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.     

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.     

Metamorphic interpretation of high-pressure-temperature metapelites with preserved growth zoning in garnet, eastern Grenville Province, Canadian Shield

Abstract High-pressure-temperature metapelites that occur in close proximity to eclogitized mafic rocks in the southern part of the Gagnon terrane (Parautochthonous Belt, eastern Grenville Province) were investigated in order to constrain depths of burial and P-T paths. Mineral assemblages and partial melting relationships in these metapelites are consistent with peak temperatures in the range between 700 and 800° C. However, growth zoning is apparently well preserved in garnets and only narrow rims (width = 100–500 μm) are obviously affected by diffusional retrograde resetting. Despite uncertainties regarding mineral assemblages and compositions of matrix minerals at early stages of garnet growth, it can be shown that the observed growth zoning profiles of garnets imply increase of both pressure and temperature up to a common maximum at pressures between 1300 and 1600 MPa, and that thermal relaxation did not occur during the initial stages of unloading. On the other hand, calculated retrograde P-T conditions are consistent with steep decompression paths. The inferred 'hair-pin'-shaped P-T path is consistent with independent evidence of rapid, tectonically driven exhumation, resulting in the preservation of growth zoning in garnets from such a high-temperature regime.     

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.     

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。     

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.     

矽卡岩中石榴子石在示踪热液流体演化和矿化分带中的研究现状及其展望

热液型矿床形成过程中流体的组成、运移、演化及其矿质沉淀机制是矿床学研究的重点内容和难点。矽卡岩矿床中具有震荡环带结构的石榴子石完整记录了热液流体的性质、组成及演化过程,这种震荡环带的出现暗示了不同成分系列的石榴子石对不同阶段热液流体成矿物化环境的特定选择性。石榴子石晶体元素化学分带现象是流体运移和矿物再沉淀过程周期性循环再现的结果,对指示早期矽卡岩阶段热液流体中主、微量元素化学分带机制具有重要意义。不同成分系列、不同期次石榴子石的Fe_2O_3和Al_2O_3含量差异显著,其对热液流体演化过程中氧化还原环境的变化具有较好的示踪作用;相对主量元素而言,微量元素在流体演化过程中具有更好的探针作用,钙铝榴石常富集Al、Ti、Zr、HREE元素,而钙铁榴石常富集As、W、Mo、Fe、LREE元素。借助EMPA和LA_ICP_MS技术对具震荡环带结构的石榴子石进行主、微量元素(包括稀土元素)的微区和原位分析是探讨成矿过程中流体组成和性质演化的重要手段,其有可能揭示矿物生长机制、成矿环境以及成矿流体组成与性质的演化,而这一地质信息对于全面理解矽卡岩型矿床的矿化分带及成矿作用非常重要。     

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.     

柴达木盆地北缘大柴旦和锡铁山榴辉岩中石榴子石环带对比及地质意义

大柴旦榴辉岩和锡铁山榴辉岩同为柴达木盆地北缘高压—超高压变质带的组成部分,但它们的岩相学特征、形成的PT条件及榴辉岩中石榴子石中保存的成分环带均具有明显的差异。大柴旦榴辉岩峰期变质的PT条件为T=620～730℃,P=2.3～2.8GPa,岩相学研究表明其经历了近等温降压或降温降压的后榴辉岩相历史,保存有进变质的矿物组合和石榴子石的生长环带及增生结构。相反,锡铁山榴辉岩的榴辉岩相的温度较高,岩相学研究显示其具有明显的后榴辉岩相的高温麻粒岩相的叠加,PT轨迹显示压力峰期早于温度峰期,具有略升温降压的后榴辉岩相变质历史,榴辉岩中石榴子石的成分环带表现为扩散环带,没有生长环带保留。大柴旦榴辉岩和锡铁山榴辉岩的不同的石榴子石环带特征反映了两者在形成过程中,特别是折返过程中不同的构造热历史。     

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.     

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.     

δ18O and yttrium zoning in garnet: time markers for fluid flow?

The relative timing of two discrete pulses of metamorphic fluid flow is constrained based on chemical zoning in several garnet crystals from Kvaløya, Troms, northern Norway. The garnet crystals measured 1–2 cm in diameter and were contained within c. 1.6 Ga, staurolite grade metasediments. Major element zoning indicates that garnet grew under normal prograde conditions in the garnet and/or staurolite zones. Timing constraints are based on comparisons between major and trace element chemical zoning, oxygen isotope (δ¹⁸O) zoning and deformational (inclusion trail) zoning in one of the garnet. We interpret at least two pulses of metamorphic fluid flow. The first pulse occurred during the syn‐tectonic growth interval. The δ¹⁸O zoning was reversed relative to ‘normal’ prograde zoning and the δ¹⁸O maximum was located within the syn‐tectonic growth zone, displaced 3–4 mm from the garnet core. The fluid might have been sourced in neighbouring calcareous pelites and may also have caused formation of an Y ring. The second (and subsequent) pulse(s) occurred during/after the post‐tectonic growth interval. δ¹⁸O was locally increased at the garnet rim, particularly where the rim was sheared. The incomplete rim was also enriched in calcium. Transport of oxygen and calcium by metamorphic fluids is well documented. Transport of Y is both problematic and poorly understood, but might have been facilitated by complexing with F and/or CO₂.     

Prograde reactions and garnet zoning reversals in staurolite schist, British Columbia: significance for thermobarometric interpretations

Abstract An outcrop of staurolite-bearing pelitic schist from the Solitude Range in the south-western Rocky Mountains, British Columbia, was examined in order to determine the nature of prograde garnet- and staurolite-producing reactions using information from garnet zoning and inclusion mineralogy. Although not present as a matrix phase, chloritoid is present as inclusions in garnet and is interpreted to have participated in the simultaneous growth of garnet and staurolite by a reaction such as chloritoid + quartz = garnet + staurolite + H₂O.
A garnet zoning trend reversal, which is most pronounced with respect to almandine and grossular components, is present in the outer core of garnets. The location of the zoning reversal corresponds to the outer limit of chloritoid inclusions in garnet. As there is no evidence for polymetamorphism, the zoning reversal is interpreted to indicate continued garnet growth by prograde reaction(s) during a single metamorphic event after the exhaustion of chloritoid as a matrix phase.
Metamorphic conditions recorded by mineral rim compositions are 550–600° C at 6–7 kbar. Because there is no evidence for partial resorption of garnet during production of staurolite, we interpret these results to represent peak conditions.     

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.     

Oscillatory zoning in eclogitic garnet and amphibole,Northern Serpentinite Melange,Cuba: a record of tectonic instability during subduction?

Exotic blocks of eclogite from distant localities along the Northern Serpentinite Melange of Cuba have comparable P–T histories that include high‐pressure prograde sections (450–600 °C, >15 kbar) associated with subduction of oceanic lithosphere, and retrograde sections within the albite–epidote amphibolite facies (<500 °C, <10 kbar) related to melange uplift. ⁴⁰Ar/³⁹Ar and Rb/Sr cooling ages (118–103 Ma) of one of the blocks indicate pre‐Aptian subduction and Aptian–Albian uplift. Detailed X‐ray imaging and profiling further reveals that minerals in these eclogite blocks (notably garnet and amphibole) display subtle but well defined oscillatory zoning that developed along the prograde trajectory of the rocks, previous to attainment of peak eclogitic conditions. The chemistry (e.g. coupled changes of Mg# and Mn in garnet, and of Si, Ti, Al and Na in amphibole) and geometry (euhedral to anhedral shapes) of the oscillations can be interpreted in terms of subtle fluctuations in P–T during the general prograde subduction‐related metamorphic path. A (near‐) equilibrium model is presented for the formation of oscillations at near peak conditions by means of recurrent dissolution‐growth reaction processes. This model for near‐peak conditions, and the chemical signatures of earlier oscillations (notably in amphibole), suggest that episodes of retrogression (upward movement?) affected parts of the subducting slab. It is proposed that these retrograde episodes record the tectonic rupture of the subducting slab and, probably, of the upper plate mantle, either due to the intrinsic dynamic behaviour of subduction systems or to the effects of the plate‐tectonic rearrangement of the Caribbean region during the Early Cretaceous.     

Disequilibrium for Ca during growth of pelitic garnet

Compositional zoning in hundreds of almandine-rich garnets in amphibolite by facies micaceous quartzites from the Picuris Range, north-central New Mexico USA, indicates that although Mn, Mg and Fe achieve chemical equilibrium at hand-sample scale during garnet growth, Ca does not. Instead, Ca concentrations at the surface of growing garnets appear to depend strongly on kinetic factors that govern the local chemical environment, yielding disequilibrium for Ca at scales larger than the region immediately surrounding an individual porphyroblast. Detailed zoning profiles were obtained for 371 garnet crystals in a small volume of a single sample of garnetiferous quartzite, and core analyses were made of 97 additional crystals. Each analysis was made on a section that passed precisely through the morphological centre of the crystal, located by means of 3-D imagery from computed X-ray tomography. The data reveal strong correlations between crystal size and concentrations of Mn, Mg and Fe (but not Ca) in garnet cores; a relationship between crystal size and isolation; rigorous cross-correlations among concentrations of Mn, Mg and Fe (but not Ca); and systematic variations in Ca concentrations as a function of crystal size and core composition that are anomalous in comparison to the behaviour of the other divalent cations. We interpret these observations as the result of thermally accelerated diffusion-controlled garnet growth, in circumstances that promoted rapid intergranular diffusion and thus rock-wide equilibration of Mn, Mg and Fe, but that prevented equilibration at similar scale for Ca because of its more sluggish intergranular diffusion. The anomalous behaviour of Ca is made evident in these garnets by the presence of sharp spikes in Ca concentration, which are demonstrably not a consequence of any simultaneous rock-wide event, such as a change in pressure, temperature, or some other intensive parameter. Instead, Ca concentrations probably reflect the local extent of reaction in the immediate vicinity of each porphyroblast. To the degree that such kinetic factors introduce departures from chemical equilibrium for Ca, thermobarometric estimates that involve grossular contents of pelitic garnet will be in error.     

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.     

Metamorphism of metapelites: calculations of equilibrium assemblages and numerical simulations of the crystallization of garnet

Abstract This work uses a simplified model of equilibrium to predict the assemblage sequence and compositional zoning in garnet that should result from prograde metamorphism of common bulk compositions of pelitic rocks. An internally-consistent set of model thermodynamic data are derived for natural mineral compositions from natural assemblages. Equilibrium assemblages can be calculated for pelitic compositions with excess quartz and either muscovite or K-feldspar at any pressure and water pressure. The compositions and abundances of phases in equilibrium assemblages can be calculated where the elements Mg, Fe and Mn are exchanged among phases. The prograde metamorphic assemblage sequences and the effects of pressure on assemblages, predicted by the simulation method presented here, are similar enough to natural observations to suggest that the simulations can be used to analyse natural equilibrium and growth processes. The calculated phase diagrams at moderate and high crustal pressures explain the mineral assemblage sequence produced by prograde metamorphism in common pelitic compositions. Garnet appears by continuous reaction of biotite and chlorite as the garnet-biotite-chlorite divariant field migrates toward higher Mg/Fe ratios over the bulk composition. Staurolite appears in common bulk compositions when garnet and chlorite become incompatible. An aluminum silicate phase can appear when staurolite and chlorite react. Staurolite breaks down at an extremum point to produce garnet. Continuous reaction of biotite and sillimanite causes growth of abundant garnet. The reaction sequence involving garnet, staurolite and aluminum silicates is probably different at low pressure, but the main reason that staurolite and garnet are rare is the restricted compositional range over which their assemblages exist. Andalusite appears by the divariant reaction of chlorite and cordierite appears at low temperature in low pressure assemblages for common bulk compositions by the extremumpoint breakdown reaction of chlorite. Compositional zoning of garnet and the systematic variation of biotite composition in metamorphic sequences indicate that garnet is probably fractionated during growth. Fractionation of garnet causes garnet-consuming, univariant reactions to become multivariant. The metastable persistence of garnet should reduce the abundance and stability range of staurolite. Fractionation of even small quantities of garnet should deplete the equilibrating bulk composition of Mn, but have little effect otherwise. The simulations show that the prograde assemblage sequence in pelitic rocks can be complex in detail, with some assemblages lasting over temperature intervals of only a few degrees. The major prograde reactions that release water are the breakdown of chlorite to form garnet at low grade and the breakdown of muscovite at high grade. The volume of water released by formation of garnet at high grade is also important. These reactions have the capacity to buffer water pressure. The density of anhydrous pelitic rock increases markedly when chlorite breaks down and by the continuous reaction forming garnet at high grade. The heat content is controlled principally by heat capacity and continuous reactions. Discontinuous reactions have little thermal buffering capacity. Simulations of garnet fractionation show that commonly-observed garnet zoning profiles can be formed by garnet growth in the assemblage garnet-biotite-chlorite in common bulk compositions. A reversal of Fe-zoning in garnet can occur when garnet resumes growth above staurolite grade in the assemblage garnetbiotite-sillimanite. Discontinuities in zoning profiles can be caused only by disequilibrium. The disequilibrium can be due to either metastable persistence during a hiatus in growth or to growth by irreversible reaction. Because the appearance of garnet is controlled by a continuous rather than a discontinuous reaction, the appearance of garnet is very sensitive to bulk composition. The early development of garnet is also sensitive to the pressure and water pressure of metamorphism. As a consequence the first garnet isograd is of limited thermometric value. Metastable persistence of kyanite and manite at high grades could reduce the abundance of garnet and allow biotite to persist. Metastable persistence would also limit the of cordierite formation.     

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.     

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.