Fluid and enthalpy production during regional metamorphism

Models for regional metamorphism have been constructed to determine the thermal effects of reaction enthalpy and the amount of fluid generated by dehydration metamorphism. The model continental crust contains an average of 2.9 wt % water and dehydrates by a series of reactions between temperatures of 300 and 750° C. Large scale metamorphism is induced by instantaneous collision belt thickening events which double the crustal thickness to 70 km. After a 20 Ma time lag, erosion due to isostatic rebound restores the crust to its original thickness in 100 Ma. At crustal depths greater than 10 km, where most metamorphism takes place, fluid pressure is unlikely to deviate significantly from lithostatic pressure. This implies that lower crustal porosity can only be maintained if rock pores are filled by fluid. Therefore, porosities are primarily dependent on the rate of metamorphic fluid production or consumption and the crustal permeability. In the models, permeability is taken as a function of porosity; this permits estimation of both fluid fluxes and porosities during metamorphism. Metamorphic activity, as measured by net reaction enthalpy, can be categorized as endothermic or exothermic depending on whether prograde dehydration or retrograde hydration reactions predominate. The endothermic stage begins almost immediately after thickening, peaks at about 20 Ma, and ends after 40 to 55 Ma. During this period the maximum and average heat consumption by reactions are on the order 11.2·10^–14 W/cm³ and 5.9·10^–14 W/ cm³, respectively. The maximum rates of prograde isograd advance decrease from 2.4·10^–8 cm/s, for low grade reactions at 7 Ma, to 7·10^–10 cm/s, for the highest grade reaction between 45 and 58 Ma. Endothermic cooling reduces the temperature variation in the metamorphic models by less than 7% (40 K); in comparison, the retrograde exothermic heating effect is negligible. Dehydration reactions are generally poor thermal buffers, but under certain conditions reactions may control temperature over depth and time intervals on the order of 1 km and 3 Ma. The model metamorphic events reduce the hydrate water content of the crust to values between 1.0 and 0.4 wt % and produce anhydrous lower crustal granulites up to 15 km in thickness. In the first 60 Ma of metamorphism, steady state fluid fluxes in the rocks overlying prograde reaction fronts are on the order of 5·10^–11 g/cm²-s. These fluid fluxes can be accommodated by low porosities (<0.6%) and are thus essentially determined by the rate of devolitalization. The quantity of fluid which passes through the metamorphic column varies from 25000 g/cm², within 10 km of the base of the crust, to amounts as large as 240000 g/cm², in rocks initially at a depth of 30 km. Measured petrologic volumetric fluid-rock ratios generated by this fluid could be as high as 500 in a 1 m thick horizontal layer, but would decrease in inverse proportion of the thickness of the rock layer. Fluid advection causes local heating at rates of about 5.9·10^–14 W/cm³ during prograde metamorphism and does not result in significant heating. The amount of silica which can be transported by the fluids is very sensitive to both the absolute temperature and the change in the geothermal gradient with depth. However, even under optimal conditions, the amount of silica precipitated by metamorphic fluids is small (<0.1 vol %) and inadequate to explain the quartz veining observed in nature. These results are based on equilibrium models for fluid and heat transport that exclude the possibility of convective fluid recirculation. Such a model is likely to apply at depths greater than 10 km; therefore, it is concluded that large scale heat and silica transport by fluids is not extensive in the lower crust, despite large time-integrated fluid fluxes.     

A regional gradient in the composition of metamorphic fluids in pelitic schist,Pecos Baldy,New Mexico

Two metamorphic isograds cut across graphitic schist near Pecos Baldy, New Mexico. The southern isograd marks the first coexistence of staurolite with biotite, whereas the northern isograd marks the first coexistence of andalusite with biotite. The isograds do not record changes in temperature or pressure. Instead, they record a regional gradient in the composition of the metamorphic fluid phase. Ortega Quartzite, which contains primary hematite, lies immediately north of the graphitic schist. Mineral compositions within the schist change gradually toward the quartzite, reflecting gradients in and . The chemical potential gradients, locally as high as 72 cal/m in and 9 cal/m in , controlled the positions of the two mapped isograds. The staurolite-biotite isograd records where fell below 0.80, at near 10^–23 bars; the andalusite-biotite isograd records where fell below 0.25, at near 10^–22 bars. Dehydration and oxidation were coupled by graphite-fluid equilibrium.The chemical potential gradients apparently formed during metamorphism, as graphite in schist reacted with hematite in quartzite. Local oxidation of graphite formed CO₂ which triggered dehydration reactions along the schistquartzite contact. This process created a C-O-H fluid which infiltrated into overlying rocks. Upward infiltration, local fluid-rock equilibration and additional infiltration proceeded until the composition of the infiltrating fluid evolved to that in equilibrium with the infiltrated rock. This point occurs very close to the staurolite-biotite isograd. Pelitic rocks structurally above this isograd show no petrographic evidence of infiltration, even though calculations indicate that volumetric fluid/rock ratios may have exceeded 15 and thin, rare calc-silicate beds show extensive K-metasomatism and quartz veining.     

Effects of fluid production on fluid flow during regional and contact metamorphism

Numerical and analytical models of fluid flow that account for fluid production during prograde regional and contact metamorphism show that expulsion of metamorphic fluids dominates the convective flux when crustal permeabilities are less than 0.1–100 μD, depending primarily on the rate of fluid production. When this is the case, fluid circulation is limited or prevented, fluid pressures are elevated above hydrostatic values, and flow throughout most of the model is up and away from the region of maximum fluid production. Fluid circulation is predicted to occur where permeability is high, in dry rocks, or after rates of fluid production decrease as peak temperatures are reached. Large changes in the pattern of flow and influx of externally derived fluids may thus occur in metamorphic terranes when dehydration wanes or ceases and cooling begins. Inclusion of an impermeable horizon in the models further inhibits fluid circulation. Earlier, shallow hydrothermal models and interpretations based on the Rayleigh number may be inappropriate for characterizing fluid flow during prograde metamorphism at depth because they do not account for fluid production.     

Volatile production and transport in regional metamorphism

Calculations show that H₂O and CO₂ produced during devolatilization of an average pelite will occupy 12 vol. % of the rock at 500°C and 5 kb. Because the tensional strength of well foliated rock at metamorphic conditions is vanishingly small, such a volume of fluid having any vertical extent will fracture the rock and escape upward owing to its lower density.In a simplified model of a sudden increase of heat flow from 0.8 to 2.5 H.F.U., the average pelitic rock will have a rate of fluid production averaging 9.4×10^–10 g cm² s^–1 between 400°C and 600°C. The escape of this fluid can be accomodated by a single fracture 1 cm long and 0.2 wide per cm² of rock. If the fracture is reduced to 0.02 then 1,000 cm of fracture per cm² would be required. This width is the minimum original width as calculated from the volume of fluid observed in fluid inclusions trapped along annealed fractures within quartz in metamorphic terrains. Fluid flow will be laminar if the fracture is <0.025 cm wide. Additional calculations show that grain boundary diffusion is not an effective means of fluid transport in regional metamorphism.The commonly observed quartz segregations in pelitic terrains appear to mark the site of major channelways for fluid escape. In this case the bulk of escaping fluid is not able to react pervasively with rocks higher in the metamorphisc pile. Regionally metamorphosed rocks will have a discrete fluid phase only when devolatization reactions are actually taking place. At other times only an absorbed surface monolayer of volatiles on the minerals will be present.Died April 2, 1980     

Graphitization of carbonaceous matter during metamorphism with references to carbonate and pelitic rocks of contact and regional metamorphisms,Japan

This study is an attempt to correlate the graphitization process of carbonaceous matter during metamorphism with metamorphic grade. Graphitization can be parameterized using crystal structure and chemical and isotopic compositions. The extent of graphitization could be characterized mainly by temperature, duration of metamorphism and rock composition. We compared the graphitization trends for two metamorphic terrains, a contact aureole of the Kasuga area and a regional metamorphic terrain of high-temperature/low pressure type of the Ryoke metamorphic terrain in Northern Kiso area, Central Japan, and for two different lithologies (carbonate and pelite), using X-ray diffractogram, DTA-TG analysis, and chemical and stable isotope analyses. During contact metamorphism, graphitization and carbon isotopic exchange reactions proceeded simultaneously in pelitic and carbonate rocks. The decreases in basal spacing d(002) of the carbonaceous matter in carbonate rocks is greatly accelerated at temperatures higher than about 400° C. Furthermore, carbon isotopic ratios of graphite in carbonate rocks also change to ¹³C-enriched values implying exchange with carbonates. The beginning of this enrichment of ¹³C in the carbonaceous matter coincides with an abrupt increase of the graphitization processes. Carbon isotopic shifting up to 5 in pelites could be observed as metamorphic temperature increased probably by about 400° C. Carbonaceous matter in pelitic rocks is sometimes a mixture of poorly crystallized organic matter and well-crystallized graphite detritus. DTA-TG analysis is an effective tool for the distinction of detrital graphitic material. Two sources for the original carbon isotopic composition of carbonaceous matter in pelites in the Kasuga contact aureole can be distinguished, about-28 and-24 regardless of the presence of detrital graphite, and were mainly controlled by depositional environment of the sediments. Graphitization in limestones and pelitic rocks in regional metamorphism proceeds further than in a contact aureole. In the low-temperature range, the differences in extent of graphitization between the two metamorphic regions is large. However, at temperatures higher than 600° C, the extent of graphitization in both regions is indistinguishable. The degree of graphitization is different in limestones and pelitic rocks from the Ryoke metamorphic terrain. We demonstrate that the graphitization involves a progressive re-construction process of the crystal structure. The sequence of the first appearance of crystal inter planar spacing correlates with the metamorphic grade and indicates the crystal growth of three-dimensional structured graphite.     

Progressive metamorphism of pelitic rocks from protolith to granulite facies, Dutchess County, New York, USA: constraints on the timing of fluid infiltration during regional metamorphism

A complete Barrovian sequence ranging from unmetamorphosed shales to sillimanite–K-feldspar zone metapelitic gneisses crops out in a region extending from the Hudson River in south-eastern New York state, USA, to the high-grade core of the Taconic range in western Connecticut. NNE-trending subparallel biotite, garnet, staurolite, kyanite, sillimanite and sillimanite–K-feldspar isograds have been identified, although the assignment of Barrovian zones in the high-grade rocks is complicated by the appearance of fibrolitic sillimanite at the kyanite isograd. Thermobarometric results and reaction textures are used to characterize the metamorphic history of the sequence. Pressure–temperature estimates indicate maximum metamorphic conditions of 475 °C, c. 3–4 kbar in the garnet zone to >720 °C, c. 5–6 kbar in the highest grade rocks exposed. Some samples in the kyanite zone record anomalous (low) peak conditions because garnet composition has been modified by fluid-assisted reactions. There is abundant petrographic and mineral chemical information indicating that the sequence (with the possible exception of the granulite facies zone) was infiltrated by a water-rich fluid after garnet growth was nearly completed. The truncation of fluid inclusion trails in garnet by rim growth or recrystallization, however, indicates that metamorphic reactions involving garnet continued subsequent to initial infiltration. The presence of these textures in some zones of a well-constrained Barrovian sequence allows determination of the timing of fluid infiltration relative to the P–T paths. Thermobarometric results obtained using garnet compositions at the boundary between fluid–inclusion-rich and inclusion-free regions of the garnet are interpreted to represent peak metamorphic conditions, whereas rim compositions record slightly lower pressures and temperatures. Assuming that garnet grew during a single metamorphic event, infiltration must have occurred at or slightly after the peak of metamorphism, i.e. 4–5 kbar and a temperature of c. 525–550 °C for staurolite and kyanite zone rocks.     

Evidence from mineral assemblages for infiltration of pelitic schists by aqueous fluids during metamorphism

Prograde mineral assemblages and compositions have been predicted for pelitic schist in the 10 component system Na₂O–K₂O–CaO–MnO–FeO–MgO–Al₂O₃–SiO₂–CO₂–H₂O for three cases of prograde metamorphism and fluid-rock interaction: (1) increasing temperature (T) at constant pressure (P) and constant pore fluid volume (1%) without infiltration (no-infiltration case); (2) increasing T at constant P accompanied by sufficient fluid infiltration that fluid composition is at all times constant (large-flux case); and (3) increasing T at constantP accompanied by a timeintegrated fluid flux f 10⁴ cm^{3 cm 2} (intermediate-flux case). Stable mineral assemblages and compositions were calculated by solving a system of non-linear equations that specify mass balance and chemical equilibrium between minerals and fluid. The model pelitic system includes quartz, muscovite, plagioclasc, chlorite, ankerite, siderite, biotite, garnet, staurolite, andalusite, kyanite, sillimanite, K-feldspar, and a coexisting, binary H₂O–CO₂ fluid. Specifically, prograde thermal metamorphism was modelled for Shaw's (1956) average low-grade pelite and for a moderate range of bulk rock compositions at P=3, 5, and 7 kb and initial fluids with Xco ₂ ^o =0.02–0.40. The model predicts a carbonate-bearing mineral assemblage for average pelite under chlorite zone conditions composed of quartz, muscovite, albite, chlorite, ankerite, and siderite. The mineral assemblages predicted for the noinfiltration case are unlike those typically observed in regional metamorphic terranes. Simulations of metamorphism for the large-flux and intermediate-flux cases, however, reproduce the sequence of mineral assemblages observed in normal Barrovian regional metamorphic terranes. These results suggest that regional metamorphism of pelitic schists is typically associated with infiltration of significant quantities of aqueous fluid.     

The effect of whole-rock MnO content on the stability of garnet in pelitic schists during metamorphism

Garnet-bearing mineral assemblages are commonly observed in pelitic schists regionally metamorphosed to upper greenschist and amphibolite facies conditions. Modelling of thermodynamic data for minerals in the system Na₂O–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O, however, predicts that garnet should be observed only in rocks of a narrow range of very high Fe/Mg bulk compositions. Traditionally, the nearly ubiquitous presence of garnet in medium- to high-grade pelitic schists is attributed qualitatively to the stabilizing effect of MnO, based on the observed strong partitioning of MnO into garnet relative to other minerals. In order to quantify the dependence of garnet stability on whole-rock MnO content, we have calculated mineral stabilities for pelitic rocks in the system MnO–Na₂O–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O for a moderate range of MnO contents from a set of non-linear equations that specify mass balance and chemical equilibrium among minerals and fluid. The model pelitic system includes quartz, muscovite. albite, pyrophyllite, chlorite, chloritoid, biotite, garnet, staurolite, cordierite, andalusite, kyanite. sillimanite, K-feldspar and H₂O fluid. In the MnO-free system, garnet is restricted to high Fe/Mg bulk compositions, and commonly observed mineral assemblages such as garnet–chlorite and garnet–kyanite are not predicted at any pressure and temperature. In bulk compositions with X_Mn= Mn/(Fe + Mg + Mn) > 0.01, however, the predicted garnet-bearing mineral assemblages are the same as the sequence of prograde mineral assemblages typically observed in regional metamorphic terranes. Temperatures predicted for the first appearance of garnet in model pelitic schist are also strongly dependent on whole-rock MnO content. The small MnO contents of normal pelitic schists (X_Mn= 0.01–0.04) are both sufficient and necessary to account for the observed stability of garnet.     

Crystallization kinetics during regional metamorphism of porphyroblastic rocks

Numerical simulations of diffusion‐controlled nucleation and growth of garnet porphyroblasts in regionally metamorphosed rocks constrain interfacial energy and rates of nucleation and Al intergranular diffusion. The 13 rocks analysed in this study were collected from seven localities exhibiting a diverse range of crystallization conditions. Kinetic parameters governing nucleation and intergranular diffusion were adjusted iteratively to achieve fits between simulated and natural porphyroblastic textures. Model fits were assessed primarily from textural characteristics precisely measured by high‐resolution X‐ray computed tomography. Interfacial energy for heterogeneous nucleation ranges from 0.007 to 0.255 J m^?2 for the sample suite, assuming shape factors in the range 0.01–1.0. Nucleation rates change through space and time due to growth and impingement of Al depletion zones surrounding porphyroblasts. In some models, the overall rock‐wide nucleation rate rises steeply, achieves a steady state, and then falls rapidly as reactants are consumed; in others, the steady state is not achieved, but instead the rate simply peaks before falling. Maximum rock‐wide nucleation rates range from 10^?14.7 to 10^?10.7 nuclei cm^?3 s^?1, and maximum local rates range from 10^?13.7 to 10^?9.7 nuclei?cm^?3 s^?1 depending on Al supersaturation. Diffusive fluxes of Al are well constrained by the simulated textures, but rates of intergranular diffusion are subject to uncertainties in Al solubility and interconnected porosity. Best estimates of Al diffusivities at 600 °C span 10^?12.3 to 10^?10.5 m² s^?1 for the sample suite, a narrow range considering natural variability and the uncertainties in solubility and porosity. Eliminating some models suspected of higher uncertainty for these quantities yields diffusivities at 600 °C near 10^?11.0 m² s^?1, with dispersion of less than half an order of magnitude. These simulations, which are among the first attempted for regionally metamorphosed rocks, emphasize that: (i) nucleation rates vary markedly in time and space during crystallization; (ii) nucleation extends well beyond equilibrium conditions; (iii) Al diffusivity likely varies over only a narrow range across common metamorphic circumstances; and (iv) better determinations of both Al solubility and interconnected porosity are needed to constrain rates of Al intergranular diffusion more precisely.     

Loss of metals from pelites during regional metamorphism

In aluminous metapelites the ratio H₂O⁺/K₂O decreases with increasing metamorphic grade and degree of reaction. This ratio is a very practical indicator for the progress of the mineral reconstitution during progressive metamorphism. With decreasing values of the ratio H₂O⁺/ K₂O the Cu concentration and the following element ratios also decrease either continuously or in stepwise fashion: Tl/K₂O, Ba/K₂O, Pb/K₂O, Bi/K₂O, Hg/K₂O, Sr/Na₂O, Zn/(Fe²⁺+Mg), Cd/(Fe²⁺+Mg); Rb/K₂O remains approximately constant. In the aluminous metapelites of the Damara Orogen in Namibia the following losses occur between the biotite isograd and anatexis: 61% Cu, 20% Tl, 34% Ba, 59% Pb, 86% Bi, 46% Hg, 30% Sr, 25% Zn, 31% Cd. Thus the potential of regional metamorphism to form hydrothermal deposits in the low grade environment should not be neglected.     

Fluid production and isograd reactions at contacts of carbonate-rich and carbonate-poor layers during progressive metamorphism

ABSTRACT With increasing temperature during prograde metamorphism reactions will occur first at the lithological contacts of mixed pelite and calcsilicate terranes. At these interfaces, a fluid of lower chemical potential of H₂O and CO₂ than that required to produce a fluid in either layer can be produced whether reaction is caused by fluid infiltration or is initially fluid absent. If the interface region does not allow fluid transport then as temperature increases, a fluid pressure greater than lithostatic can develop. At some degree of over-pressure relative to rock pressure, the fluid hydraulically fractures the rock and a gradient in fluid composition away from the contact can be produced. These phenomena occur at the compositional interfaces whenever univariant reactions in the differing layers cross on a temperature vs. mole fraction of CO₂ diagram with slopes of opposite sign. The first occurrence of these reaction products at lithological contacts delineates an isograd that defines temperature as well as the mole fraction of CO₂ at constant pressure in systems open to fluid transport. These isograds can be contrasted with fluid-producing isograds in closed systems. As an illustration of possible effects, the reactions quartz + clinozoisite + muscovite = anorthite + K-feldspar + H₂O and phlogopite + quartz + calcite = tremolite + K-feldspar + H₂O + CO₂ at 4 kbar are analysed and equations for fluid production and transport are developed.     

Monazite U-Pb dating of staurolite grade metamorphism in pelitic schists

A study of the occurrence of and relations between rare-earth element (REE) minerals in pelitic schists indicates that monazite forms at or near the P and T of the staurolite isograd. Samples at staurolite grade from the Silurian Perry Mountain Formation in the Rumford quadrangle of Maine yield monazite in sufficient quantities to permit accurate dating of the metamorphic events forming the monazites. The bulk chemistry of the metapelites, as seen in the major element abundances and REE patterns, does not vary significantly across the study area. Thus the appearance and disappearance of REE phases is assumed to reflect changes in metamorphic grade. In a sample from the biotite zone, scanning electron microscope and microprobe studies show allanite and monazite intimately associated on a 10 m scale. The texture suggest that metastable detrital monazite breaks down, distributing its REE components to allanite. From samples below staurolite grade in which monazite is not present, our observations suggest that REEs are partitioned into allanite. At or near the staurolite isograd monazite forms as a metamorphic mineral, initiating its role as a geochronometer. Garnet-biotite geothermometry on samples at this grade from this and other studies places constraints on the minimum temperature necessary to form monazite: 525° C±25°C at 3.1±0.25 kbar. A total of 15 separates from nine schist samples ranging up to sillimanite grade have been dated. Each date is remarkably concordant, even though petrologic and textural studies by previous workers have shown that the rocks in the area have been affected by at least three metamorphic episodes. Calculations indicate insignificant Th disequilibrium in these monazites. The conditions associated with the metamorphic events suggest that monazite remains closed to lead loss provided that subsequent metamorphisms are at or below sillimanite grade. Two distinct metamorphic events are resolved, one at around 400 Ma and one at about 370 Ma. The latter was due to thermal effects of a nearby pluton that yields concordant monazite ages of 363 Ma. This work suggests that in addition to dating plutonism and high-grade metamorphism, monazite should be viewed as a reliable geochronometer for moderate metamorphism of pelitic schists.     

The role of the fluid phase during regional metamorphism and deformation

Evidence from rock microstructures, mass transfer and isotopic exchange indicates that substantial quantities of aqueous fluids are involved in low- and medium-grade regional metamorphism. Similar conclusions are drawn from many retrograde environments, whereas high-grade metamorphic fluids may be melt dominated. The mobile fluids play essential roles in metamorphic reactions, mass transport and deformation processes. These processes are linked by the mechanical consequences of metamorphic fluid pressures (P_f) generally being greater than or equal to the minimum principal compressive stress. Under such conditions metamorphic porosity comprises grain boundary tubules and bubbles together with continuously generated (and healed) microfractures. Deformation results in significant interconnected porosity and hence enhanced permeability. Lithologically and structurally controlled permeability variations may cause effective fluid channelling.
Simple Rayleigh-Darcy modelling of a uniformly permeable, crustal slab shows that convective instability of metamorphic fluid is expected at the permeabilities suggested for the high P_f metamorphic conditions. Complex, large-scale convective cells operating in overpressured, but capped systems may provide a satisfactory explanation for the large fluid/rock ratios and extensive mass transport demonstrated for many low- and medium-grade metamorphic environments. Such large-scale fluid circulation may have important consequences for heat transfer in and the thermal evolution of metamorphic belts.     

Fluid infiltration and regional metamorphism of the Waits River Formation, north-east Vermont, USA

Abstract The Siluro-Devonian Waits River Formation of north-east Vermont was deformed, intruded by plutons and regionally metamorphosed during the Devonian Acadian Orogeny. Five metamorphic zones were mapped based on the mineralogy of carbonate rocks. From low to high grade, these are: (1) ankerite-albite, (2) ankerite-oligoclase, (3) biotite, (4) amphibole and (5) diopside zones. Pressure was near 4.5kbar and temperature varied from c. 450° C in the ankerite-albite zone to c. 525° C in the diopside zone. Fluid composition for all metamorphic zones was estimated from mineral equilibria. Average calculated χ_co2[= CO₂/(CO₂+ H₂O)] of fluid in equilibrium with the marls increases with increasing grade from 0.05 in the ankerite-oligoclase zone, to 0.25 in the biotite zone and to 0.44 in the amphibole zone. In the diopside zone, χ_CO2 decreases to 0.06. Model prograde metamorphic reactions were derived from measured modes, mineral chemistry, and whole-rock chemistry. Prograde reactions involved decarbonation with an evolved volatile mixture of χ_CO2 > 0.50. The χ_CO2 of fluid in equilibrium with rocks from all zones, however, was generally <0.40. This difference attests to the infiltration of a reactive H₂O-rich fluid during metamorphism. Metamorphosed carbonate rocks from the formation suggests that both heat flow and pervasive infiltration of a reactive H₂O-rich fluid drove mineral reactions during metamorphism. Average time-integrated volume fluxes (cm³ fluid/cm² rock), calculated from the standard equation for coupled fluid flow and reaction in porous media, are (1) ankerite-oligoclase zone: c. 1 × 10⁴; (2) biotite zone: c. 3 × 10⁴; (3) amphibole zone: c. 10 × 10⁴; and diopside zone: c. 60 × 10⁴. The increase in calculated flux with increasing grade is at least in part the result of internal production of volatiles from prograde reactions in pelitic schists and metacarbonate rocks within the Waits River Formation. The mapped pattern of time-integrated fluxes indicates that the Strafford-Willoughby Arch and the numerous igneous intrusions in the field area focused fluid flow during metamorphism. Many rock specimens in the diopside zone experienced extreme alkali depletion and also record low χ_CO2. Metamorphic fluids in equilibrium with diopside zone rocks may therefore represent a mixture of acid, H₂O-rich fluids given off by the crystallizing magmas, and CO₂-H₂O fluids produced by devolatilization reactions in the host marls. Higher fluxes and different fluid compositions recorded near the plutons suggest that pluton-driven hydrothermal cells were local highs in the larger regional metamorphic hydrothermal system.     

Ductility contrast induced by silicification in pelitic schist of the Ryoke metamorphic belt,Japan

Contrasting ductility is recognized in the rocks of Cretaceous Ryoke metamorphic belt in Iwakuni area, southwest Japan. Pelitic schist is ubiquitous in the region and differences in mineral assemblages mark increase in metamorphic grade. The area has been graded as chlorite-biotite zone in the north progressing into biotite- and muscovite-cordierite zones in the south. Pelitic schist near the boundary between the biotite- and muscovite-cordierite zones has undergone partial silicification to form whitish silicified schist layers which contain two types of quartz veins: those parallel to foliation in the host rock are called schistosity-concordant veins, and those inclined to host rock foliation, schistosity-discordant veins. In this study we examined the quartz structure in the silicified schist and in both types of veins to understand the ductility contrast induced by the silicification process. Crystallographic orientations of quartz in the veins and silicified schist rocks were studied using the Scanning Electron Microscopy (SEM) based Electron Back Scatter Diffraction (EBSD) technique. Quartz c-axis orientations in the silicified schist are nearly random, demonstrating an absence of post-silicification ductile deformation. Quartz grains in the schistosity-concordant veins have preferred c-axis orientations perpendicular to the schistosity indicating ductile shortening. In contrast, schistosity-discordant veins display distinct quartz c-axis fabric than that found in the schistosity-concordant veins. This is because the two types of host rocks exhibit a difference in ductility during deformation. The presence of deformed quartz veins in the undeformed silicified schist indicates transformation of the ductile pelitic schist into the brittle silicified schist at mid-crustal levels where these rocks originate, hence forming contrasting rock layers. Schistosity-concordant veins in the biotite-rich pelitic schist deformed with its host rock in a ductile manner while the schistosity-discordant veins in the neighboring silicified schist were left intact. Silicification of the pelitic schist may have been caused by the silica-rich geofluids produced by subsurface processes. Geofluids responsible for the occurrence of such mechanically contrasting layers mark an increase in seismic reflectivity at mid-crustal depths and may be potential reflectors of seismic waves giving rise to the so-called “bright spots”.     

Alpine metamorphism of pelitic schists in the Nufenen Pass area, Lepontine Alps

Abstract The effects of Tertiary Alpine metamorphism on pelitic Mesozoic cover rocks have been studied along a cross-section in the central Lepontine Alps in the Nufenen Pass area, Switzerland. Greenschist facies to amphibolite facies conditions are indicated by the formation of the index minerals chloritoid, garnet, staurolite and kyanite in pelitic rocks. Regional metamorphism reached maximum conditions during the interkinematic period between a main Alpine penetrative (D2) and a late Alpine (D3) crenulation type deformation phase or synchronous with the late Alpine deformation. Based on AFM phase relationships four different metamorphic zones can be distinguished: (1) chloritoid zone; (2) staurolite + chlorite zone; (3) staurolite + biotite zone; and, (4) kyanite zone. The isograds that separate these zones can be modelled by univariant reactions in the KFMASH system. The conditions of metamorphism calculated from geological ther-mobarometers for the maximum post-D2 por-phyroblast stage are from North to South: 500° C at 5-6 kbar and 600° C at 7-8 kbar. Detailed thermobarometry of garnet por-phyroblasts with complex textures suggests that maximum temperature was reached later than maximum pressure. Early garnet growth occurred along a prograde P-T-path, post-D2 rims grew with increasing temperature but decreasing pressure, and finally post-D3 garnet formed along a retrograde P-T-path. It may be concluded from the calculated pressure and temperature difference over a short distance (3 km) across the mapped area that the isogradic surfaces of the post-D2 metamorphism are steeply oriented. The data also suggest that isobaric and isothermal surfaces are parallel. Much of the observed metamorphic pattern can be explained as the result of a significant post-D2 differential uplift of the hot Pennine area relative to the Helvetic area along a tectonic contact zone. The closely spaced isograds (isotherms) in the North may then be interpreted as a thermal effect owing to the emplacement of the hot Pennine rocks against the Got-thard massif with its cover. Whereas, in the Pennine metasediments, post-D2 porphyroblast formation can be related to the decompression path which was steep enough for dehydration reactions to proceed. It is also remarkable that late kyanite porphyroblasts probably formed with decreasing pressure. The interpretation given here for the Nufenen Pass area may also apply to the Luk-manier Pass area where similar metamorphic patterns have been reported by Fox (1975). The formation of the ‘Northern Steep Belt’;, as denned by Milnes (1974b), and the associated late Alpine fold zones may, therefore, have significantly modified the metamorphic pattern of the Helvetic-Penninic contact zone.     

Regional metamorphism of pelitic rocks around Kandra,Singhbhum, Bihar

A suite of pelitic rocks around Kandra, Singhbhum District, Bihar, displays a metamorphic gradient registered by the index minerals chlorite, biotite, garnet, staurolite and sillimanite in a Barrovian sequence. Metamorphism was by and large coeval with folding movements, and correlating the internal fabric of minerals and deformational characters, a regular sequence of the index minerals is derived. It is argued that the chronological order by itself is not sufficient to prove that metamorphism was progressive in time.Among the index minerals, garnet appears to have formed by the reaction chlorite+biotite_a+quartz garnet+biotite_b+H₂O. For the origin of sillimanite, a new reaction, 3 staurolite+muscovite+quartz=7 sillimanite+biotite+3H₂O, is suggested on the basis of significant textural features. Textural and petrological indications regarding the formation of staurolite are in discordance. Staurolite was either derived from the biotite zone phases, or should be taken to have formed, against textural evidences, from chloritoids of the garnet zone.Graphical analysis of the assemblages by Thompson's AFM projection reveals that chlorite and staurolite are excess phases owing to retrogression and incomplete reaction. Shifting of apices of triangular fields and intersection of garnet-biotite tie lines within a zone can be satisfactorily explained in terms of extra components CaO and MnO or their ratios. It is pointed out that if MgO/(MgO + FeO) between two phases show a linear relation, their tie lines will be concurrent on the AF side of the projection, the point of concurrence reflecting equilibrium and temperature of recrystallisation.     

Magnitudes of departures from equilibrium during regional metamorphism of porphyroblastic rocks

Numerical models of diffusion‐controlled nucleation and growth of garnet crystals, which successfully replicate diverse textures in 13 porphyroblastic rocks, yield quantitative estimates of the magnitudes of departures from equilibrium during crystallization. These estimates are derived from differences in chemical potential between subvolumes containing stable product assemblages and those containing persistent but metastable reactant assemblages. The magnitude of disequilibrium is evaluated in terms of the thermal overstepping, which is commonly referenced to the garnet‐in isograd; the reaction affinity in the intergranular fluid at the site and time of each nucleation event, and on average throughout the rock, and the ‘latent energy of reaction’ per unit volume, a measure of the average unreacted capacity of the bulk rock, which describes its overall metastability. Across all of the models, the first crystals nucleate after 5–67 °C of thermal overstepping (correspondingly, 0.7–5.8 kJ mol^?1 of 12‐oxygen garnet); the maximum reaction affinity averaged across the intergranular fluid is between 4.7 and 16.0 kJ mol^?1 of 12‐oxygen garnet; and the maximum latent energy of reaction ranges from 7.3 to 51.7 J cm^?3. These results demonstrate that impediments to crystallization significantly delay nucleation and retard reaction, with the consequence that nucleation of new crystals extends throughout nearly the entire crystallization interval. This potential for protracted reaction during prograde metamorphism, with reactions continuing to temperatures and pressures well beyond equilibrium conditions, suggests the likelihood of overstepping of multiple – possibly competing – reactions that can progress simultaneously. Isograds and ranges of stability for metamorphic assemblages along a metamorphic field gradient may therefore be significantly offset from the positions predicted from calculations based on equilibrium assumptions, which poses a substantial challenge to accurate interpretations of metamorphic conditions and processes.