Asymmetrically zoned reaction rims: assessment of grain boundary diffusivities and growth rates related to natural diffusion-controlled mineral reactions

This study explores garnet coronas around hedenbergite, which were formed by the reaction plagioclase + hedenbergite→garnet + quartz, to derive information about diffusion paths that allowed for material redistribution during reaction progress. Whereas quartz forms disconnected single grains along the garnet/hedenbergite boundaries, garnet forms ～20‐μm‐wide continuous polycrystalline rims along former plagioclase/hedenbergite phase boundaries. Individual garnet crystals are separated by low‐angle grain boundaries, which commonly form a direct link between the reaction interfaces of the plagioclase|garnet|hedenbergite succession. Compositional variations in garnet involve: (i) an overall asymmetric compositional zoning in Ca, Fe²⁺, Fe³⁺ and Al across the garnet layer; and (ii) micron‐scale compositional variations in the near‐grain boundary regions and along plagioclase/garnet phase boundaries. These compositional variations formed during garnet rim growth. Thereby, transfer of the chemical components occurred by a combination of fast‐path diffusion along grain boundaries within the garnet rim, slow diffusion through the interior of the garnet grains, and by fast diffusion along the garnet/plagioclase and the garnet/hedenbergite phase boundaries. Numerical simulation indicates that diffusion of Ca, Al and Fe²⁺ occurred about three to four, four and six to seven orders of magnitude faster along the grain boundaries than through the interior of the garnet grains. Fast‐path diffusion along grain boundaries contributed substantially to the bulk material transfer across the growing garnet rim. Despite the contribution of fast‐path diffusion, bulk diffusion through the garnet rim was too slow to allow for chemical equilibration of the phases involved in garnet rim formation even on a micrometre scale. Based on published garnet volume diffusion data the growth interval of a 20‐μm‐wide garnet rim is estimated at ～10³–10⁴ years at the inferred reaction conditions of 760 ± 50 °C at 7.6 kbar. Using the same parameterization of the growth law, 100‐μm‐ and 1‐mm‐thick garnet rims would grow within 10⁵–10⁶ and 10⁶–10⁷ years respectively.     

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.     

Garnet reaction rims from the breakdown of Staurolite in polymetamorphic micashists from the Rappold complex, Austroalpine basement, Eastern Alps

In polymetamorphic pelites of the Rappold complex in the Wölz crystalline basement (Eastern Alps) reaction rim garnets at staurolite-quartz interfaces (type I) and single grain garnets along previous staurolite-white mica interfaces (type II) were formed. The garnet reaction rims were formed during the Cretaceous amphibolite facies metamorphic overprint of the pre-existing mineral assemblages comprising garnet, staurolite, and kyanite from an amphibolite facies metamorphic event probably of Variscian age. The newly formed garnet may take the form of reaction rims along the margins of large pre-existing staurolite blasts. The initial growth increments of garnet have low grossular content, and reaction rim growth was controlled by the transfer of Fe, Mg and Mn components from the staurolite-garnet interface to the quartz-garnet interface. Later garnet growth increments have relatively high grossular content due to consumption of matrix plagioclase, which was destabilized by successive pressure increase. The grossular content of newly formed garnet shows systematic increase towards sites where plagioclase breaks down indicating that transport of calcium through the matrix was sluggish. On the basis of reaction microstructures it is demonstrated that the mineral assemblage garnet?+?kyanite?+?biotite?+?paragonite was formed at the conditions of eo-alpine amphibolite facies overprint while staurolite and plagioclase broke down successively with increasing pressure.     

Garnet re‐equilibration by coupled dissolution–reprecipitation: evidence from textural,major element and oxygen isotope zoning of ‘cloudy’ garnet

The analysis of texture, major element and oxygen isotope compositions of cloudy garnet crystals from a metapelite sampled on Ikaria Island (Greece) is used to assess the model of growth and re‐equilibration of these garnet crystals and to reconstruct the pressure–temperature–fluid history of the sample. Garnet crystals show complex textural and chemical zoning. Garnet cores (100–200 μm) are devoid of fluid inclusions. They are characterized by growth zoning demonstrated by a bell‐shaped profile of spessartine component (7–3 mol.%), an increase in grossular from 14 to 22 mol.% and δ¹⁸O values between 9.5 ± 0.3‰ and 10.4 ± 0.2‰. Garnet inner rims (90–130 μm) are fluid inclusion‐rich and show a decreasing grossular component from 22 to 5 mol.%. The trend of the spessartine component observed in the inner rim allows two domains to be distinguished. In contrast to domain I, where the spessartine content shows the same trend as in the core, the spessartine content of domain II increases outwards from 2 to 14 mol.%. The δ¹⁸O values decrease towards the margins of the crystals to a lowest value of 7.4 ± 0.2‰. The outer rims (<10 μm) are devoid of fluid inclusions and have the same chemical composition as the outermost part of domain II of the inner rim. Garnet crystals underwent a four‐stage history. Stage 1: garnet growth during the prograde path in a closed system for oxygen. Garnet cores are remnants of this growth stage. Stage 2: garnet re‐equilibration by coupled dissolution–reprecipitation at the temperature peak (630 < T < 650 °C). This causes the creation of porosity as the coupled dissolution–reprecipitation process allows chemical (Ca) and isotopic (O) exchange between garnet inner rims and the matrix. The formation of the outer rim is related to the closure of porosity. Stage 3: garnet mode decreases during the early retrograde path, but garnet is still a stable phase. The resulting garnet composition is characterized by an increasing Mn content in the inner rim’s domain II caused by intracrystalline diffusion. Stage 4: dissolution of garnet during the late retrograde path as garnet is not a stable phase anymore. This last stage forms corroded garnet. This study shows that coupled dissolution–reprecipitation is a possible re‐equilibration process for garnet in metamorphic rocks and that intra‐mineral porosity is an efficient pathway for chemical and isotopic exchange between garnet and the matrix, even for otherwise slow diffusing elements.     

Growth zoning of garnet porphyroblasts: Grain boundary and microtopographic controls

Chemical zoning in the outer few 10s of microns of garnet porphyroblasts has been investigated to assess the scale of chemical equilibrium with matrix minerals in a pelitic schist. Garnet porphyroblasts from the Late Proterozoic amphibolite facies regional metamorphic mica schists from Glen Roy in the Scottish Highlands contain typical prograde growth zoning patterns. Edge compositions have been measured via a combination of analysis of traverses across the planar edges of porphyroblast surfaces coupled to X-ray mapping of small areas within polished thin sections at the immediate edge of the porphyroblasts. These approaches reveal local variation in garnet composition, especially of grossular (Ca) and almandine (Fe) components, with a range at the edge from <7 mol.% grs to >16 mol.% grs, across distances of less than 50 µm. This small-scale patchy compositional zoning is as much variation as the core–rim compositional zoning across the whole of a 3 mm porphyroblast. Ca and Fe heterogeneity occurs on a scale suggesting a combination of inefficient diffusive exchange across grain boundaries during prograde growth and the evolving microtopography of the porphyroblast surface control garnet composition. The latter creates haloes of compositional zoning adjacent to some inclusions, which typically extend from the inclusion towards the porphyroblast edge during further growth. The lack of a consistent equilibrium composition at the garnet edge is also apparent in the internal zoning of the porphyroblast and so processes occurring during entrapment of some mineral inclusions have a profound influence on the overall chemical zoning. Garnet compositions and associated zoning patterns are widely used by petrologists to reconstruct P–T–t paths for crustal rocks. The evidence of extremely localized (10–50 µm scale) equilibrium during growth further undermines these approaches.     

Reaction kinetics of dolomite rim growth

Reaction rims of dolomite (CaMg[CO₃]₂) were produced by solid-state reactions at the contacts of oriented calcite (CaCO₃) and magnesite (MgCO₃) single crystals at 400 MPa pressure, 750–850 °C temperature, and 3–146 h annealing time to determine the reaction kinetics. The dolomite reaction rims show two different microstructural domains. Elongated palisades of dolomite grew perpendicular into the MgCO₃ interface with length ranging from about 6 to 41 µm. At the same time, a 5–71 µm wide rim of equiaxed granular dolomite grew at the contact with CaCO₃. Platinum markers showed that the original interface is located at the boundary between the granular and palisade-forming dolomite. In addition to dolomite, a 12–80 µm thick magnesio-calcite layer formed between the dolomite reaction rims and the calcite single crystals. All reaction products show at least an axiotactic crystallographic relationship with respect to calcite reactant, while full topotaxy to calcite prevails within the granular dolomite and magnesio-calcite. Dolomite grains frequently exhibit growth twins characterized by a rotation of 180° around one of the $[11\bar{2}0]$ equivalent axis. From mass balance considerations, it is inferred that the reaction rim of dolomite grew by counter diffusion of MgO and CaO. Assuming an Arrhenius-type temperature dependence, activation energies for diffusion of CaO and MgO are E _a (CaO) = 192 ± 54 kJ/mol and E _a (MgO) = 198 ± 44 kJ/mol, respectively.     

Compositional zoning of calcite in a high-pressure metamorphic calc-schist: clues to heterogeneous grain-scale fluid distribution during exhumation

Calcite in former aragonite–dolomite-bearing calc-schists from the ultrahigh-pressure metamorphic (UHPM) oceanic complex at Lago di Cignana, Valtournanche, Italy, preserved different kinds of zoning patterns at calcite grain and phase boundaries. These patterns are interpreted in terms of lattice diffusion and interfacial mass transport linked with a heterogeneous distribution of fluid and its response to a changing state of stress. The succession of events that occurred during exhumation is as follows: As the rocks entered the calcite stability field at T=530–550 °C, P ca. 1.2 GPa, aragonite occurring in the matrix and as inclusions in poikilitic garnet was completely transformed to calcite. Combined evidence from microstructures and digital element distribution maps (Mn-, Mg-, Fe- and Ca–Kα radiation intensity patterns) indicates that transformation rates have been much higher than rates of compositional equilibration of calcite (involving resorption of dolomite and grain boundary transport of Mg, Fe and Ca). This rendered the phase transformation an isochemical process. During subsequent cooling to T ca. 490 °C (where lattice diffusion effectively closed), grains of matrix calcite have developed diffusion-zoned rims, a few hundred micrometres thick, with Mg and Fe increasing and Ca decreasing towards the phase boundary. Composition profiles across concentrically zoned, large grains in geometrically simple surroundings can be successfully modelled with an error function describing diffusion into a semi-infinite medium from a source of constant composition. The diffusion rims in matrix calcite are continuous with quartz, phengite, paragonite and dolomite in the matrix. This points to an effective mass transport on phase boundaries over a distance of several hundred micrometres, if matrix dolomite has supplied the Mg and Fe needed for incorporation in calcite. In contrast, diffusion rims are lacking at calcite–calcite and most calcite–garnet boundaries, implying that only very minor mass transport has occurred on these interfaces over the same T–t interval. From available grain boundary diffusion data and experimentally determined fluid–solid grain boundary structures, inferred large differences in transport rates can be best explained by the discontinuous distribution of aqueous fluid along grain/phase boundaries. Observed patterns of diffusion zoning indicate that fluid was distributed not only along grain-edge channels, but spread out along most calcite–white mica and calcite–quartz two-grain junctions. On the other hand, the inferred non-wetting of calcite grain boundaries in carbonate-rich domains is compatible with fluid–calcite–calcite dihedral angles >60° determined by Holness and Graham (1995) for a wide range of fluid compositions under the P–T conditions of interest. Whereas differential stress has been very low at the stage of diffusion zoning (T > 490 °C), it increased as the rocks were cooling below 440 °C (at 0.3–0.5 GPa). Dislocation creep and the concomitant increase of strain energy in matrix calcite induced migration recrystallisation of high-angle grain boundaries. For that stage, the compositional microstructure of recrystallised calcite grain boundary domains indicates significant mass transport along calcite two-grain junctions, which at the established low temperatures is likely to have been accomplished by ionic diffusion within a hydrous grain boundary fluid film (“dynamic wetting” of migrating grain boundaries). Received: 10 January 2000 / Accepted: 10 April 2000     

Diffusion along interphase boundaries and its effect on retrograde zoning patterns of metamorphic minerals

In this study we use two dimensional chemical patterns and numerical modeling to estimate the relative rates of chemical transport along interphase boundaries (ib) and through grain (s) interiors during retrograde Fe–Mg exchange between garnet and biotite at a garnet–biotite–quartz triple junction. We demonstrate that systematic variations in garnet–rim compositions, which are frequently observed along garnet–quartz interfaces, and deviations from concentric retrograde zoning patterns start to develop when chemical transport along the interphase boundaries becomes slow during cooling. The capacities for chemical transport along an interphase boundary depend on the product D ^ib K ^ib/s a, where D ^ib is the diffusion coefficient of the exchangeable components within the interphase boundary medium, K ^ib/s is the equilibrium partitioning coefficient between the cation exchange partners and the interphase boundary medium and a is the interphase boundary width. The model is applied to analyze the retrograde zoning patterns in garnets from the Mozambique belt (SE-Kenya), which cooled from 820°C at a rate of ca. 2°C/my. It is found that non-equilibrated compositions in garnet along garnet/quartz interphase boundaries started to develop below 700°C due to insufficient rates of chemical transport along these boundaries. The transport capacities of garnet/quartz interphase boundaries was estimated to have been between about 1E-23 cm³/s (575°C) and 1E-20 cm³/s (700°C) from modeling the observed X _Fe pattern in garnet close to a garnet–quartz–biotite triple junction and relying on published data on the diffusivity of Fe²⁺ in garnet. Similar transport capacities are obtained; when the interphase boundary is assumed to be filled with a material that has the transport properties and chemical composition of a free melt in equilibrium with garnet, biotite and quartz at the respective conditions. In contrast, if the transport properties of the interphase boundary medium are related to the diffusivities and solubility of Fe²⁺ and FeOH⁺ within a free aqueous solution, chemical transport along the interphase boundaries would be much more efficient, and exchange equilibrium would have been maintained during the entire cooling history of the rocks. The observation of systematic deviations from local equilibrium along the garnet–quartz interphase boundaries leads us to exclude the presence of an aqueous fluid along the interphase boundary at any time during cooling.     

The duration of near‐peak metamorphism from diffusion modelling of garnet zoning

Garnet in a staurolite–kyanite zone sample from central Vermont displays a bell‐shaped Mn growth zoning with diffusional modification over the outer 100 μm. The diffusion is driven by the prograde net transfer reaction garnet + chlorite = kyanite + biotite as is evidenced by a well‐defined resorption zone on the rim. Analysis of the reaction history and resorbed garnet composition suggests that the peak temperature attained was 620–660 °C. Diffusional modelling of the rim diffusion provides an estimate of the duration of the metamorphic episode over which significant garnet diffusion occurs. The duration is a function of the assumed peak temperature and garnet diffusivities and range from a few hundred thousand years to a few million years. Such short durations require rapid tectonic burial and exhumation of relatively thin tectonic slices.     

Growth of plagioclase rims around metastable kyanite during decompression of high‐pressure felsic granulites (Bohemian Massif)

Samples of high‐pressure felsic granulites from the Bohemian Massif (Variscan belt of Central Europe) characterized by a peak metamorphic (high‐pressure) mineral assemblage of garnet – kyanite – plagioclase – K‐feldspar – quartz ± biotite show well‐developed plagioclase reaction rims around kyanite grains in two microstructural settings. In one setting, kyanite is randomly distributed in the polyphase matrix, whereas in the other setting, it is enclosed within large perthitic K‐feldspar. Kyanite is regarded as a relict of the high‐pressure metamorphic assemblage that became metastable during transition to a low‐pressure overprint. Plagioclase rims from both microstructural settings show continuous outwards decrease of the anorthite content from An_32–25 at the contact with kyanite to An_20–19 at the contact with the matrix or to the perthitic K‐feldspar respectively. Based on mass balance considerations, it is shown that in some cases, a small amount of kyanite was consumed in the rim‐forming reaction to provide the Al₂O₃ component for the growth of plagioclase, whereas in other cases no Al₂O₃ from kyanite was necessary. In a majority of examples, the necessary Al₂O₃ was supplied with CaO and Na₂O from the surrounding matrix material. For kyanite in perthite, a thermodynamic analysis reveals that the kyanite became metastable at the interface with the host perthite at the peak metamorphic pressure, and therefore the plagioclase rim started to grow at ～ 18 kbar. In contrast, kyanite in the polyphase matrix remained stable down to pressures of ～ 16 kbar, and the plagioclase rim only started to grow at a later stage during the decompression. Plagioclase rims around kyanite inclusions within large perthite have a radial thickness of up to 50 μm. In contrast, the radial thickness of plagioclase rims around kyanite in the polycrystalline matrix is significantly larger, up to 200 μm. Another peculiarity is that the plagioclase rims around kyanite in the matrix are polycrystalline, whereas the plagioclase rims around kyanite inclusions in perthitic hosts are single crystals with the same crystallographic orientation as the host perthite. The difference in rim thickness for the two microstructural settings is ascribed to the differences in the efficiency of chemical mass transfer next to the reaction site. The comparatively large thickness of the plagioclase rims grown around kyanite in the matrix is probably due to efficient material transport along the grain and phase boundaries in the matrix. In contrast, chemical mass transfer was comparatively slow in the large perthitic K‐feldspar grains.     

Reaction of zoning of garnet

Compositional zoning of garnet in metamorphic or igneous rocks preserves evidence of the equilibration history of the sample and can be interpreted in terms of a growth-fractionation, diffusion-exchange, or diffusion-reaction model. Diffusion zoning is usually assumed to result from exchange reactions between garnet and other phases as the partitioning coefficient varies in response to changing environmental conditions, primarily temperature. However, in many natural environments where garnet grew originally in divariant equilibrium with other phases, changing conditions can promote continuous or “divariant” reactions and consequent compositional shifts of phases that can be much greater in some systems showing these reactions than those related to the small changes of partitioning. Diffusional zoning related to overstepping of these continuous reactions must be related to incongruent reaction and necessitates formulation of a kinetic diffusion-reaction model involving moving phase boundaries as well as solid-state diffusion. Three samples containing zoned garnets from the metamorphic aureole around the Ronda ultramafic intrusion in southern Spain are used to illustrate two possible models of diffusion-reaction processes. The examples are particularly informative because the reactions are demonstrably irreversible and evidence of the reaction system is preserved. Partitioning data indicates that compositions of product phases are not in equilibrium with the original garnet and do not vary with extent of reaction; therefore, exchange reactions with garnet were not possible and garnet changed composition only by incongruent reaction. After a small amount of reaction, Mg/Fe of the rim composition approaches a value apparently in equilibrium with product phases, but the garnets are zoned inward to the original garnet composition preserved in the interior. Grossularite content is approximately constant and spessartite content variable but small, thus, the rim composition of pyrope or almandine is assumed to be fixed by the external reaction process and is taken as a boundary condition in the following models. The zoning profile of pyrope or almandine component between the fixed rim and core compositions (assumed to extend to ∞) is described in semiinfinite, half-space models appropriate for large garnets with narrow rims. The first model corresponds to a reaction system in which all garnet compositions are metastable (case 1) and zoning depends on the independent variables of the diffusion constant, velocity of the interface between garnet and matrix, and time. The second model, corresponding to systems in which the initial garnet composition is metastable but an equilibrium composition is stable (case 2), depends on the independent variables diffusion constant, time, and a function of reaction compositions. In case 1 the consumption velocity is assumed constant and a steady state zoning profile is reached at large time, whereas, in case 2, the velocity decreases with the concentration gradient and steady state is not possible. The models were tested using a reaction time estimated from cooling models of the aureole, mass of garnet consumed, determined petrographically, and phase compositions. The two cases are somewhat independent in that different parameters are independent variables. The estimate of the diffusion constant of 10^?18±2 cm²/sec (assumed to be a mutual or binary coefficient for almandine and pyrope) is considered reasonable for the temperature range of reaction (probably 600–900° C), and the two models are consistent considering the probable error and possible real temperature differences. It is obvious that details of the metamorphic reaction system must be known to successfully apply diffusion models. Kinetic models, involving consumption or growth of the phase as well as diffusion are probably necessary when dealing with natural rocks. Several possible and interesting complications, such as cross coupling between components, can be investigated if more data were available. Experimental determination of diffusion constants allow natural reaction rates to be estimated by this method. Diffusion zoning is an important consideration that could increase the efficiency of experimentation with chemically recalcitrant phases.     

Experimental growth of åkermanite reaction rims between wollastonite and monticellite: evidence for volume diffusion control

Growth rates of monomineralic, polycrystalline åkermanite (Ca₂MgSi₂O₇) rims produced by solid-state reactions between monticellite (CaMgSiO₄) and wollastonite (CaSiO₃) single crystals were determined at 0.5 GPa dry argon pressure, 1,000–1,200°C and 5 min to 60 h, using an internally heated pressure vessel. Inert Pt-markers, initially placed at the monticellite–wollastonite interface, indicate symmetrical growth into both directions. This and mass balance considerations demonstrate that rim growth is controlled by transport of MgO. At 1,200°C and run durations between 5 min and 60 h, rim growth follows a parabolic rate law with rim widths ranging from 0.4 to 16.3 μm indicating diffusion-controlled rim growth. The effective bulk diffusion coefficient \( D_{\text{eff,MgO}}^{\text{Ak}} \) is calculated to 10^?15.8±0.1 m² s^?1. Between 1,000°C and 1,200°C, the effective bulk diffusion coefficient follows an Arrhenius law with E _a = 204 ± 18 kJ/mol and D ₀ = 10^?8.6±1.6 m² s^?1. Åkermanite grains display a palisade texture with elongation perpendicular to the reaction interface. At 1,200°C, average grain widths measured normal to elongation, increase with the square root of time and range from 0.4 to 5.4 μm leading to a successive decrease in the grain boundary area fraction, which, however, does not affect \( D_{\text{eff,MgO}}^{\text{Ak}} \) to a detectible extent. This implies that grain boundary diffusion only accounts for a minor fraction of the overall chemical mass transfer, and rim growth is essentially controlled by volume diffusion. This is corroborated by the agreement between our estimates of the effective MgO bulk diffusion coefficient and experimentally determined volume diffusion data for Mg and O in åkermanite from the literature. There is sharp contrast to the MgO–SiO₂ binary system, where grain boundary diffusion controls rim growth.     

Thermal pulse induced by emplacement of Ramba leucogranites in southern Tibet

The thermal histories of Himalayan leucogranites provide critical information for unravelling the post-collisional geodynamics of the Himalayas. The Ramba Dome is located at the intersection of the Tethyan Himalayan leucogranite belt with the Yadong–Gulu Rift and hosts several generations of granitic intrusions. Of these intrusions, the 8-Ma two-mica granites and garnet leucogranite dykes are the youngest of Himalayan leucogranites. In this study, we focus on the carbonaceous staurolite schist located ~1.3 km from the intrusion to constrain the thermal history of the aureole that marked the cessation of leucogranite magmatism. The schist contains euhedral garnet and staurolite porphyroblasts in a foliated matrix of muscovite + biotite + chlorite + plagioclase + quartz + graphite. The staurolite shows minor compositional variations from the inclusion-free core to the inclusion-rich rim. By contrast, the garnet features a distinctive bell-shaped Mn profile and increasing Mg# from the garnet core to rims. In a graphite-bearing equilibrium phase diagram for a modified bulk composition with garnet cores removed, the garnet rim composition suggests a peak temperature of ~550°C, consistent with an independent thermometer based on the Raman spectra of carbonaceous materials (RSCM; 548 ± 9°C). The P–T condition lies within the narrow low-variance field bracketed by the staurolite-in and chlorite-out boundaries, indicating minimal overstepping of staurolite nucleation and growth. On the other hand, the garnet core composition indicates 520°C at 2.5 kbar, about 40°C higher than the predicted garnet-in boundary (~480°C). This apparent temperature overstep corresponds to a small chemical affinity (<5 kJ/mol 12 O) for garnet nucleation, comparable to previous estimates. The sharp boundaries of the high-Ca sector zoning in the core indicate limited diffusion modification (~1.5 Ma if at the peak temperature). The short thermal pulse involves advective heat transfer by leucogranite emplacement, followed by rapid cooling toward the end of Himalayan magmatism and rapid exhumation likely facilitated by the Yadong–Gulu Rift.     

Kinetics of a garnet granulite reaction

It is necessary to understand the mechanisms of disequilibrium reactions in metamorphic rocks in order to (1) model the rate of reaction in response to changing state variables during tectonic process, and (2) interpret the assemblages of natural disequilibrium samples in terms of tectonic history. A sample was selected from an area of known tectonic history to examine in detail and document the kinetics of reaction. The sample preserves evidence of the garnet granulite to gabbro transition.Orthopyroxene and anorthite coronas around garnet and orthopyroxene rims around clinopyroxene are textural observations suggesting the overall reaction: garnet+clinopyroxene+quartz+plagioclase(matrix) orthopyroxene+ anorthite (corona). The disequilibrium nature of reaction is evident from compositional zoning of garnet, some zoning of clinopyroxene, and difference between corona anorthite (An₉₀) and matrix plagioclase (An₃₅).Several texturally-distinguished microenvironments in a single thin section were investigated to determine how components were redistributed during reaction; T and P are assumed to have been the same throughout. The compositional data are best explained by a partial equilibrium model in which orthopyroxene, garnet rims, Fe-rich clinopyroxene, and a hypothetical intergranular fluid approach equilibrium and are not in equilibrium with reactant garnet cores and matrix plagioclase. Corona texture suggests that intergranular diffusion had some effect but the composition data indicate that it was not rate-limiting. The fact that garnet rim compositions are nearly in equilibrium with product phases (with respect to Mg-Fe partitioning) suggests that diffusion in garnet can be considered a rate-limiting reaction step. Combining the differential equation of zoning for this system with mass and volume balance equations of reaction enables one to predict the density change with time by numerical integration.I conclude that comparison of core compositions of zoned minerals in high-grade rocks is meaningful only if a compositional plateau is preserved that can be proven not to be altered by diffusion. Diffusion in pyroxene is apparently too fast at high grade to make relict pyroxenes useful tracers of metamorphic conditions. The rim composition of zoned phases depends on the relative rate of reaction and internal diffusion; the approach of the rim of a reactant phase to equilibrium with products is a measure of the degree to which intragranular diffusion is rate-limiting. In general, this work supports reaction models that assume that intergranular diffusion is rapid and that interface kinetics or intragranular diffusion are usually rate-limiting factors.Reactions controlled by diffusion in garnet are slow geologically. Tectonic hysteresis can be produced because garnet can form in granulite assemblages more rapidly than it is consumed with changing heat flow. The rate of gabbro-garnet granulite transition depends on whether plagioclase reacts by zoning or separate product grains nucleate.     

Modeling of retrograde diffusion zoning in garnet: evidence for slow cooling of granulites from the Highland Complex of Sri Lanka

Summary ?Diffusion modeling of zoning profiles in garnet rims from mafic granulites is used to estimate cooling rates in the Proterozoic basement of Sri Lanka, which represents a small, but important fragment of the Gondwana super-continent. Metamorphic peak temperatures and pressures, estimated with two-pyroxene thermometry and garnet–clinopyroxene–plagioclase–quartz (GADS) barometry, yield 875±20 °C and 9.0±0.1 kbar. These peak metamorphic conditions are slightly higher than results obtained by garnet-biotite Fe–Mg exchange thermometry of 820±20 °C. Reset flat zoning profiles were observed in most garnets. Only narrow garnet rims touching biotite exhibit retrograde zoning in terms of Fe and Mg exchange. The garnet zoning observed requires a slow cooling history. Equilibrium was achieved along grain boundaries during or close to peak metamorphism. During subsequent cooling to lower temperatures, only local exchange between garnet and biotite occurred. A cooling rate of 1–5 °C/Ma is estimated. The estimated temperature-time history from garnet profiles is in good agreement with the cooling history inferred from mineral radiogenic ages in the literature. Received December 11, 2001; revised version accepted August 28, 2002     

On the mechanism of resorption zoning in metamorphic garnet

Abstract An analytical electron microscope study of almandine garnet from a metamorphosed Al–Fe‐rich rock revealed detailed composition profiles and defect microstructures of resorption zoning along fluid‐infiltrated veins and even into the garnet/ilmenite (inclusion) interface. This indicates a limited volume diffusion for the cations in substitution (mainly Ca and Fe) and an interface‐controlled partition for the extension of a composition‐invariant margin. A corrugated interface between the Ca‐rich margin/zone and the almandine garnet core is characterized by dislocation arrays and recovery texture further suggesting a resorption process facilitated by diffusion‐induced recrystallization, diffusion‐induced dislocation migration and diffusion–induced grain boundary migration. Integrated microstructural and chemical studies are essential for understanding the underlying mechanisms of processes such as garnet zoning and its modification. Without this understanding, it will not be possible to reliably use garnet compositions for thermobarometry and other applications that rely on garnet chemical information.     

Interaction of chemical and physical processes during deformation at fluid-present conditions: a case study from an anorthosite–leucogabbro deformed at amphibolite facies conditions

We present microstructural and chemical analyses of chemically zoned and recrystallized plagioclase grains in variably strained samples of a naturally deformed anorthosite–leucogabbro, southern West Greenland. The recorded microstructures formed in the presence of fluids at mid-crustal conditions (620–640 °C, 7.4–8.6 kbar). Recrystallized plagioclase grains (average grain size 342 μm) with a random crystallographic orientation are volumetrically dominant in high-strain areas. They are characterized by asymmetric chemical zoning (An₈₀ cores and An₆₄ rims) that are directly associated with areas exhibiting high amphibole content and phase mixing. Analyses of zoning indicate anisotropic behaviour of bytownite plagioclase with a preferred replacement in the $ \left\langle {0 10} \right\rangle $ direction and along the (001) plane. In areas of high finite strain, recrystallization of plagioclase dominantly occurred by bulging recrystallization and is intimately linked to the chemical zoning. The lack of CPO as well as the developed asymmetric zoning can be explained by the activity of grain boundary sliding accommodated by dissolution and precipitation creep (DPC). In low-strain domains, grain size is on average larger and the rim distribution is not related to the inferred stress axes indicating chemically induced grain replacement instead of stress-related DPC. We suggest that during deformation, in high-strain areas, pre-existing phase mixture and stress induced DPC-caused grain rotations that allowed a deformation-enhanced heterogeneous fluid influx. This resulted in local plagioclase replacement through interface-coupled dissolution and precipitation and chemically induced grain boundary migration, accompanied by bulging recrystallization, along with neocrystallization of other phases. This study illustrates a strong interaction and feedback between physical and chemical processes where the amount of stress and fluids dictates the dominant active process. The interaction is a cause of deformation and external fluid infiltration with a result of strain localization and chemical re-equilibration at amphibolite facies conditions.     

胶北荆山群富铝岩系石榴石扩散环带特征及其成因指示意义

通过详细的微区成分测定，发现胶北荆山群富铝岩系中石榴石普遍发育扩散环带，但扩散环带的发育程度及样式很不均匀，明显受与其相邻矿物的控制。与黑云母接触时，石榴石晶体边部的镁含量最低，环带最为发育，与堇青石接触时次之，与长英质矿物接触时则环带发育较弱或不发育。这种特征的石榴石扩散环带样式与传统认识有很大差异，反映降温过程中石榴石与黑云母等镁铁矿物之间的Fe-Mg交换作用主要是通过彼此接触的界面来实现，粒间流体对组分的传输作用有限。但是当岩石中黑云母大量存在而石榴石含量又较低时，由于体系水活度增高，粒间流体也会传输一定的Fe、Mg组分，导致与长英质矿物相邻的石榴石晶体边部发育微弱的扩散环带。通过分析，确定粒径大于1500斗m的石榴石晶体核部可以保存变质峰期的平衡成分，基质中远离石榴石等镁铁矿物处于长英质矿物之间的大颗粒黑云母颗粒核部也基本可以保存变质峰期的平衡成分。     

Intergranular diffusion rates from the analysis of garnet surfaces: Implications for metamorphic equilibration

Novel approaches to garnet analysis have been used to assess rates of intergranular diffusion between different matrix phases and garnet porphyroblasts in a regionally metamorphosed staurolite‐mica‐schist from the Barrovian‐type area in Scotland. X‐ray maps and chemical traverses of planar porphyroblast surfaces reveal chemical heterogeneity of the garnet grain boundary linked to the nature of the adjacent matrix phase. The garnet preserves evidence of low temperature retrograde exchange with matrix minerals and diffusion profiles documenting cation movement along the garnet boundaries. Garnet–quartz and garnet–plagioclase boundaries preserve evidence of sluggish Mg, Mn and Fe diffusion at comparable rates to volume diffusion in garnet, whereas diffusion along garnet–biotite interfaces is much more effective. Evidence of particularly slow Al transport, probably coupled to Fe³⁺ exchange, is locally preserved on garnet surfaces adjacent to Fe‐oxide phases. The Ca distribution on the garnet surface shows the most complex behaviour, with long‐wavelength heterogeneities apparently unrelated to the matrix grain boundaries. This implies that the Ca content of garnet is controlled by local availability and is thought likely to reflect disequilibrium established during garnet growth. Geochemical anomalies on the garnet surfaces are also linked to the location of triple junctions between the porphyroblasts and the matrix phases, and imply enhanced transport along these channels. The slow rates of intergranular diffusion and the characteristics of different boundary types may explain many features associated with the prograde growth of garnet porphyroblasts. Thus, minerals such as quartz, Fe‐oxides and plagioclase whose boundaries with garnet are characterized by slow intergranular diffusion rates appear to be preferentially trapped as inclusions within porphyroblasts. As such grain boundary diffusion rates may be a significant kinetic impediment to metamorphic equilibrium and garnet may struggle to maintain chemical and textural equilibrium during growth in pelites.     

Statistical microanalysis applied to garnet growth zoning and to cordierite fluid content

An analytical study to evaluate quantitatively weak zoning of a garnet from a high-grade kinzigite has been performed with an electron microprobe. The technique consists of the reconstruction of a profile step-by-step by successive analyses performed during relatively long counting times (30 s), along a radial profile of 2,500 μm length. The successive analytical data along this profile are statistically treated by Fisher's test and compared with the χ² values (Pearson's law). These statistical tests were applied to assess microprobe stability and analysis homogeneity, and as a consequence to assure high credibility of the radial variations of the garnet. From core to rim, and for each element, zoning appears as the radial juxtaposition of stationary Poissonian samples. These samples being associated, the garnet appears to be constituted of successive concentric domains with stationary compositions. Different substitutions between Mg, Fe, Mn and Ca are evidenced. Such an analytical approach to chemical zoning can be useful for understanding growth mechanisms, and the possible diffusion reactions with the environment at each growth step. In addition, such a procedure can be used to evaluate accurately the fluid content of cordierite, and to appreciate the nature of the fluids concerned. As an example, the fluid content of a cordierite from a similar high-grade kinzigite has been evaluated.