Constraints on the duration of high-pressure metamorphism in the Tauern Window from diffusion modelling of discontinuous growth zones in eclogite garnet

An eclogite sample from the Grossgockner region of the Hohe Tauern, Austria contains garnet with a pronounced compositional discontinuity between a Mn‐rich core and an Fe‐rich rim. This jump in composition was caused by a garnet‐consuming reaction followed by growth of the garnet rim + omphacite and marks the prograde transition from epidote–amphibolite to eclogite facies metamorphism. Garnet growth ended at peak metamorphic conditions of 570 °C, 17 kbar, but intracrystalline diffusion continued until about 450 °C, 4 kbar on the retrograde path. This garnet overgrowth texture represents a natural diffusion couple and a time span of 1 Myr was calculated from the diffusion profile developing out of the original sharp compositional step. For typical crustal densities, this time corresponds to a minimum average velocity in the range 4.6–7.4 cm yr^?1 (for vertical movement), which is one of the fastest exhumation rates reported. The diffusion of all divalent cations of four profiles was modelled, both analytically and numerically. Both approaches gave comparable results, but the times computed for each element were always discrepant up to a factor of 2. Variations of diffusion coefficients within 2 in analytical calculations remedied this and gave consistent upper time limits. Numerical modelling does not require the simplifications introduced in the analytical approach. On the other hand, error propagation was computationally unfeasible with this method.     

Temperature–time path for the low-pressure Ryoke metamorphism, Japan, based on chemical zoning in garnet

Garnet crystals from low-pressure/high-temperature (LPHT) Ryoke metamorphic rocks in the Yanai district, south-western Japan, show several kinds of chemical zoning patterns that systematically vary with grain radius between c . 0.1 and 0.5  mm. Large grains (> c . 0.4  mm) show normal zoning and small grains (< c . 0.4  mm) show unzoned or reversely zoned cores. Observations of the chemical zoning and of the spatial and size distributions of the garnet grains between c . 0.1 and 0.5  mm in radius suggest that they were formed by continuous nucleation and diffusion-controlled growth.
A previously estimated temperature–time path ( T  – t path) for the Ryoke metamorphism, using 1-D numerical simulation, is characterized by a rapid increase in temperature, 0.0017  °C yr⁻¹ on average, and a period of high temperature (>600  °C) shorter than 0.5 Myr, which was presumably caused by the intrusion of a granodiorite sheet. Chemical zoning of garnet grains with different radii simulated for the T  – t path using a numerical model of continuous nucleation and diffusion-controlled growth, in combination with intracrystalline diffusion, compares well with the observed zoning patterns in garnet grains with different radii. This is in spite of the fact that the simulated zoning patterns vary greatly, depending on subtle differences in the T–t history. Therefore, they suggest that the T–t path gives a good explanation for the LPHT Ryoke metamorphism. Although this study only refers to the Ryoke metamorphism, the technique may be applicable to thermal modelling of other metamorphic terranes.     

On the interpretation of peak metamorphic temperatures in light of garnet diffusion during cooling

Abstract Finite difference models of Fe-Mg diffusion in garnet undergoing cooling from metamorphic peak conditions are used to infer the significance of temperatures calculated using garnet-biotite Fe-Mg exchange thermometry. For rocks cooled from high grades where the garnet was initially homogeneous, the calculated temperature (T_calc) using garnet core and matrix biotite depends on the size of the garnet, the ratio of garnet to biotite in the rock (V_garnet/V_biotite) and the cooling rate. For garnets with radii of 1 mm and V_garnet/V_biotite<1, T_calc is 633, 700 and 777°C for cooling rates of 1, 10 and 100°C/Ma. For V_garnet/V_biotite= 1 and 4 and a cooling rate of 10° C/Ma, T_calc is approximately 660 and 610° C, respectively. Smaller and larger garnets have lower and higher T_calc, respectively. These results suggest that peak metamorphic temperatures may be reliably attained from rocks crystallized at conditions below T_calc of the garnet core, provided that V_garnet/V_biotite is sufficiently small (<0.1) and that the composition of the biotite at the metamorphic peak has not been altered during cooling. Numerical experiments on amphibolite facies garnets with nominal peak temperatures of 550–600° C generate a ‘well’in Fe/(Fe + Mg) near the rim during cooling. Maximum calculated temperatures for the assemblage garnet + chlorite + biotite + muscovite + plagioclase + quartz using the Fe/(Fe + Mg) at the bottom of the ‘well’with matrix biotite range from 23–43° C to 5–12° C below the peak metamorphic temperature for cooling rates of 1 and 100° C/Ma, respectively. Maximum calculated temperatures for the assemblage garnet + staurolite + biotite + muscovite + plagioclase + quartz are approximately 70° C below the peak metamorphic temperature and are not strongly dependent on cooling rate. The results of this study indicate that it may be very difficult to calculate peak metamorphic temperatures using garnet-biotite Fe-Mg exchange thermometry on amphibolite facies rocks (T_max > 550° C) because the rim composition of the garnet, which is required to calculate the peak temperature, is that most easily destroyed by diffusion.     

Constraints on the early cooling rates of Mt. Dabie from diffusion modeling of chemical zoning of garnet

Diffusion modeling of zoning profiles in eclogite garnets from three different tectonic units of Mt. Dabie, UHPM unit, HPM unit and northern Dabie, was used to estimate the relative time span and cooling rates of these rocks. Modeling result for the Huangzhen eclogite garnet shows that the maximal time span for the diffusion-adjustment process is about 22 Ma since the peak-temperature metamorphism, which is the maximum time span from amphibolite facies metamorphism to greenschist facies metamorphism. The Bixiling eclogites had subjected to a cooling process at a rate of - 10℃/Ma from 750℃ to 560℃ during 20 Ma. The second cooling stage of the Raobazhai eclogite following granulite-facies metamorphism is an initial fast cooling process at a rate of about 25℃/Ma and then slowed down gradually. All these belong to a coherent Dabie collision orogen with differences in subduction depth and exhumation/uplifting path.     

Pressure-temperature path of Sanbagawa prograde metamorphism deduced from grossular zoning of garnet

The zonal structure of prograde garnet in pelitic schists from the medium-grade garnet zone and the higher-grade albite-biotite zone was examined to investigate the evolution of prograde P–T paths of the Sanbagawa metamorphism. The garnet studied shows a bell-shaped chemical zoning of the spessartine component, which decreases in abundance from the core towards the rim. Almandine and pyrope contents and X_Mg [=Mg/(Mg+Fe²⁺)] increase monotonously outwards. The general scheme of the zonal structure for grossular content [X_Grs=Ca/(Fe²⁺+Mn+Mg+Ca)] can be summarized as: (1) X_Grs increases outwards (inner segment) and reaches a maximum at an intermediate position between the crystal core and the rim, then decreases towards the outermost rim (outer segment) (2) the inner segment of garnet in the garnet zone samples tends to have a higher X_Grs/X_Sps values for a given X_Sps than those in the albite–biotite zone samples (3) average X_Sps at the maximum X_Grs position in the albite–biotite zone samples ranges from 0.02 to 0.12 and is lower than that in the garnet zone samples (0.13–0.32) (4) the maximum X_Grs in the albite–biotite zone samples (0.34–0.39 on average) tends to be higher than that in the garnet zone samples (0.26–0.36), and (5) differences of X_Grs between the maximum and rim in the albite–biotite zone samples are between 0.10 and 0.14 and higher than those in the garnet zone samples (< 0.11). These facts imply that albite–biotite zone materials (a) were recrystallized under lower dP/dT conditions at an early stage of the prograde metamorphism (b) began their exhumation under higher P–T conditions and (c) have been continuously heated during exhumation for a longer duration than the garnet zone materials. The systematic changes of prograde P–T paths can be interpreted as documenting the evolution of the Sanbagawa subduction zone.     

Peak metamorphic temperatures from cation diffusion zoning in garnet

A model that relates the characteristic diffusion length and average cooling rate to peak temperature was developed for chemical diffusion in spherical geometries on the basis of geospeedometry principles and diffusion theory. The model is quantitatively evaluated for cation diffusion profiles in garnet. Important model parameters were calibrated empirically using diffusion zoning of Ca in garnet from the Pikwitonei Granulite Domain, a terrane for which the thermal history has been well characterized. The results are used: (i) to empirically test diffusion parameters for Mg and Fe(II) and (ii) to develop a tool that uses the diffusion zoning of these cations in garnet to constrain peak temperature conditions for garnet‐bearing rocks. The thermometric approach was externally tested by applying it to garnet crystals from various metamorphic terranes worldwide and comparing the results to published peak temperature estimates. The results overlap within uncertainties in all cases, but result that are based on Fe(II) and Mg chemical‐diffusion profiles are up to three times more precise than those acquired by conventional methods. The remarkable consistency of the results implies that the model is robust and provides a reliable means of estimating peak temperatures for different types of high‐grade metamorphic rock. The tool could be of particular advantage in rocks where critical assemblages for conventional thermometry do not occur or have been replaced during retrogression.     

Petrological significance of prograde homogenization of growth zoning in garnet: an example from the Llano Uplift'pa

In the Llano Uplift of central Texas (USA), prograde homogenization of garnet growth zoning took place during moderate- to high-pressure dynamothermal metamorphism over a narrow temperature range near the transition from the amphibolite to the granulite facies. This subtle record of early dynamothermal metamorphism survived subsequent static metamorphism at low pressures in the middle-amphibolite facies, despite the destruction of most high-pressure mineral assemblages that originated in the early metamorphic episode. Geographically systematic variations in the degree of homogenization indicate that the uplift as a whole underwent high-pressure metamorphism, in accord with emerging tectonic models for the mid-Proterozoic evolution of the southern margin of the North American continent.     

Quantitative temperature-time information from retrograde diffusion zoning in garnet: constraints for the P–T–t history of the Central Black Forest, Germany

Garnet from a kinzigite, a high-grade gneiss from the central Black Forest (Germany), displays a prominent and regular retrograde diffusion zoning in Fe, Mn and particularly Mg. The Mg diffusion profiles are suitable to derive cooling rates using recent datasets for cation diffusion in garnet. This information, together with textural relationships, thermobarometry and thermochronology, is used to constrain the pressure–temperature–time history of the high-grade gneisses. The garnet–biotite thermometer indicates peak metamorphic temperatures for the garnet cores of 730–810  °C. The temperatures for the outer rims are 600–650  °C. Garnet–Al₂SiO₅–plagioclase–quartz (GASP) barometry, garnet–rutile–Al₂SiO₅–ilmenite (GRAIL) and garnet–rutile–ilmenite–plagioclase–quartz (GRIPS) barometry yield pressures from 6–9  kbar. U–Pb ages of monazite of 341±2  Ma date the low- P high- T metamorphism in the central Black Forest. A Rb/Sr biotite–whole rock pair defines a cooling age of 321±2  Ma. The two mineral ages yield a cooling rate of about 15±2  °C Ma⁻¹. The petrologic cooling rates, with particular consideration of the f O₂ conditions for modelling retrograde diffusion profiles, agree with the geochronological cooling rate. The oldest sediments overlying the crystalline basement indicate a minimum cooling rate of 10  °C Ma⁻¹.     

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.     

Modelling grain‐recycling zoning during metamorphism

Chemical zoning, recorded by grain growth during metamorphism, is a key source of information about P–T–t paths. Interpretation of these data must be carried out using appropriate models and recognizing their inherent assumptions. To assist with defining how zoned minerals form, a set of geometric criteria for three types of chemical zoning developed in minerals (diffusion, growth and grain recycling) is outlined. Re‐equilibration of minerals by lattice diffusion causes zoning if the re‐equilibration is incomplete. Growth of porphyroblasts is commonly considered in pelites, but in metagranitoids, large monophase domains undergo coarsening by recycling of material from one grain to another as grain boundaries migrate driven by surface energy. This type of grain size increase is termed here ‘grain recycling’. Zoning developed during grain recycling due to equilibration of the recycled material with grain‐boundary chemistry is termed ‘grain‐recycling zoning’. Furthermore, short lattice diffusion lengths relative to grain sizes cause metamorphic fractionation because material in the grain cores is not in communication thermodynamically with the rest of the rock. A new model is derived for this sort of grain size increase coupled with metamorphic reactions using Theriak–Domino. An example is given of plagioclase undergoing an increase in anorthite content as epidote breaks down during amphibolite facies metamorphism of a metagranitoid. Agreement between naturally occurring zoning profiles and those derived from modelled P–T–t paths shows that this model can be used to extract metamorphic conditions from rocks which are not accessible using conventional thermobarometry.     

Origins of yttrium and rare earth element distributions in metamorphic garnet

Highly variable distributions of yttrium and rare earth elements (Y+REEs) are documented in pelitic garnet from the Picuris Mountains, New Mexico, and from Passo del Sole, Switzerland, and in mafic garnet from the Franciscan Complex, California. The wide variety of these Y+REE zoning patterns, and those described previously in other occurrences, imply diverse origins linked to differing degrees of mobility of these elements through the intergranular medium during garnet growth. In the Picuris Mountains, large, early‐nucleating crystals have radial profiles of Y+REE dominated by central peaks and annular maxima, in patterns that vary systematically with atomic number. Superimposed on these features are narrow spikes in HREEs and MREEs, located progressively rimward with decreasing atomic number. In contrast, profiles in small, late‐nucleating crystals contain only broad central maxima for all Y+REEs. In garnet from Passo del Sole, Y+REE zoning varies radically from sample to sample: in some rocks, crystals of all sizes display only central peaks for all Y+REEs; in others, profiles exhibit irregular fluctuations in Y+REE contents that match up with small‐scale patchy zoning in Y and Ca X‐ray maps. In the Franciscan Complex, Y+REE in garnet cores fluctuate unsystematically, but mantles and rims display concentric oscillatory zoning for both major elements and Y+REEs. Our interpretation of the complexity of Y+REE distributions in metamorphic garnet centres on the concept that these distributions vary primarily in response to the length scales over which these elements can equilibrate during garnet growth. Very short length scales of equilibration, due to low intergranular mobility, produce overprint zoning characterized by small‐scale irregularities. Higher but still restricted mobility yields diffusion‐controlled uptake, characterized by patterns of central peaks and annular maxima that vary with atomic number and are strongly influenced by T–t paths during garnet growth. Still greater mobility permits progressively greater, potentially rock‐wide, equilibration with major‐ and accessory‐phase assemblages, leading to mineralogical controls: an unchanging mineral assemblage during garnet growth produces bell‐shaped profiles resembling those produced by Rayleigh fractionation, whereas changes in major‐ and/or accessory‐phase assemblages produce profiles with distinct annuli and sharp discontinuities in concentration. The very high mobility associated with influxes of Y+REE‐bearing fluids can cause these element distributions to be dominated by factors external to the rock, yielding profiles characterized by abrupt shifts or oscillations that are not correlated to changes in mineral assemblages.     

苏北高压变质带绿片岩中石榴石内文石包裹体的发现

苏北高压变质带位于苏鲁超高压变质带东南缘,露头多为绿片岩相的中—晚元古代云台岩群,典型的蓝片岩仅见于灌云县杨集的钻孔岩心中。本文通过拉曼光谱研究,在连云港地区的绿片岩内石榴石中发现文石(CaCO3)包裹体。文石呈细小包裹体残留于细粒半自形石榴石斑晶中。这些石榴石作为低扩散的刚性矿物,经历了多期变质变形作用,变质反应证据保存在石榴石的成分环带及包体矿物组合中。文石包裹体的存在证明苏北高压变质带北部的、即本区出露的这套岩系是早期经历了高压变质作用、晚期又叠加了绿片岩相变质作用的高压变质地体。     

Chromium and manganese zoning in pelitic garnet and kyanite: Spiral,overprint, and oscillatory (?) zoning patterns and the role of growth rate

X‐ray composition maps and quantitative analyses for Mn, Ca and Cr have been made for six pelitic and calc‐pelitic garnet crystals and Al, Fe and Cr analyses maps have been made for two kyanite crystals, from lower and mid/upper amphibolite facies rocks from the Grenville Province of western Labrador, using an electron microprobe analyser and a laser ablation ICP‐MS. Garnet with spiral (‘snowball’) internal fabrics (S_i) has spiral zoning in major elements, implying that growth was concentrated in discrete regions of the crystal at any one time (spiral zoning). Cr zoning is parallel to S_i in low amphibolite facies garnet with both straight and spiral internal fabrics, indicating that the garnet overprinted a fabric defined by Cr‐rich (mica±chlorite±epidote) and Cr‐poor (quartz±plagioclase) layers during growth (overprint zoning) and that Cr was effectively immobile. In contrast, in mid/upper amphibolite facies garnet porphyroblasts lacking S_i, Cr zoning is concentric, implying that Cr diffusion occurred. Cr zoning in kyanite porphyroblasts appears superficially similar to oscillatory zoning, with up to three or four annuli of Cr enrichment and/or depletion present in a single grain. However, the variable width, continuity, Cr concentration and local bifurcation of individual annuli suggest that an origin by overprint zoning may be more likely. The results of this study explain previously observed nonsystematic Cr zoning in garnet and irregular partitioning of Cr between coexisting metamorphic mineral pairs. In addition, this study points to the important role of crystal growth rate in determining the presence or absence of inclusions and the type of zoning exhibited by both major and trace elements. During fast growth, inclusions are preferentially incorporated into the growing porphyroblast and slow diffusing elements such as Cr are effectively immobile, whereas during slow growth, inclusions are not generally included in the porphyroblast and Cr zoning is concentric.     

Eclogites with a short-lived granulite facies overprint in the Moldanubian Zone,Czech Republic: petrology,geochemistry and diffusion modelling of garnet zoning

The petrology and geochemistry of a newly discovered suite of high-pressure garnet + clinopyroxene-bearing rocks from the Monotonous Series of the Moldanubian Zone of the Bohemian Massif, southwest Czech Republic have been investigated. Three types [common eclogites, quartz ± kyanite ± (clino)zoisite eclogites and garnet-hornblende-clinopyroxenites] are distinguished by petrography and geochemistry. All underwent a significant degree of partial breakdown under granulite and amphibolite facies conditions during exhumation. Important features include the growth of orthopyroxene in breakdown domains after garnet and omphacite and anorthite + spinel ± corundum ± exceedingly peraluminous sapphirine replacing kyanite. Garnet zoning and inclusion patterns support a prograde evolution from low pressures for at least some of the samples. The post-eclogite stage granulite facies overprint indicates that high temperatures prevailed during exhumation, but preservation of zoning in some garnets and the results of diffusion modelling suggest that this overprint took place over a very short time-scale. The geochemical and petrological results allow characteristic differences to be recognized between these eclogites and metabasites found in other tectonic units of South Bohemia and consequently the assigning of all high-pressure rocks to a single, now disrupted, tectonic unit is a gross simplification that seriously misrepresents the tectono-metamorphic history of the region.     

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.     

西藏知不拉铜多金属矿床地质、石榴子石分带特征及其地质意义

西藏知不拉铜多金属床是冈底斯成矿带东段典型的矽卡岩矿床,石榴子石是矿区最主要的矽卡岩矿物,其颗粒间的空隙是金属矿物的主要赋存部位。本文通过详细的钻孔编录,结合岩矿鉴定及电子探针分析,划分出两种不同类型的石榴子环带,并在垂向上具有明显的分带:产于顶板凝灰岩中的石榴子石以钙铁榴石为主,环带中心颜色深,向外逐渐变浅,由纯钙铁榴石过渡到钙铝榴石;而位于底板大理岩附近石榴子石多以钙铝榴石为主,从环带核部向外颜色变深,化学组成由钙铝榴石向钙铁榴石变化,其它化学成分变化不大。反映该区上下两套不同性质围岩在石榴子石形成过程中所起的作用不同,其中上部凝灰岩主要提供了Fe,底部大理岩则是Ca的来源,热液流体贡献Si、Al及部分Fe,并随着环境和物质成分改变导致环带外侧具有不同于核部的变化趋势。这很好地解释了石榴子石矽卡岩在空间上具有上部为钙铁榴石、向下逐渐过渡到钙铝榴石的空间分带。石榴子石特征及分带显示了其属热液接触交代成因,这为矿床类型的确定提供了依据,也为在该区域内寻找类似矿床指明了方向。     

Well-preserved garnet growth zoning in granulite from the Dabie Mountains, central China

Ultra-high pressure eclogites and granulites both occur in the Dabie Mountains, central China. A garnet porphyroblast from felsic granulite in the Dabie Mountains has been analysed for compositional zoning by electron microprobe. Two segments of the porphyroblast have opposite compositional variations. Segment I (from centre outward 9  mm to analytical point 18) has decreasing X_Sps and increasing X_Pyr, while Segment II (from analytical point 18, 1  mm outward to the rim) has increasing X_Sps and X_Alm and decreasing X_Pyr and X_Grs. The compositional zoning in segment I is considered as growth zoning and that in Segment II as diffusive retrograde zoning. Garnet growth zoning records a P–T  path prior to the peak granulite metamorphism. The minimum P – T  conditions are estimated to be 1.35  GPa and 850  °C for peak metamorphism, based on the highest Mg/(Fe+Mg) composition in the garnet (analytical point 18) and matrix hypersthene, biotite and plagioclase. A symplectitic corona surrounds the porphyroblast and appears to have formed at 0.6  GPa and 700  °C. The well-preserved growth zoning in garnet suggests a short residence time for the granulite at peak metamorphism and thus rapid tectonic uplift history. The P–T  path is consistent with that of ultra-high-pressure eclogite in the area. Tectonic movements during a collisional event could have brought both the granulite and the eclogite to their present positions.     

Chemical and textural equilibration of garnet during amphibolite facies metamorphism: The influence of coupled dissolution–reprecipitation

Metamorphic equilibration requires chemical communication between minerals and may be inhibited through sluggish volume diffusion and or slow rates of dissolution in a fluid phase. Relatively slow diffusion and the perceived robust nature of chemical growth zoning may preclude garnet porphyroblasts from readily participating in low‐temperature amphibolite facies metamorphic reactions. Garnet is widely assumed to be a reactant in staurolite‐isograd reactions, and the evidence for this has been assessed in the Late Proterozoic Dalradian pelitic schists of the Scottish Highlands. The 3D imaging of garnet porphyroblasts in staurolite‐bearing schists reveals a good crystal shape and little evidence of marginal dissolution; however, there is also lack of evidence for the involvement of either chlorite or chloritoid in the reaction. Staurolite forms directly adjacent to the garnet, and its nucleation is strongly associated with deformation of the muscovite‐rich fabrics around the porphyroblasts. “Cloudy” fluid inclusion‐rich garnet forms in both marginal and internal parts of the garnet porphyroblast and is linked both to the production of staurolite and to the introduction of abundant quartz inclusions within the garnet. Such cloudy garnet typically has a Mg‐rich, Mn‐poor composition and is interpreted to have formed during a coupled dissolution–reprecipitation process, triggered by a local influx of fluid. All garnet in the muscovite‐bearing schists present in this area is potentially reactive, irrespective of the garnet composition, but very few of the schists contain staurolite. The staurolite‐producing reaction appears to be substantially overstepped during the relatively high‐pressure Barrovian regional metamorphism reflecting the limited permeability of the schists in peak metamorphic conditions. Fluid influx and hence reaction progress appear to be strongly controlled by subtle differences in deformation history. The remaining garnet fails to achieve chemical equilibrium during the reaction creating distinctive patchy compositional zoning. Such zoning in metamorphic garnet created during coupled dissolution–reprecipitation reactions may be difficult to recognize in higher grade pelites due to subsequent diffusive re‐equilibration. Fundamental assumptions about metamorphic processes are questioned by the lack of chemical equilibrium during this reaction and the restricted permeability of the regional metamorphic pelitic schists. In addition, the partial loss of prograde chemical and textural information from the garnet porphyroblasts cautions against their routine use as a reliable monitor of metamorphic history. However, the partial re‐equilibration of the porphyroblasts during coupled dissolution–reprecipitation opens possibilities of mapping reaction progress in garnet as a means of assessing fluid access during peak metamorphic conditions.     

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.     

Strontium isotope zoning in garnet: implications for metamorphic matrix equilibration,geochronology and phase equilibrium modelling

In principle, garnet growth rates may be calculated from ⁸⁷Rb/⁸⁶Sr and ⁸⁷Sr/⁸⁶Sr measurements in garnet subsamples and the surrounding rock matrix. Because of low Rb/Sr, garnet should passively record the matrix decay of ⁸⁷Rb to ⁸⁷Sr as a progressive increase in ⁸⁷Sr/⁸⁶Sr from core to rim. This concept was tested by collecting Rb‐Sr data for five garnet grains from four major orogenic belts: eastern Vermont (c. 380 Ma), western New Hampshire (c. 320 Ma), southern Chile (c. 75 Ma) and northwestern Italy (c. 35 Ma). Both normal Sr isotope zoning (increasing ⁸⁷Sr/⁸⁶Sr from core to rim) and inverse Sr zoning (decreasing ⁸⁷Sr/⁸⁶Sr from core to rim) were observed. Garnet and matrix isotope data commonly yielded grossly inaccurate model ages. Incomplete Rb and Sr equilibration among matrix minerals is invoked to explain the deviations between theoretical v. measured zoning patterns and the age disparities. Initially, the reactive matrix is dominated by rapidly equilibrating Rb‐rich mica, which imparts high ⁸⁷Sr/⁸⁶Sr values in garnet cores. Progressive participation of slower equilibrating Sr‐rich plagioclase buffers or even reduces ⁸⁷Sr/⁸⁶Sr, possibly leading to flat or decreasing ⁸⁷Sr/⁸⁶Sr from garnet cores to rims. Unusually high ⁸⁷Sr/⁸⁶Sr in garnet in combination with bulk matrix compositions causes erroneously young apparent ages, so metamorphic ages, growth rates, and associated heating and loading rates are likely suspect. Although Rb‐Sr may be the most susceptible because of the profound disparities between mica and feldspar, zircon reactivity might influence the Lu‐Hf system by up to a few per cent. The Sm‐Nd system seems generally immune to these effects. Pseudosection analysis and conventional garnet geochronology, which presume complete matrix equilibration during metamorphism, may require modification to account for differences between whole‐rock v. reactive matrix compositions.