Prograde destruction and formation of monazite and allanite during contact and regional metamorphism of pelites: petrology and geochronology

The conditions at which monazite and allanite were produced and destroyed during prograde metamorphism of pelitic rocks were determined in a Buchan and a Barrovian regional terrain and in a contact aureole, all from northern New England, USA. Pelites from the chlorite zone of each area contain monazite that has an inclusion-free core surrounded by a highly irregular, inclusion-rich rim. Textures and ²⁰⁸Pb/²³²Th dates of these monazites in the Buchan terrain, obtained by ion microprobe, suggest that they are composite grains with detrital cores and very low-grade metamorphic overgrowths. At exactly the biotite isograd in the regional terrains, composite monazite disappears from most rocks and is replaced by euhedral metamorphic allanite. At precisely the andalusite or kyanite isograd in all three areas, allanite, in turn, disappears from most rocks and is replaced by subhedral, chemically unzoned monazite neoblasts. Allanite failed to develop at the biotite isograd in pelites with lower than normal Ca and/or Al contents, and composite monazite survived at higher grades in these rocks with modified texture, chemical composition, and Th-Pb age. Pelites with elevated Ca and/or Al contents retained allanite in the andalusite or kyanite zone. The best estimate of the time of peak metamorphism at the andalusite or kyanite isograd is the mean Th-Pb age of metamorphic monazite neoblasts that have not been affected by retrograde metamorphism: 364.3Dž.5 Ma in the Buchan terrain, 352.9NJ.9 Ma in the Barrovian terrain, and 403.4LJ.9 Ma in the contact aureole. Some metamorphic monazites from the Buchan terrain have ages partially to completely reset during an episode of retrograde metamorphism at 343.1Nj.1 Ma. Interpretation of Th-Pb ages of individual composite monazite grains is complicated by the occurrence of subgrain domains of detrital material intergrown with domains of material formed or recrystallized during prograde and retrograde metamorphism.     

Quartz deformation mechanisms during Barrovian metamorphism: Implications from crystallographic orientation of different generations of quartz in pelites

The behaviour of quartz during metamorphism is studied based on two case studies from the Barrovian terrains of Sulitjelma in arctic Scandinavia and Loch Tay in the Central Highlands Dalradian of Scotland. Both terrains preserve evidence for metamorphism in pelites involving nucleation and growth of garnet at different times in the deformation history. Data are presented on the size, shape and crystallographic orientation of quartz preserved as inclusions in garnet and as grains in the surrounding matrix. While quartz-grains remain small and dispersed between mica grains, deformation appears to be dominated by grain-boundary sliding accommodated by dissolution–precipitation. At amphibolite facies, textural coarsening occurs by dissolution of small quartz grains and growth of larger quartz grains, coupled with segregation of quartz from mica. As a result, quartz deforms by dislocation creep, developing crystallographic preferred orientations (CPO) consistent with both coaxial and non-coaxial strain. Quartz CPOs with <0001> axes lying parallel to foliation and stretching direction are commonly developed, and best explained by mechanical rotation of inequant (detrital?) quartz grains. There is no evidence for selective entrapment of quartz inclusions in garnet on the basis of quartz crystallographic orientation.     

Production of carbonic fluids during metamorphism of graphitic pelites in a collisional orogen—An assessment from fluid inclusions

Fluid inclusions in quartz veins within Proterozoic metamorphic rocks in the Black Hills, South Dakota, were examined by microthermometry and Raman spectroscopy to assess the evolution of fluid compositions during regional metamorphism of organic-rich shales and late-orogenic magmatism, both of which were related to the collision of the Wyoming and Superior crustal blocks. Fluid inclusions occur in veins that began to be generated before or during regional compression and metamorphism that reached at least garnet-grade conditions, and in veins within the aureole of the Harney Peak Granite (HPG), where temperatures reached second-sillimanite grade conditions. Early veins in the schists have undergone recrystallization during heating and deformation that modified the composition of early CH₄ or CO₂ and N₂-dominated inclusions. These fluids were apparently trapped under conditions of immiscibility with a saline aqueous fluid phase. They are interpreted to represent components generated during maturation of organic matter and dehydration of phyllosilicates during incipient metamorphism at reducing fO₂ conditions. Most inclusions in the quartz veins are, however, secondary CO₂-bearing. They imply a transition to higher fO₂ conditions with increasing temperature of regional metamorphism. The fO₂ conditions may have been controlled by the mineral assemblage in the host metapelites. The prevalence of bimodal distributions of trapped CO₂-N₂ and aqueous endmembers in the biotite and garnet zones also suggests that two immiscible fluid phases existed during the regional metamorphism.In the aureole of the HPG, graphite was evidently consumed by influx of magmatic fluids. CO₂-H₂O fluid inclusions dominate, but they have significantly less N₂ than inclusions at lower metamorphic grades. All inclusions define secondary trails in mostly unstrained quartz. The bimodality of inclusion compositions is not as well defined as at lower grades, with many inclusions containing intermediate CO₂-H₂O compositions. This suggests that a single fluid phase existed at the high temperatures in the granite aureole, but then unmixed during cooling. A set of late quartz veins with graphitized and tourmalinized selvages in the granite aureole contains CH₄-bearing inclusions with little N₂. The existence of CH₄ in these inclusions is attributed to complexing of magmatic B with hydroxyl anions taken from the CO₂-H₂O fluid phase, effectively causing reduction in fO₂ and promoting precipitation of graphite.     

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.     

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.     

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.     

The fate of graphite in prograde metamorphism of pelites: An example from the Ballachulish aureole, Scotland

Graphite-bearing slates and phyllites (0.4–1.2 vol.% graphite) are progressively metamorphosed in the 3 kbar aureole of the 425 Ma Ballachulish intrusion, Scotland. Two major dehydration reactions are crossed: the chlorite-out reaction at ca. 550 °C (forming cordierite + biotite), and the muscovite-out reaction at 625 °C (forming Al₂SiO₅ + K-feldspar). Graphite persists to the highest grades and shows no significant variation in abundance with grade, except for a possible decrease in the highest grade rocks. Variable graphite abundance in rocks at the same grade reflects primary sedimentological heterogeneity. Texturally, graphite grains and aggregates in the rock matrix become coarser grained and more widely separated as grade increases. These thermally induced textural modifications of graphite are superimposed on mechanically induced features, such as graphite segregations along cleavages and crenulations, that formed prior to contact metamorphism. Mass balance modelling, assuming internal fluid generation, shows that the amount of graphite consumed during contact metamorphism in the aureole ranges between 0.1 and 0.3 vol.%, depending on the amount of chlorite and muscovite in the protolith. Because the amount of C dissolved in a C–O–H fluid decreases with increasing pressure, and the Ballachulish aureole is at relatively low pressure, these results are a maximum for regional metamorphism, suggesting that graphite will persist through a regional metamorphic cycle if it is initially present in volumes > ca. 0.2 vol.%.     

Dehydration-related deformation during regional metamorphism, NW Sardinia, Italy

The relationship between deformation and dehydration has been investigated in Hercynian regionally metamorphosed rocks exposed on NW Sardinia. Two episodes of prograde mineral growth (M₁ & M₂) involving dehydration are recognized: growth of chlorite/phengite porphyroblasts at anchizone metamorphic conditions, contemporaneous with the first phase of deformation, D₁, and growth of biotite from chlorite and phengite coincident with the second phase of deformation, D₂. Deformation during both episodes of dehydration is characterized by penetrative axial planar foliations defined by well-developed phyllosilicate preferred orientations quantified by XRD textural goniometry, tight to isoclinal similar folds (interlimb angles <40°), and mineral-filled veins (hydrofractures) orientated parallel to axial planar foliations, that formed contemporaneously with the development of the penetrative foliations. No prograde mineral growth occurred during D₂ at chlorite-zone conditions. D₂ deformation in the absence of dehydration is characterized by non-penetrative crenulation cleavages, poorly developed phyllosilicate preferred orientations, relatively open (interlimb angles >40°), low-strain similar folds and minor brittle deformation. Systematic variations in macrofold interlimb angles, with respect to the timing of mineral growth, indicate that enhanced shortening (c. 80%) occurred during dehydration. Microfabrics show that the onset of dehydration is associated with the transition from a crenulation cleavage to a penetrative foliation. The presence of axial planar hydrofractures that formed coevally with dehydration and fabric development requires that supralithostatic fluid pressures and low differential stresses (<c. 20 MPa) accompanied dehydration. These features demonstrate a connection between the timing of dehydration and the style of deformation.     

Fluid production rate during the regional metamorphism of a pelitic schist

Phase equilibria modeling of the pressure–temperature (P–T) path of regional metamorphism and associated fluid expulsion, combined with constraints on the timescale of garnet growth by Sm–Nd geochronology, elucidates the fluid production rate and fluid flux during Barrovian metamorphism of pelitic rocks from Townshend Dam, VT, USA. This modeling builds on a published companion study that utilized Sm–Nd geochronology of concentric growth zones in multiple garnet grains, to constrain the duration of garnet growth in a large sample of schist at Townshend Dam to 3.8?±?2.2 million years (Gatewood et al., Chem Geol 401:151–168, 2015). P–T pseudosections combined with observed mineral compositions constrain garnet growth conditions, and were utilized to construct P–T path-dependent thermodynamic forward models. These models determine that garnet growth was initiated at ~?0.6 GPa and ~?525 °C, with a roughly linear loading and heating P–T trajectory to >?0.8 GPa and ~?610 °C. Loading and heating rates of 2.4 km·Myear^?1 (with a range of 1.6 to 5.8 km·million year^?1) and 23 °C·million year^?1 (with a range of 14 to 54 °C·million year^?1), respectively, are consistent with model estimates and chronologic constraints for tectono-metamorphic rates during orogenesis. Phase equilibria modeling also constrains the amount of water release during garnet growth to be ~?0.7 wt% (or >?2 vol%), largely resulting from the complete consumption of chlorite. Coupling this estimate with calculated garnet growth durations provides a fluid production rate of 5.2 kg·m^?3·million year^?1 (with a range of 3.2 to 12.2 kg·m^?3·million year^?1) and when integrated over the overlying crustal column, a regional-scale fluid flux of 0.07–0.37 kg·m^?2·million year^?1. This range of values is consistent with those derived by numerical models and theory for regional-scale, pervasive fluid flow. This study signifies the first derivation of a fluid production rate and fluid flux in regional metamorphism using a direct chronology of water-producing (garnet-forming) reactions and can provide a framework for future studies on elucidating the nature and timescales of fluid release.     

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.     

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.     

Review and classification of structural controls on fluid flow during regional metamorphism

Mechanisms for kilometre-scale, open-system fluid flow during regional metamorphism remain problematic. Debate also continues over the degree of fluid flow channellization during regional metamorphism, and the mechanisms for pervasive fluid flow at depth. The requirements for pervasive long-distance fluid flow are an interconnected porosity and a large regional gradient in fluid pressure and hydraulic head (thermally or structurally controlled) that dominates over local perturbations in hydraulic head due to deformation. In contrast, dynamic or transient porosity interconnection and fluid flow accompanying deformation of heterogeneous rock suites should result in moderately to strongly channellized flow at a range of scales, of which there are many examples in the literature. Classification of fluid flow types based on scale and degree of equilibration between fluid and rock, wallrock permeability, and mode of fluid transport contributes to an understanding of key factors that control fluid flow. Closed-system fluid behaviour, with restricted fluid flow in microcracks or cracks and limited fluid–rock interaction, occurs over a range of strains and crustal depths, but requires low permeabilities and/or small fluid fluxes. Long-distance, open-system fluid flow in channels is favoured in heterogeneous rocks at high strains, moderate (but variable) permeabilities, and moderate to high fluid fluxes. Long-distance, broad, pervasive fluid flow during regional metamorphism requires that the rocks are not accumulating high strains and have high permeabilities, low permeability contrasts, and high fluid fluxes. The ideal situation for such fluid flow is in situations where the rocks are undergoing stress relaxation immediately after a major deformation phase. In the mid-crust, fairly specific conditions are thus required for pervasive fluid flow. During active orogenesis, structurally controlled fluid flow (with focused open systems surrounding regions of closed-system behaviour) predominates in most, but not all, regional metamorphic situations, at a range of scales.     

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.     

Mechanical controls on fluid flow during regional metamorphism: some numerical models

The control of fluid flow by plastic deformation during metamorphism is critical to our understanding of metamorphic processes. Various geological observations and field studies demonstrate the consequences of fluid flow control by deformation, so that the concept appears to be accepted, at least for small-scale PUBLIC (for example faults and vein PUBLIC). However, the concept appears to be less well recognized at regional scales. Considered here are examples of simple, conceptual models based on fully coupled mechanical–fluid flow concepts; they include deformation of a section of fluid-saturated crust containing a block or a layer of material of different properties from its surrounds. In particular, rheological and permeability contrasts between rock types during deformation associated with regional metamorphism are sufficient to control the form of fluid flow over the range of a few kilometres. Low contrasts and small strains allow pervasive fluid flow, whereas greater contrasts and increasing strains cause focusing of the flow. Such focusing is generally associated with localization of the deformation, especially for a strongly dilatant elastic–plastic material. However, a rate of fluid flow much greater than the rate of deformation may result in pervasive flow, although for most models pervasive flow is difficult to attain over regional distances. Furthermore, lateral and downward fluid flow may occur, demonstrated here by simple models for folding and for deformation of regions containing plutons. Therefore, such modelling may be used as a means of testing the various hypotheses concerning the volumes of fluid predicted to have passed through some rock volumes. Numerical models of the future will become increasingly complex and powerful, allowing greater coupling of thermal, mechanical, chemical and fluid flow effects, and based more on the physical processes involved. Combined field and laboratory studies will provide correspondingly greater understanding and will permit the determination of the timing of fluid flow and structural controls on fluid flow patterns.     

Regional metamorphism of some Dalradian pelites in the Buchan area,N.E. Scotland

Regional metamorphic zones, based on mineral assemblages in pelites, are presented for the Dalradian rocks of Aberdeenshire and Banffshire, in the type area of Buchan metamorphism; electron microprobe analyses of cordierite (C), staurolite (S), chlorite (Chl), biotite (B) and white mica (Ms) are reported for rocks from the classic sections of the Banffshire coast and the valley of the Ythan.A low grade biotite zone, separates two NE-SW trending sets of higher grade zones, in which the sequence s defined by the entry of cordierite, andalusite (A) and (in the west only) staurolite. The zones are characterised by the assemblages (with quartz and muscovite) B-Chl, C-B-Chl, A-C-B and S-A-B.The western sequence contains a transition towards higher pressure, Barrovian type, metamorphism. The isograds arise from continuous reactions affecting rocks of restricted bulk composition (M/FM). With increasing grade, there is a regular trend towards more magnesian ranges of composition for the assemblages C-B-Chl, A-C-B and finally (as P increases in the west), S-A-B. The isograds form when these assemblages intersect the most Fe⁺⁺-rich rock compositions present which occurs in each case when the biotite M/FM=40. A complex of divariant equilibria, derived for the system KFMASH, is used to model the natural reactions.     

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     

The magnesium and calcium contents of sediments,especially pelites,as a function of age and degree of metamorphism

The silicate and carbonate fraction of 98 non-metamorphic shale samples from the Australian platform and of different geological age were analysed for calcium, magnesium, ferrous iron and carbonate. Cainozoic and Mesozoic shales prove to be essentially calcitic, Cambrian and Proterozoic shales are essentially dolomitic and sideritic. A similar trend of high MgO values can be demonstrated for the silicate fraction of the old shales. Extensive literature study confirms these trends for shales and carbonate rocks from all over the world. Slates, hornfelses and schists are Mg rich and Ca poor, whether young or old.Ronov's model of the evolution of the earth's crust ocean and atmosphere, explaining these trends, is critically reviewed but rejected because of impossible storage problems of calcium in the Proterozoic. The increased magnesium content of the old sediments is explained by calcium carbonate sweating out of the sedimentary column, magnesium introduction from altering volcanic rocks within the sedimentary pile and magnesium introduction from connate brines in sandstones. The increasing calcium content of all kinds of sediments with decreasing age is claimed to be related to preferential weathering of extrusive volcanic rocks and sweating out of calcium carbonate from the sedimentary column.     

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.     

Low-pressure metamorphism of Palaeozoic pelites in the Aspromonte, southern Calabria: constraints for the thermal evolution in the Calabrian crustal cross-section during the Hercynian orogeny

During Hercynian low-pressure/high-temperature metamorphism of Palaeozoic metasediments of the southern Aspromonte (Calabria), a sequence of metamorphic zones at chlorite, biotite, garnet, staurolite–andalusite and sillimanite–muscovite grade was developed. These metasediments represent the upper part of an exposed tilted cross-section through the Hercynian continental crust. P–T information on their metamorphism supplements that already known for the granulite facies lower crust of the section and allows reconstruction of the thermal conditions in the Calabrian crust during the late Hercynian orogenic event. Three foliations formed during deformation of the metasediments. The peak metamorphic assemblages grew mainly syntectonically (S2) during regional metamorphism, but mineral growth outlasted the deformation. This is in accordance with the textural relationships found in the lower part of the same crustal section exposed in the northern Serre. Pressure conditions recorded for the base of the upper crustal metasediments are c. 2.5 kbar and estimated temperatures range from <350 °C in the chlorite zone, increasing to 500 °C in the lower garnet zone, and reaching 620 °C in the sillimanite–muscovite zone. Geothermal gradients for the peak of metamorphism indicate a much higher value for the upper crust (c. 60 °C km^?1) than for the granulite facies lower crust (30–35 °C km^?1). The small temperature difference between the base of the upper crust (620 °C at c. 2.5 kbar) and the top of the lower crust (690 °C at 5.5 kbar) can be explained by intrusions of granitoids into the middle crust, which, in this crustal section, took place synchronously with the regional metamorphism at c. 310– 295 Ma. It is concluded that the thermal structure of the Calabrian crust during the Hercynian orogeny – as it is reflected by peak metamorphic assemblages – was mainly controlled by advective heat input through magmatic intrusions into all levels of the crust.