Controls on metamorphic equilibration: the importance of intergranular solubilities mediated by fluid composition

A dramatic demonstration of the role of intergranular solubility in promoting chemical equilibration during metamorphism is found in the unusual zoning of garnet in pelitic schist exposed at Harpswell Neck, Maine, USA. Many garnet crystals have irregular, patchy distributions of Mn, Cr, Fe and Mg in their inclusion‐rich interiors, transitioning to smooth, concentric zoning in their inclusion‐poor outer rims; in contrast, zoning of Ca and Y is comparatively smooth and concentric throughout. We re‐assess the disputed origin of these zoning features by examining garnet growth in the context of the thermal and structural history of the rocks, and by evaluating the record of fluid–rock interaction revealed in outcrop‐scale veining and fluid‐inclusion assemblages. The transition in the character of garnet zoning correlates with the onset of a synkinematic, simple‐shear‐dominated phase of garnet growth and with a shift in the composition of the intergranular fluid from CO₂‐rich to H₂O‐rich. Compositional variations in garnet are therefore best explained by a two‐stage growth history in which intergranular diffusive fluxes reflect differences in the concentration of dissolved species in these two contrasting fluids. Interiors of garnet crystals grew in the presence of a CO₂‐rich fluid, in which limited solubility for Mn and Cr (and perhaps Fe and Mg) produced patchy disequilibrium overprint zoning, while appreciable solubility for Ca and Y permitted their rock‐wide equilibration. Rims grew in the presence of an H₂O‐rich fluid, in which high intergranular concentrations for all elements except Cr enabled diffusion over length scales sufficient for rock‐wide equilibration. This striking example of partial chemical equilibrium during reaction and porphyroblast growth implies that thermal effects may commonly be subsidiary in importance to solubilities in the intergranular medium as determinants of length scales for metamorphic equilibration.     

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.     

Variscan relicts in Alpine high-P pelitic rocks from Samos (Greece): evidence from multi-stage garnet and its included minerals

Porphyroblastic garnet schists from northern Samos contain in their matrix the assemblage Ca‐rich garnet + phengite + paragonite ± chloritoid equilibrated at ～530 °C and ～19 kbar during early Tertiary metamorphism. These high‐pressure/low‐temperature (HP‐LT) metapelitic rocks also exhibit mineralogical and microstructural evidence of an older, higher temperature metamorphism. Large, centimetre‐sized Fe‐rich garnet showing growth zoning developed discontinuous, <0.5 mm thick, Ca‐rich and Mn‐poor overgrowths, compositionally matching small (<1 mm) high‐P matrix garnet. Because the discontinuous garnet rims are in textural and chemical equilibrium with Alpine high‐P minerals, the central parts of the garnet porphyroblasts were found to have formed prior to the Tertiary metamorphism. This is supported by electron microprobe U‐Th‐Pb dating of monazite inclusions yielding partly reset Variscan ages between 360 and 160 Ma. Monazite‐xenotime and garnet‐muscovite thermometry applied to inclusions in the pre‐Alpine garnet yielded temperatures of 600–625 °C (at 3–8 kbar). Prismatic Al‐rich pseudomorphs, possibly after kyanite/sillimanite, and inclusions in garnet composed of white K‐Na mica + quartz ± albite ± K feldspar, interpreted as possible replacements of an intermediate K‐Na feldspar, further support Variscan amphibolite facies conditions. The Samos metapelites thus experienced higher temperatures during the Variscan than during Alpine metamorphism. Diffusional relaxation was very limited between pre‐Alpine garnet and Alpine garnet; both were filled with Alpine garnet along overgrowths and fractures. Fluid‐mediated intergranular element transport, enhanced by deformation, appears crucial in transforming the Variscan garnet into a grossular richer composition during Alpine subduction‐zone metamorphism. At such conditions, dissolution–reprecipitation appears to be a much more effective mechanism for modifying garnet compositions than diffusion. Amphibolite facies conditions are typical for Variscan basement relics exposed in central Cycladic and Dodecanese islands as well as in eastern Crete. The Samos metapelites studied comprise a north‐eastern extension of these basement occurrences.     

Geochemistry of major and rare earth elements in garnet of the Kal-e Kafi skarn,Anarak Area,Central Iran: Constraints on processes in a hydrothermal system

Grossular-andradite (grandite) garnets, precipitated from hydrothermal solutions is associated with contact metamorphism in the Kal-e Kafi skarn show complex oscillatory chemical zonation. These skarn garnets preserve the records of the temporal evolution of contact metasomatism. According to microscopic studies and microprobe analysis profiles, the studied garnet has two distinct parts: the intermediate (granditic) composition birefringent core that its andradite content based on microprobe analysis varies between 0.68–0.7. This part is superimposed with more andraditic composition, and the isotropic rim which its andradite content regarding microprobe analysis ranges between 0.83–0.99. Garnets in the studied sample are small (0.5–2 mm in diameter) and show complex oscillatory zoning. Electron microprobe analyses of the oscillatory zoning in grandite garnet of the Kal-e Kafi area showed a fluctuation in chemical composition. The grandite garnets normally display core with intermediate composition with oscillatory Fe-rich zones at the rim. Detailed study of oscillatory zoning in grandite garnet from Kal-e Kafi area suggests that the garnet has developed during early metasomatism involving monzonite to monzodiorite granitoid body intrusion into the Anarak schist- marble interlayers. During this metasomatic event, Al, Fe, and Si in the fluid have reacted with Ca in carbonate rocks to form grandite garnet. The first step of garnet growth has been coeval with intrusion of the Kal-e Kafi granitoid into the Anarak schist- marble interlayers. In this period of garnet growth, change in fluid composition may cause the garnet to stop growing temporarily or keep growing but in a much slower rate allowing Al to precipitate rather than Fe. The next step consists of pervasive infiltration of Fe rich fluids and Fe rich grandite garnets formation as the rim of previously formed more Al rich garnets. Oscillatory zoning in the garnet probably reflects an oscillatory change in the fluid composition which may be internally and/or externally controlled. The rare earth elements study of these garnets revealed enrichment in light REEs (LREE) with a maximum at Pr and Nd and a negative to no Eu anomaly. This pattern is resulted from the uptake of REE out of hydrothermal fluids by growing crystals of calcsilicate minerals principally andradite with amounts of LREE controlled by the difference in ionic radius between Ca⁺⁺ and REE³⁺ in garnet x site.     

Deformation-induced garnet zoning

Compositional zoning patterns in garnet porphyroblasts from kyanite-bearing samples of the Devonian Littleton Formation, north-central Massachusetts, reveal complex patterns of growth that are related to multiple deformation and metamorphic events. Garnet porphyroblasts exhibit asymmetrical and irregular zoning patterns in X_Mn, X_Ca and Fe/(Fe + Mg). Zoning reversals in Mn and Fe/(Fe + Mg) and patch distribution in Ca appear to occur around the boundaries of the textural zones. Also, the compositions of the garnet at the textural boundaries are variable for all traverses. These observations suggest that the garnet zoning was not only modified from diffusion processes, but was also influenced by pre-existing microfabrics through the effects of preferential dissolution and resorption in partial disequilibrium. Relationships between chemical and textural truncations indicate that the zoning patterns of garnet were strongly modified from preferential dissolution and precipitation during the development of successive foliations that occurred in zones of high strain/stress (cleavage seams) and zones of low strain/stress, respectively.     

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.     

Decoding the complex internal chemical structure of garnet porphyroblasts from the Zermatt area,Western Alps

Garnet is a prototypical mineral in metamorphic rocks because it commonly preserves chemical and textural features that can be used for untangling its metamorphic development. Large garnet porphyroblasts may show extremely complex internal structures as a result of a polycyclic growth history, deformation, and modification of growth structures by intra‐ and intercrystalline diffusion. The complex internal structure of garnet porphyroblasts from garnet–phengite schists (GPS) of the Zermatt area (Western Alps) has been successfully decoded. The centimetre‐sized garnet porphyroblasts are composed of granulite facies garnet fragments overgrown by a younger generation of grossular‐rich eclogite facies garnet. The early granulite facies garnet (G‐Grt) formed from low‐P, high‐T metamorphism during a pre‐Alpine orogenic event. The late garnet (E‐Grt) is typical of high‐pressure, low‐temperature (HPLT) metamorphism and can be related to Alpine subduction of the schists. Thus, the garnet of the GPS are polycyclic (polymetamorphic). G‐Grt formation occurred at ~670 MPa and 780°C, E‐Grt formed at ~1.7 GPa and 530°C. The G‐Grt is relatively rich in Prp and poor in Grs, while E‐Grt is rich in Grs and poor in Prp. The Alm content (mol.%) of G‐Grt is 68 of E‐Grt 55. After formation of E‐Grt between and around fragmented G‐Grt at 530°C, the GPS have been further subducted and reached a maximum temperature of 580°C before exhumation started. Garnet composition profiles indicate that the initially very sharp contacts between the granulite facies fragments of G‐Grt and fracture seals of HPLT garnet (E‐Grt) have been modified by cation diffusion. The profiles suggest that Ca did not exchange at the scale of 1 µm, whereas Fe and Mg did efficiently diffuse at the derived maximum temperature of 580°C for the GPS at the scale of 7–8 µm. The Grt–Grt diffusion profiles resulted from spending c. 10 Ma at 530–580°C along the P–T–t path. The measured Grt composition profiles are consistent with diffusivities of log D_MgFe = ?25.8 m²/s from modelled diffusion profiles. Mg loss by diffusion from G‐Grt is compensated by Fe gain by diffusion from E‐Grt to maintain charge balance. This leads to a distinctive Fe concentration profile typical of uphill diffusion.     

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.     

Chemical composition and evolution of the garnets in the Astamal Fe-LREE distal skarn deposit,Qara-Dagh–Sabalan metallogenic belt,Lesser Caucasus,NW Iran

The chemistry of garnet can provide clues to the formation of skarn deposits. The chemical analyses of garnets from the Astamal Fe-LREE distal skarn deposit were completed using an electron probe micro-analyzer. The three types of garnet were identified in the Astamal skarn are: (I) euhedral coarse-grained isotropic garnets (10–30 mm across), which are strongly altered to epidote, calcite and quartz in their rim and core, with intense pervasive retrograde alteration and little variation in the overall composition (Adr_94.3–84.4 Grs_8.5–2.7 Alm_1.9–0.2) (garnet I); (II) anhedral to subhedral brecciated isotropic garnets (5–10 mm across) with minor alteration, a narrow compositional range along the growth lines (Adr_82–65.4 Grs_21.9–11.7 Alm_11.1–2.4) and relatively high Cu (up to 1997 ppm) and Ni (up to 1283 ppm) (garnet II); and (III) subhedral coarser grained garnets (> 30 mm across) with moderate alteration, weak diffusion and irregular zoning of discrete grossular-almandine-rich domains (Adr_84.2–48.8 Grs_32.4–7.6 Alm_19.9–3.5) (garnet III). In the third type, the almandine content increases with increasing grossular/andradite ratio and increasing substitutions of Al for Fe^3 +.Almost all three garnet types have been replaced by fine-grained, dark-brown allanite that is typically disseminated and has the same relief as andradite. The Cu content increases while Ni content decreases slightly towards the rim of garnet II and garnet III. Copper in garnet II is positively correlated with increasing almandine content and decreasing andradite content, indicating that the almandine structure, containing relatively more Fe^2 +, is more suitable than andradite and grossular to host divalent cations such as Cu^2 +. Nickel in garnet II is positively correlated with increasing andradite content, total Fe, and decreasing almandine content. This is because Ni^2 + substitutes for Fe^3 + in the Y (octahedral) position. There are unusual discrete grossular-almandine rich domains within andraditic garnet III, indicating the low diffusivity of Ca compared to Fe at high temperatures.     

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.     

Complex chemical zoning in eclogite facies garnet reaction rims: the role of grain boundary diffusion

In metapelites of the Saualpe complex (Eastern Alps) continuous 10 µm to 20 µm wide garnet reaction rims formed along biotite-plagioclase and biotite-perthite interfaces. The pre-existing mineral assemblages are remnants of low pressure high temperature metamorphism of Permian age. The garnet reaction rims grew during the Cretaceous eclogite facies overprint. Reaction rim growth involved transfer of Fe and Mg components from the garnet-biotite interface to the garnet-feldspar interface and transfer of the Ca component in the opposite direction. The garnets show complex, asymmetrical chemical zoning, which reflects the relative contributions of short circuit diffusion along grain boundaries within the polycrystalline garnet reaction rims and volume diffusion through the grain interiors on bulk mass transfer. It is demonstrated by numerical modelling that the spacing of the grain boundaries, i.e. the grain size of the garnet in the reaction rim is a first order control on its internal chemical zoning.     

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

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

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.     

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.     

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.     

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.     

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.     

Cold subduction and the formation of lawsonite eclogite – constraints from prograde evolution of eclogitized pillow lava from Corsica

A new discovery of lawsonite eclogite is presented from the Lancône glaucophanites within the Schistes Lustrés nappe at Défilé du Lancône in Alpine Corsica. The fine‐grained eclogitized pillow lava and inter‐pillow matrix are extremely fresh, showing very little evidence of retrograde alteration. Peak assemblages in both the massive pillows and weakly foliated inter‐pillow matrix consist of zoned idiomorphic Mg‐poor (<0.8 wt% MgO) garnet + omphacite + lawsonite + chlorite + titanite. A local overprint by the lower grade assemblage glaucophane + albite with partial resorption of omphacite and garnet is locally observed. Garnet porphyroblasts in the massive pillows are Mn rich, and show a regular prograde growth‐type zoning with a Mn‐rich core. In the inter‐pillow matrix garnet is less manganiferous, and shows a mutual variation in Ca and Fe with Fe enrichment toward the rim. Some garnet from this rock type shows complex zoning patterns indicating a coalescence of several smaller crystallites. Matrix omphacite in both rock types is zoned with a rimward increase in X_Jd, locally with cores of relict augite. Numerous inclusions of clinopyroxene, lawsonite, chlorite and titanite are encapsulated within garnet in both rock types, and albite, quartz and hornblende are also found included in garnet from the inter‐pillow matrix. Inclusions of clinopyroxene commonly have augitic cores and omphacitic rims. The inter‐pillow matrix contains cross‐cutting omphacite‐rich veinlets with zoned omphacite, Si‐rich phengite (Si = 3.54 apfu), ferroglaucophane, actinolite and hematite. These veinlets are seen fracturing idiomorphic garnet, apparently without any secondary effects. Pseudosections of matrix compositions for the massive pillows, the inter‐pillow matrix and the cross‐cutting veinlets indicate similar P–T conditions with maximum pressures of 1.9–2.6 GPa at temperatures of 335–420 °C. The inclusion suite found in garnet from the inter‐pillow matrix apparently formed at pressures below 0.6–0.7 GPa. Retrogression during initial decompression of the studied rocks is only very local. Late veinlets of albite + glaucophane, without breakdown of lawsonite, indicate that the rocks remained in a cold environment during exhumation, resulting in a hairpin‐shaped P–T path.     

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。     

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.