SPH99-7 and SPH99-1a can be explained by thrusting and accretion of thin slices of underplated wedge material facilitated by slab rollback and gravitational collapse.     

Determining the amount of overstepping required to nucleate garnet during Barrovian regional metamorphism,Connecticut Valley Synclinorium

The novel method of inclusion barometry coupled with the calculation of the required affinity for garnet nucleation is applied to three samples from the previously well‐characterized Connecticut Valley Synclinorium in central Vermont. Raman shifts for quartz inclusions record a range of maximum peak shifts of the quartz 464 cm^?1 peak from 2.4 to 3.0 cm^?1. Temperature of garnet nucleation was constrained by calculating mineral assemblage diagrams in the MnNCKFMASHT system and plotting the intersection of quartz inclusion in garnet barometry (QuiG, quartz‐in‐garnet) with Zr‐in‐rutile thermometry. Utilizing the intersection of Zr‐in‐rutile thermometry with QuiG barometry, garnet nucleation is inferred to have occurred within a P–T range of ~8.6–9.5 kbar and ~560–575°C. These P–T conditions for garnet nucleation are significantly higher than calculated equilibrium garnet‐in isograds for the three samples. Affinities for garnet nucleation were calculated as the difference between the free energy of a fictive garnet composition based on the matrix assemblage and the free energy of the nucleated garnet. The calculated nucleation affinity varied from 300 to 600 kJ/mol O for St–Ky grade samples. These results suggest that the assumption that metamorphism proceeds as a sequence of near‐equilibrium conditions cannot, in general, be made for regional metamorphic terranes. This body of work agrees with numerous recent studies showing that garnet‐producing reactions must be overstepped in order to for garnet to nucleate.