Characterisation of a garnet population from the Sikkim Himalaya: insights into the rates and mechanisms of porphyroblast crystallisation

The compositional zoning of a garnet population contained within a garnet-grade metapelitic schist from the Lesser Himalayan Sequence of Sikkim (India) provides insight into the rates and kinetic controls of metamorphism, and the extent of chemical equilibration during porphyroblast crystallisation in the sample. Compositional profiles across centrally sectioned garnet crystals representative of the observed crystal size distribution indicate a strong correlation between garnet crystal size and core composition with respect to major end-member components. Systematic steepening of compositional gradients observed from large to small grains is interpreted to reflect a progressive decrease in the growth rate of relatively late-nucleated garnet as a result of an increase in interfacial energies during progressive crystallisation. Numerical simulation of garnet nucleation and growth using an equilibrium approach accounting for chemical fractionation associated with garnet crystallisation reproduces both the observed crystal size distribution and the chemical zoning of the entire garnet population. Simulation of multicomponent intracrystalline diffusion within the population indicates rapid heating along the pressure–temperature path, in excess of 100 \(^{\circ }\)C Myr\(^{-1}\). Radial garnet growth is correspondingly rapid, with minimum rates of 1.4 mm Myr\(^{-1}\). As a consequence of such rapid crystallisation, the sample analysed in this study provides a close to primary record of the integrated history of garnet nucleation and growth. Our model suggests that nucleation of garnet occurred continuously between incipient garnet crystallisation at \(\sim\)520 \(^{\circ }\)C, 4.5 kbar and peak metamorphic conditions at \(\sim\)565 \(^{\circ }\)C, 5.6 kbar. The good fit between the observed and predicted garnet growth zoning suggests that the departure from equilibrium associated with garnet nucleation and growth was negligible, despite the particularly fast rates of metamorphic heating. Consequently, rates of major element diffusion in the intergranular medium during garnet crystallisation are interpreted to have been correspondingly rapid. It is, therefore, possible to simulate the prograde metamorphic history of our sample as a succession of equilibrium states of a chemical system modified by chemical fractionation associated with garnet crystallisation.     

Prograde garnet growth along complex <Emphasis Type="Italic">P–T–t</Emphasis> paths: results from numerical experiments on polyphase garnet from the Wölz Complex (Austroalpine basement)

Garnet in metapelites from the Wölz Complex of the Austroalpine crystalline basement east of the Tauern Window characteristically consists of two growth phases, which preserve a comprehensive record of the geothermal history during polymetamorphism. From numerical modelling of garnet formation, detailed information on the pressure–temperature–time (P–T–t) evolution during prograde metamorphism is obtained. In that respect, the combined influences of chemical fractionation associated with garnet growth, modification of the original growth zoning through intragranular diffusion and the nucleation history on the chemical zoning of garnet as P and T change during growth are considered. The concentric chemical zoning observed in garnet and the homogenous rock matrix, which is devoid of chemical segregation, render the simulation of garnet growth through successive equilibrium states reliable. Whereas the first growth phase of garnet was formed at isobaric conditions of ～3.8 kbar at low heating/cooling rates, the second growth phase grew along a Barrovian P–T path marked with a thermal peak of ～625°C at ～10 kbar and a maximum in P of ～10.4 kbar at ～610°C. For the heating rate during the growth of the second phase of garnet, average rates faster than 50°C Ma^?1 are obtained. From geochronological investigations the first growth phase of garnet from the Wölz Complex pertains to the Permian metamorphic event. The second growth phase grew in the course of Eo-Alpine metamorphism during the Cretaceous.     

Strain rates at high temporal resolution from curved inclusion trails in garnet,Passo del Sole,Central Swiss Alps

Quantitative strain rates at outcrop scale are very difficult to obtain, but they may be estimated from crystals with curved inclusion trails by calculating rotation rates from growth rates and corresponding deflections of the internal foliation. Garnet in a quartzose pelite at Passo del Sole in the central Swiss Alps is extraordinarily valuable for calculation of strain rates during Alpine orogenesis, because the unusual zoning patterns clearly define the kinetics of its nucleation and growth. Complex concentric zoning patterns can be correlated from one crystal to another in a hand sample, based on compositional and microstructural similarities; the ubiquity of these features demonstrates that all garnet crystals nucleated at nearly the same time. Compositional bands whose radial widths are proportional to crystal size provide evidence for growth governed by the kinetics of intergranular diffusion of locally sourced nutrients. Together, these constraints increase the reliability of estimates of rates of garnet growth, and the strain‐rate calculations that depend on them. To obtain growth rates, P–T conditions during garnet crystallization were modelled in a series of pseudosections, and compositional evolution was connected to rates of garnet growth by means of an independently determined heating rate. These growth rates, combined with measured amounts of curvature of inclusion trails, indicate that the time‐averaged strain rate at Passo del Sole during Alpine metamorphism was on the order of 10^?14 s^?1. Strain rates calculated using rotational v. non‐rotational models are similar in magnitude. The constraints on crystallization kinetics also allow direct calculation of strain rates during individual stages of garnet growth, revealing short‐term increases to values on the order of 10^?13 s^?1. These higher strain rates are correlated with the growth of concentric high‐Ca or high‐Mn zones in garnet, which implies that strain softening associated with the transient passage of fluids is responsible for acceleration of deformation during these intervals.     

Controls on porphyroblast size along a regional metamorphic field gradient

Garnet-bearing schists from the Waterville Formation of south-central Maine provide an opportunity to examine the factors governing porphyroblast size over a range of metamorphic grade. Three-dimensional sizes and locations for all garnet porphyroblasts were determined for three samples along the metamorphic field gradient spanning lowest garnet through sillimanite grade, using high-resolution X-ray computed tomography. Comparison of crystal size distributions to previous data sets obtained by stereological methods for the same samples reveals significant differences in mode, mean, and shape of the distributions. Quantitative textural analysis shows that the garnets in each rock crystallized in a diffusion-controlled nucleation and growth regime. In contrast to the typical observation of a correlation between porphyroblast size and position along a metamorphic field gradient, porphyroblast size of the lowest-grade specimen is intermediate between the high- and middle-grade specimens’ sizes. Mean porphyroblast size does not correlate with peak temperatures from garnet-biotite Fe-Mg exchange thermometry, nor is post-crystallization annealing (Ostwald Ripening) required to produce the observed textures, as was previously proposed for these rocks. Robust pseudosection calculations fail to reproduce the observed garnet core compositions for two specimens, suggesting that these calc-pelites experienced metasomatism. For each of these two specimens, Monte Carlo calculations suggest potential pre-metasomatism bulk compositions that replicate garnet core compositions. Pseudosection analyses allow the estimation of the critical temperatures for garnet growth: ∼481, ∼477, and ∼485°C for the lowest-garnet-zone, middle-garnet-zone, and sillimanite-zone specimens, respectively. Porphyroblast size appears to be determined in this case by a combination of the heating rate during garnet crystallization, the critical temperature for the garnet-forming reaction and the kinetics of nucleation. Numerical simulations of thermally accelerated, diffusion-controlled nucleation, and growth for the three samples closely match measured crystal size distributions. These observations and simulations suggest that previous hypotheses linking the garnet size primarily to the temperature at the onset of porphyroblast nucleation can only partially explain the observed textures. Also important in determining porphyroblast size are the heating rate and the distribution of favorable nucleation sites.     

The effect of metamorphic fluid flow on the nucleation and growth of garnets from Troms, North Norway

A spatial association is observed between the size distribution of garnet porphyroblasts and the size distribution of quartz veins in greenschist facies metapelites from Troms, North Norway. The size distribution of quartz veins reflects the flow regime of metamorphic fluids. The hypothesis that the flow regime of metamorphic fluids is also responsible for the size distribution of garnet crystals was tested by ascribing empirical acceleration parameters to the nucleation and growth rates of garnet crystals.
In regions where fluid flow was interpreted as pervasive', acceleration parameters for nucleation were high, whereas in regions where fluid flow was interpreted as channelled', acceleration parameters for growth were high. Accelerated crystal growth is further implied from the chemical zoning and crystal morphologies of garnets collected near discrete veins.
This spatial association may imply that fluid flow can be instrumental in controlling garnet crystallization. Fluid flow could affect garnet crystallization kinetics by facilitating thermal advection and/or mass transfer. In the study area, rhodochrosite (MnCO₃) veins provide evidence for mass transfer of Mn by fluid flow. An influx of Mn would expand the stability field of garnet to lower temperatures. The resulting thermal overstep could accelerate nucleation and/or growth of garnets.
The corollary of this study is that size distributions and chemical zoning of garnets, or other porphyroblast phases, can be used to study metamorphic fluid flow.     

The significance of intergranular diffusion to the mechanisms and kinetics of porphyroblast crystallization

The spatial disposition, compositional zoning profiles, and size distributions of garnet crystals in 11 specimens of pelitic schist from the Picuris Range of New Mexico (USA) demonstrate that the kinetics of intergranular diffusion controlled the nucleation and growth mechanisms of porphyroblasts in these rocks. An ordered disposition of garnet centers and a significant correlation between crystal radius and near-neighbor distances manifest suppressed nucleation of new crystals in diffusionally depleted zones surrounding pre-existing crystals. Compositional zoning profiles require diffusionally controlled growth, the rate of which increases exponentially as temperature increases with time; an acceleration factor for growth rate can be estimated from a comparison of compositional profiles for crystals of different sizes in each specimen. Crystal size distributions are interpreted as the result of nucleation rates that accelerate exponentially with increasing temperature early in the crystallization process, but decline in the later stages because of suppression effects in the vicinity of earlier-formed nuclei. Simulations of porphyroblast crystallization, based upon thermally accelerated diffusionally influenced nucleation kinetics and diffusionally controlled growth kinetics, quantitatively replicate textural relations in the rocks. The simulations employ only two variable parameters, which are evaluated by fitting of crystal size distributions. Both have physical significance. The first is an acceleration factor for nucleation, with a magnitude reflecting the prograde increase during the nucleation interval of the chemical affinity for the reaction in undepleted regions of the rock. The second is a measure of the relative sizes of the porphyroblast and the diffusionally depleted zone surrounding it. Crystal size distributions for the Picuris Range garnets correspond very closely to those in the literature from a variety of other localities for garnet and other minerals. The same kinetic model accounts quantitatively for crystal size distributions of porphyroblastic garnet, phlogopite, sphene, and pyroxene in rocks from both regional and contact metamorphic occurrences. These commonalities indicate that intergranular diffusion may be the dominant kinetic factor in the crystallization of porphyroblasts in a wide variety of metamorphic environments.     

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.     

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.     

Constraining the conditions of Barrovian metamorphism in Sikkim,India: P–T–t paths of garnet crystallization in the Lesser Himalayan Belt

Garnet crystallization in metapelites from the Barrovian garnet and staurolite zones of the Lesser Himalayan Belt in Sikkim is modelled utilizing Gibbs free energy minimization, multi‐component diffusion theory and a simple nucleation and growth algorithm. The predicted mineral assemblages and garnet‐growth zoning match observations remarkably well for relatively tight, clockwise metamorphic P–T paths that are characterized by prograde gradients of ～30 °C kbar^?1 for garnet‐zone rocks and ～20 °C kbar^?1 for rocks from the staurolite zone. Estimates for peak metamorphic temperature increase up‐structure toward the Main Central Thrust. According to our calculations, garnet stopped growing at peak pressures, and protracted heating after peak pressure was absent or insignificant. Almost identical P–T paths for the samples studied and the metamorphic continuity of the Lesser Himalayan Belt support thermo‐mechanical models that favour tectonic inversion of a coherent package of Barrovian metamorphic rocks. Time‐scales associated with the metamorphism were too short for chemical diffusion to substantially modify garnet‐growth zoning in rocks from the garnet and staurolite zones. In general, the pressure of initial garnet growth decreases, and the temperature required for initial garnet growth was reached earlier, for rocks buried closer toward the MCT. Deviations from this overall trend can be explained by variations in bulk‐rock chemistry.     

Oriented growth of garnet by topotactic reactions and epitaxy in high‐pressure,mafic garnet granulite formed by dehydration melting of metastable hornblende‐gabbronorite (Jijal Complex,Kohistan Complex,north Pakistan)

Garnet growth in high‐pressure, mafic garnet granulites formed by dehydration melting of hornblende‐gabbronorite protoliths in the Jijal complex (Kohistan palaeo‐island arc complex, north Pakistan) was investigated through a microstructural EBSD‐SEM and HRTEM study. Composite samples preserve a sharp transition in which the low‐pressure precursor is replaced by garnet through a millimetre‐sized reaction front. A magmatic foliation in the gabbronorite is defined by mafic‐rich layering, with an associated magmatic lineation defined by the shape‐preferred orientation (SPO) of mafic clusters composed of orthopyroxene (Opx), clinopyroxene (Cpx), amphibole (Amp) and oxides. The shape of the reaction front is convoluted and oblique to the magmatic layering. Opx, Amp and, to a lesser extent, Cpx show a strong lattice‐preferred orientation (LPO) characterized by an alignment of [001] axes parallel to the magmatic lineation in the precursor hornblende‐gabbronorite. Product garnet (Grt) also displays a strong LPO. Two of the four 〈111〉 axes are within the magmatic foliation plane and the density maximum is subparallel to the precursor magmatic lineation. The crystallographic relationship 〈111〉_Grt // [001]_Opx,Cpx,Amp deduced from the LPO was confirmed by TEM observations. The sharp and discontinuous modal and compositional variations observed at the reaction front attest to the kinetic inhibition of prograde solid‐state reactions predicted by equilibrium‐phase diagrams. The P–T field for the equilibration of Jijal garnet granulites shows that the reaction affinities are 5–10 kJ mol.^?1 for the Grt‐in reaction and 0–5 kJ mol.^?1 for the Opx‐out reaction. Petrographic and textural observations indicate that garnet first nucleated on amphibole at the rims of mafic clusters; this topotactic replacement resulted in a strong LPO of garnet. Once the amphibole was consumed in the reaction, the parallelism of [001] axes of the mafic‐phase reactants favoured the growth of garnet crystals with similar orientations over a pyroxene substrate. These aggregates eventually sintered into single‐crystal garnet. In the absence of deformation, the orientation of mafic precursor phases conditioned the nucleation site and the crystallographic orientation of garnet because of topotaxial transformation reactions and homoepitaxial growth of garnet during the formation of high‐pressure, mafic garnet‐granulite after low‐pressure mafic protoliths.     

A garnet population in Yellowknife schist, Canada

Abstract Data are presented on a garnet population in a specimen of garnet-biotite-plagioclase-quartz schist from the cordierite zone of an Archaean thermal dome in the Southern Slave Province of the Canadian Shield. Garnet crystals are bounded by planar dodecahedral faces and by trapezohedral faces which on the 10-μm scale are corrugated. Crystal distribution, as revealed by dissection of a small cubic volume of rock, is random. The size distribution is normal, with a mean diameter of 0.81 mm and a standard deviation of 0.32 mm. In the largest crystal of the population (mean radius 0.83 mm), [Mn] = 100 Mn/(Fe + Mg + Mn + Ca) decreases from 14.5 at the centre to 7.5 and then increases in the outer margin to 8.5; [Fe] increases continuously from 67 at the centre to 77 at the surface; [Mg] increases from 12.5 to 13.5 and then falls sharply to 11; [Ca] remains unchanged at 4.0 and then drops to 3.3. Progressively smaller crystals have progressively lower [Mn] and higher [Fe] concentrations at their centres, while all crystals have the same margin composition. Growth vectors extending from given concentration contours to crystal surfaces are of equal length regardless of the size of the crystal in which the vector is located. A garnet-forming model is presented in which reaction was initiated by a rise in temperature. Nucleation sites were randomly selected. The nucleation rate increased with time and then declined. Crystal faces advanced at a constant linear rate, which implies an increase in volume proportional to surface area. Initially, the composition of garnet deposited on crystal surfaces was determined by van Laar equations of equilibrium, which demanded the withdrawal of Mn and Fe from within chlorite crystals. This transfer reaction was then accompanied by an ion exchange reaction which moved Mn and Fe to garnet surfaces from biotite, in exchange for Mg. The exchange reaction provides an explanation for the high overall concentration of Mn and Fe in garnet and for the observed Mn and Mg reversals in the margins of crystals. The increase of garnet volume in the garnet population is found to be parabolic, i.e. Vαα⁵.     

Ostwald ripening of garnet in high P/T metamorphic rocks

This paper presents a theoretical formulation of Ostwald ripening of garnet and discusses the importance of the process during high pressure and low temperature (high P/T) metamorphism. The growth rate of garnet due to Ostwald ripening is formulated for the system consisting of minerals and an intergranular medium. Crystal size distribution (CSD) of garnets are examined and compared with the theoretical distribution for Ostwald ripening. Two types of CSDs are recognized. One is consistent with the theoretical prediction of size distribution while the other is wider than the theoretical distribution. The former CSD applies to samples in which garnets show homogeneous spatial distributions. The latter CSD applies to samples in which garnets show heterogeneous spatial distributions such as in clusters or layers. These relations suggest that the heterogeneity of spatial distributions results in a heterogeneity of concentration of garnet, causing the wide distributions. The mean diameter (dg) has a large variation in samples having narrow distributions. Ostwald ripening explains well the similar patterns of CSD in these samples with different dg because of a scaling law. Compositional profiles of garnets with different size are consistent with Ostwald ripening rather than nucleation and growth kinetics. This suggests that the CSDs result from Ostwald ripening. Magnitude of heating rate will determine which mechanism controls CSD. Nucleation and growth kinetics are dominant when heating rate is large. On the other hand, Ostwald ripening is dominant when heating rate is small. CSDs of garnets in high P/T metamorphic rocks are consistent with the latter case.     

陕西丹凤秦岭群石榴子石变质结晶动力学研究

本文运用晶体大小分布理论对陕西丹凤秦岭群石榴子石进行了变质结晶动力学的研究,通过对石榴子石在岩石中出现的频率及其大小值的系统测定,有关变质结晶动力学的分析计算,最终得出了丹凤秦岭群石榴子石的变质结晶初始成核密度、成核速度、晶体生长速度、生长时间及冷却过程中体积转移量等诸动力学要素,并从晶体大小分布研究中获得了多期复杂变质这一与地质事实一致的重要地质信息。     

The clustered nucleation and growth processes of garnet in regional metamorphic rocks from north-west Connecticut,USA

Serial sectioning and imaging with a flatbed scanner yielded the three-dimensional size and spatial distribution of garnet porphyroblasts in two garnet schists and one staurolite-bearing schist from the Everett Formation, north-west Connecticut. The dominant garnet-producing reaction in all samples was chlorite+quartz=garnet+H₂O. The appearance of staurolite, and additional garnet growth in the staurolite-bearing sample, was due to the reaction chloritoid=garnet+staurolite+chlorite. Statistical measures of garnet spatial distributions, using the pair correlation function (PCF), indicate that garnet crystals are weakly to strongly clustered at length scales between 2 and 10 mm. Such clustered nucleation may reflect minor bulk compositional variations. Covariance measures between garnet size and nearest-neighbour distance, using the mark covariance function (MCF), suggest a very weak correlation between crystal size and nearest-neighbour distance for length scales of 2 mm or less. These statistical data suggest that if diffusional gradients were present around growing garnet crystals, they did not influence nucleation and growth patterns at length scales greater than c. 2 mm. Compositional maps, through the garnet centres, show that the smaller crystals have lower Mn core compositions relative to larger crystals, consistent with progressive nucleation during pro-grade metamorphism. Radius-rate plots calculated from compositional X-ray maps show similar growth rates for garnet crystals of different size, consistent with an interface-controlled growth model for garnet. The presence of minor diffusional gradients around growing garnet cannot be entirely dismissed, but the lack of observable reaction rims, the clustered spatial distribution and the radius-rate data are most consistent with an interface-controlled garnet growth model.     

Diffusion control of garnet growth,Harpswell Neck,Maine, USA

A detailed analysis of chemical zoning in two garnet crystals from Harpswell Neck, Maine, forms the basis of an interpretation of garnet nucleation and growth mechanisms. Garnet apparently nucleates initially on crenulations of mica and chlorite and quickly overgrows the entire crenulation, giving rise to complex two‐dimensional zoning patterns depending on the orientation of the thin section cut. Contours of Ca zoning cross those of Mn, Fe and Mg, indicating a lack of equilibrium among these major garnet constituents. Zoning of Fe, Mg and Mn is interpreted to reflect equilibrium with the rock matrix, whereas Ca zoning is interpreted to be controlled by diffusive transport between the matrix and the growing crystal. Image analysis reveals that the growth of garnet is more rapid along triple‐grain intersections than along double‐grain boundaries. Moreover, different minerals are replaced by garnet at different rates. The relative rate of replacement by garnet along double‐grain boundaries is ordered as muscovite > chlorite > plagioclase > quartz. Flux calculations reveal that replacement is limited by diffusion of Si along double‐grain boundaries to or from the local reaction site. It is concluded that multiple diffusive pathways control the bulk replacement of the rock matrix by garnet, with Si and Al transport being rate limiting in these samples.     

Diffusion gradients in an eclogite xenolith from the Roberts Victor kimberlite pipe: (2) kinetics and implications for petrogenesis

In a bimineralic eclogite xenolith (sample JJG41) from the Roberts Victor kimberlite, compositional gradients in clinopyroxene are related to garnet exsolution. Two principal reactions involving clinopyroxene and garnet occur: (i) The net-transfer Al₂Si^-1Mg^-1 which is responsible for garnet growth according to the equation 2Di+Al₂Si^-1Mg^-1=Grossular+MgCa^-1 (reaction 1). This has created substantial compositional gradients in Al, Si and Mg within clinopyroxene. (ii) The exchange of Fe–Mg between garnet and clinopyroxene (reaction 2). During the stage of garnet growth (reaction 1) the lamellae crystallized sequentially as a result of a temperature decrease from around 1400 to 1200° C. This exsolution growth-stage was under the control of Al diffusion in clinopyroxene and at around 1200° C further growth of garnet lamellae became impeded by the sluggishness of Al diffusion in the clinopyroxene host. However, reaction 2 continued during further cooling down to about 1000° C; this temperature being inferred from the constant Fe–Mg partitioning at clinopyroxene-garnet interfaces for the whole set of lamellae. The initial clinopyroxene in JJG41 was probably formed by crystallization from a melt in Archaean time. The cessation of Fe–Mg exchange between garnet and clinopyroxene at about 1000° C may well predate the eruption of the eclogite in kimberlite at around 100 Ma. Kinetic models of reaction are examined for both reactions. Modelling of reaction 1, involving both diffusion and interface migration, allows several means of estimating the diffusion coefficient of Al in clinopyroxene; the estimates are in the range 10^-16-10^-20 cm²/s at 1200° C. These estimates bracket the experimentally determined data for Al diffusion in clinopyroxene, and from these experimental data a preferred cooling rate of about 300° C/Ma is obtained for the period of growth of garnet exsolution lamellae. A geospeedometry approach (Lasaga 1983) suitable for a pure-exchange process (reaction 2) is used to estimate the cooling rate in the later stages of the thermal history (after garnet growth); values 4–40° C/Ma are consistent with the shape of the Fe-diffusion gradients in the clinopyroxene. The extensive thermal history recorded by JJG41, including probable melt involvement at ca. 1400° C, demonstrates the complex evolution of rocks within the mantle. Whilst the notion of formation of mantle eclogites from subducted oceanic crust has become fashionable, it is clear that tracing eclogite geochemical and P-T characteristics backwards from their nature at the time of xenolith eruption, through high-temperature mantle events to the characteristics of the original subducted oceanic crust, will be very complex.     

Variations in rates of nucleation and growth of biotite porphyroblasts

Differences in rates of nucleation and diffusion‐limited growth for biotite porphyroblasts in adjacent centimetre‐scale layers of a garnet‐biotite schist from the Picuris Mountains of New Mexico are revealed by variations in crystal size and abundance between two layers with strong compositional similarity. Relationships between fabrics recorded by inclusion patterns in biotite and garnet porphyroblasts are interpreted to reflect garnet growth following biotite growth, without substantial alteration of the biotite sizes. Sizes and locations of biotite crystals, obtained via high‐resolution X‐ray computed tomography, document that of the two adjacent layers, one has a larger mean crystal volume (9.5 × 10^?4v. 2.4 × 10^?4 cm³), fewer biotite crystals per unit volume (232 v. 576 crystals cm^?3), and a higher volume fraction of biotite (23%v. 14%). The two layers have similar mineral assemblages and mineral chemistry. Both layers show evidence for diffusional control of nucleation and growth. Pseudosection analysis suggests that the large‐biotite layer began to crystallize biotite at a temperature ～67 °C greater than the small‐biotite layer. Diffusion rates differed between layers, because of their different temperature ranges of crystallization, but this effect can be quantified. The bulk compositional difference between the layers, manifested in different modal amounts of biotite, has an effect on the biotite sizes that is also quantifiable and insufficient to account for the difference in biotite size. After these other possible causes of variation in crystal sizes have been eliminated, variability in nucleation and diffusion rates remain as the dominant factors responsible for the difference in porphyroblastic textures. Numerical simulations suggest that relative to the small‐biotite layer, the large‐biotite layer experienced elevated diffusion rates because of the higher crystallization temperature, as well as increased nucleation rates in order to achieve the observed size and number density of crystals. The simulations can replicate the observed textures only by invoking unreasonably large values for the thermal dependence of nucleation rates (activation energies), strongly suggesting that the observed textural differences arise from variations between layers in the abundance and energetics of potential nucleation sites.     

Prograde pressure–temperature paths in the pelitic schists of the Sambagawa metamorphic belt, SW Japan

Prograde P–T paths recorded by the chemistry of minerals of subduction‐related metamorphic rocks allow inference of tectonic processes at convergent margins. This paper elucidates the changing P–T conditions during garnet growth in pelitic schists of the Sambagawa metamorphic belt, which is a subduction related metamorphic belt in the south‐western part of Japan. Three types of chemical zoning patterns were observed in garnet: Ca‐rich normal zoning, Ca‐poor normal zoning and intrasectoral zoning. Petrological studies indicate that normally‐zoned garnet grains grew keeping surface chemical equilibrium with the matrix, in the stable mineral assemblage of garnet + muscovite + chlorite + plagioclase + paragonite + epidote + quartz ± biotite. Pressure and temperature histories were inversely calculated from the normally‐zoned garnet in this assemblage, applying the differential thermodynamic method (Gibbs' method) with the latest available thermodynamic data set for minerals. The deduced P–T paths indicate slight increase of temperature with increasing pressure throughout garnet growth, having an average dP/dT of 0.4–0.5 GPa/100 °C. Garnet started growing at around 470 °C and 0.6 GPa to achieve the thermal and baric peak condition near the rim (520 °C, 0.9 GPa). The high‐temperature condition at relatively low pressure (for subduction related metamorphism) suggests that heating occurred before or simultaneously with subduction.     

Garnet growth during crustal thickening in the Cascades Crystalline Core,Washington, USA

Garnet Sm–Nd and zircon U–Pb ages, and pressure–temperature–time paths elucidate Late Cretaceous crustal thickening which occurred within magmatic arc rocks of the Insular Superterrane. Voluminous tonalitic magma of the Mount Stuart batholith intruded at <3 kbar into upper crustal sedimentary rocks between 96 and 91 Ma, with initial intrusion prior to garnet growth in the metasedimentary rocks. Arc plutonism then shifted northward as crustal thickening commenced. Initial garnet growth, locally with kyanite and staurolite replacing andalusite, at c. 91 Ma was directly associated with intrusion of granodiorite to tonalite sheets at 7 kbar, north of the Mount Stuart batholith, within the Nason Ridge Migmatitic Gneiss. Subsequent heating and garnet growth, which postdates emplacement of large plutons, occurred between 88 and 86 Ma. This late garnet growth occurred at pressures of 6–8 kbar. The history of garnet growth and intrusion indicates that initial garnet zone and higher temperature metamorphism was restricted to contact aureoles. However, later widespread garnet growth at higher pressure probably resulted from heating as the orogenic wedge approached thermal equilibrium after crustal thickening. We conclude that metasedimentary rocks outside narrow contact aureoles remained at temperatures significantly below those of garnet growth and that the growth of garnet lasted <6 Myr. Heating to temperatures that stabilized garnet after pluton emplacement is compatible with intrusion of arc plutons into an accretionary wedge (Chiwaukum Schist) which was tectonically thickened and/or overthrust causing loading and thermal relaxation.     

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.