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.     

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

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

A model for garnet and plagioclase growth in pelitic schists: implications for thermobarometry and P-T path determinations

Numerical models of the progressive evolution of pelitic schists in the NCMnKFMASH system with the assemblage garnet + biotite + chlorite ± staurolite + plagioclase + muscovite + quartz + H₂O are presented with the goal of predicting compositional changes in garnet and plagioclase along different P-T paths. The numerical models support several conclusions that should prove useful for interpreting the P-T paths of natural parageneses: (i) Garnet may grow along P-T vectors ranging from heating with decompression to cooling with compression. P-T paths deduced from garnet zoning that are inconsistent with these growth vectors are self-contradictory. (ii) There is a systematic relation between garnet and plagioclase composition and growth such that for most P-T paths, garnet growth requires plagioclase consumption. Furthermore, mass balance in a closed system requires that as plagioclase is consumed the remaining plagioclase becomes increasingly albitic. Inclusions of plagioclase in the core of garnet should be more anorthitic than those near the rim and zoned matrix plagioclase should have rims that are more albitic than the cores. Complex plagioclase textures may arise from the local variability of growth and precipitation kinetics. (iii) A decrease of Fe/(Fe + Mg) in a garnet zoning profile is a reliable indicator of increasing temperature for the assemblage modelled. However, there is no single reliable ΔP monitor and inferences about ΔP can only be made by considering plagioclase and garnet together. (iv) Consumption of garnet during the production of staurolite removes material from the outer shell of a garnet and may make recovery of peak metamorphic compositions and P-T conditions impossible. Low ‘peak’temperatures typically recorded by staurolite-bearing assemblages may reflect this phenomenon. (v) Diffusional homogenization of garnet affects the computed P-T path and results in a clockwise rotation of the computed P-T vector relative to the true P-T path.     

Garnet crystal plasticity in the continental crust,new example from south Madagascar

Garnet (10 vol.%; pyrope contents 34–44 mol.%) hosted in quartzofeldspathic rocks within a large vertical shear zone of south Madagascar shows a strong grain‐size reduction (from a few cm to ～300 μm). Electron back‐scattered diffraction, transmission electron microscopy and scanning electron microscope imaging coupled with quantitative analysis of digitized images (PolyLX software) have been used in order to understand the deformation mechanisms associated with this grain‐size evolution. The garnet grain‐size reduction trend has been summarized in a typological evolution (from Type I to Type IV). Type I, the original porphyroblasts, form cm‐sized elongated grains that crystallized upon multiple nucleation and coalescence following biotite breakdown: biotite + sillimanite + quartz = garnet + alkali feldspar + rutile + melt. These large garnet grains contain quartz ribbons and sillimanite inclusions. Type I garnet is sheared along preferential planes (sillimanite layers, quartz ribbons and/or suitably oriented garnet crystallographic planes) producing highly elongated Type II garnet grains marked by a single crystallographic orientation. Further deformation leads to the development of a crystallographic misorientation, subgrains and new grains resulting in Type III garnet. Associated grain‐size reduction occurs via subgrain rotation recrystallization accompanied by fast diffusion‐assisted dislocation glide. This plastic deformation of garnet is associated with efficient recovery as shown by the very low dislocation densities (10¹⁰ m^?3 or lower). The rounded Type III garnet experiences rigid body rotation in fine‐grained matrix. In the highly deformed samples, the deformation mechanisms in garnet are grain‐size‐ and shape‐dependent: dislocation creep is dominant for the few large grains left (>1 mm; Type II garnet), rigid body rotation is typical for the smaller rounded grains (300 μm or less; Type III garnet) whereas diffusion creep may affect more elliptic garnet (Type IV garnet). The P–T conditions of garnet plasticity in the continental crust (≥950 °C; 11 kbar) have been identified using two‐feldspar thermometry and GASP conventional barometry. The garnet microstructural and deformation mechanisms evolution, coupled with grain‐size decrease in a fine‐grained steady‐state microstructure of quartz, alkali feldspar and plagioclase, suggests a separate mechanical evolution of garnet with respect to felsic minerals within the shear zone.     

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.     

Constraining the P–T path of a MORB-type eclogite using pseudosections, garnet zoning and garnet-clinopyroxene thermometry: an example from the Bohemian Massif

A mid‐ocean ridge basalt (MORB)‐type eclogite from the Moldanubian domain in the Bohemian Massif retains evidence of its prograde path in the form of inclusions of hornblende, plagioclase, clinopyroxene, titanite, ilmenite and rutile preserved in zoned garnet. Prograde zoning involves a flat grossular core followed by a grossular spike and decrease at the rim, whereas Fe/(Fe + Mg) is also flat in the core and then decreases at the rim. In a pseudosection for H₂O‐saturated conditions, garnet with such a zoning grows along an isothermal burial path at c. 750 °C from 10 kbar in the assemblage plagioclase‐hornblende‐diopsidic clinopyroxene‐quartz, then in hornblende‐diopsidic clinopyroxene‐quartz, and ends its growth at 17–18 kbar. From this point, there is no pseudosection‐based information on further increase in pressure or temperature. Then, with garnet‐clinopyroxene thermometry, the focus is on the dependence on, and the uncertainties stemming from the unknown Fe³⁺ content in clinopyroxene. Assuming no Fe³⁺ in the clinopyroxene gives a serious and unwarranted upward bias to calculated temperatures. A Fe³⁺‐contributed uncertainty of ±40 °C combined with a calibration and other uncertainties gives a peak temperature of 760 ± 90 °C at 18 kbar, consistent with no further heating following burial to eclogite facies conditions. Further pseudosection modelling suggests that decompression to c. 12 kbar occurred essentially isothermally from the metamorphic peak under H₂O‐undersaturated conditions (c. 1.3 mol.% H₂O) that allowed the preservation of the majority of garnet with symplectitic as well as relict clinopyroxene. The modelling also shows that a MORB‐type eclogite decompressed to c. 8 kbar ends as an amphibolite if it is H₂O saturated, but if it is H₂O‐undersaturated it contains assemblages with orthopyroxene. Increasing H₂O undersaturation causes an earlier transition to SiO₂ undersaturation on decompression, leading to the appearance of spinel‐bearing assemblages. Granulite facies‐looking overprints of eclogites may develop at amphibolite facies conditions.     

Kinetics of a garnet granulite reaction

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

Compositional variability of spinel-group minerals from the shergol serpentinized peridotites along indus suture zone,ladakh himalaya (India): constraints on tectonomagmatic history

The Shergol ophiolitic peridotites along ISZ, Ladakh Himalaya are serpentinized to various degrees and are harzburgite in composition. Electron microprobe analyses of spinels from Shergol Serpentinized Peridotites (SSPs) were carried out in order to evaluate their compositional variation with alteration. Chemical discontinuity was observed from core to rim in analyzed spinel grains with Cr-rich cores rimmed by Cr-poor compositions. From unaltered cores to rims it was observed that Cr³⁺# and Fe³⁺# increases while Mg²⁺# decreases due to Mg²⁺ − Fe²⁺ and Al³⁺ (Cr³⁺) − Fe³⁺ exchange with surrounding silicates during alteration. These peridotites contain Al-rich spinels forming subhedral to anhedral grains with lobate and corroded grain boundaries; altered to ferritchromite or magnetite along cracks and boundaries by later metamorphism episode. The unaltered Cr-spinel cores are identified as Al-rich and are characterized by lower values of Cr³⁺# (0.34–0.40), high Al³⁺# (0.58–0.68) and Mg²⁺# (0.52–0.70). Mineral chemistry of these Al-rich Cr-spinels suggest that host peridotites have an affinity to abyssal and alpine-type peridotites. High TiO₂ concentration of magmatic Cr-spinel cores are in agreement with MORB melt-residual peridotite interaction. Presence of unaltered magmatic Cr-spinel cores suggest that they do not have re-equilibrated completely with metamorphic spinel rims and surrounding silicates. Cr-spinel core compositions of SSPs suggest an ophiolitic origin derivation by low degrees of melting of a less-moderate depleted peridotite in a mid-ocean ridge tectonic setting. Based on textural and chemical observations the alteration conditions of studied spinel-group minerals match those of transitional greenschist-amphibolite facies metamorphism consistent with estimated metamorphic equilibration temperature of ∼ 500–600 ^°C.     

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

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

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

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

Crustal thickening of the lower crust of the Kohistan arc (N. Pakistan) deduced from Al zoning in clinopyroxene and plagioclase

The lower-crustal rocks of the Kohistan complex (northern Pakistan) are mostly composed of metabasic rocks such as pyroxene granulites, garnet granulites and amphibolites. We have investigated P–T trajectories of the relic two-pyroxene granulites, which are the protolith of the amphibolites within the Kamila amphibolite belt. Aluminous pyroxene retains igneous textures such as exsolution lamellae developed in the core. The significant amount of Al in clinopyroxene is buffered by breakdown reactions of plagioclase accompanied by film-like quartz as a product at grain boundaries between plagioclase and clinopyroxene. Distinct Al zoning profiles are preserved in pyroxene with exsolution lamellae in the core and in plagioclase adjacent to clinopyroxene in pyroxene granulites. In the northern part of the Kamila amphibolite belt, Al in clinopyroxene increases towards the rim and abruptly decreases at the outer rim, and anorthite in plagioclase decreases towards the rim and abruptly increases near the grain boundary between plagioclase and clinopyroxene. In the southern part of the Kamila amphibolite belt, Al in clinopyroxene and anorthite in plagioclase simply increase towards the margins of the grains. The anorthite zoning in plagioclase is in agreement with the zoning profiles of Ca-Tschermaks and jadeite components inferred from variations of Al, Na, Ti and Fe³⁺ in clinopyroxene. Assuming that the growth surface between them was in equilibrium, geothermobarometry based on Al zoning in clinopyroxene coexisting with plagioclase indicates that metamorphic pressures significantly increased with increasing temperature under granulite facies metamorphism. The peak of granulite facies metamorphism occurred at conditions of about 800 °C and 800–1100 MPa. These prograde P–T paths represent a crustal thickening process of the Kohistan arc during the Early to Middle Cretaceous. The crustal thickening of the Kohistan arc was caused by accretion of basaltic magma at mid-crustal depths.     

Monazite as a monitor of melting,garnet growth and feldspar recrystallization in continental lower crust

Monazite is a common accessory phase in felsic granulite ribbon mylonites exposed in the Upper Deck domain of the Athabasca granulite terrane, western Canadian Shield. Field relationships, bulk rock geochemistry and phase equilibria modelling in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃ system are consistent with the garnet‐rich rocks representing the residual products of ultrahigh temperature melting of biotite‐bearing paragneisses driven by intraplating of mafic magma in continental lower crust. The c. 2.64–2.61 Ga Y‐rich resorbed monazite cores included in garnet are interpreted as relicts of detrital grains deposited on the Earth's surface after c. 2.61 Ga. Yttrium‐poor monazite domains in garnet are depleted in Sm and Gd and linked to fluid‐absent melting of biotite + plagioclase + quartz ± sillimanite during a prograde loading path from ≤0.8 to ≥1.4 GPa. The c. 2.61–2.55 Ga Y‐depleted, Th‐rich monazite domains crystallized in the presence of garnet + ternary feldspar ± orthopyroxene + peraluminous melt. The c. 2.58–2.52 Ga monazite rims depleted in Th + Ca and enriched in Eu are linked to localized melt extraction synchronous with growth of high‐pressure (HP) grossular‐rich garnet at the expense of plagioclase during crustal thickening, culminating at >950 °C. Re‐heating and dextral transpressive lower crustal reactivation at c. 1.9 Ga resulted in syn‐kinematic growth of (La + Ce)‐enriched monazite and a second generation of garnet, concurrent with recrystallization of feldspar and orthopyroxene at 1.0–1.2 GPa and 600–700 °C. Monazite grains in this study are marked by positive Eu‐anomalies relative to chondrite. A direct link is implied between Y, Sm, Eu and Gd in monazite and two major phases in continental lower crust: garnet and plagioclase. Positive Eu‐anomalies in lower crustal monazite associated with modally abundant garnet appear to be directly related to Eu‐enrichment and depletions of Y, Sm and Gd that are consequences of garnet growth and plagioclase breakdown during HP melting of peraluminous bulk compositions.     

Metamorphic evolution of low-T eclogite from the North Qilian orogen, NW China: evidence from petrology and calculated phase equilibria in the system NCKFMASHO

Low‐T eclogites in the North Qilian orogen, NW China share a common assemblage of garnet, omphacite, glaucophane, epidote, phengite, quartz and rutile with or without paragonite. Phase relations for the low‐T eclogites can be modelled well in the system NCKFMASHO with the updated solid‐solution models for amphibole and clinopyroxene. Garnet in the eclogite typically exhibits growth zonations in which pyrope increases while grossular somewhat decreases from core to rim, which is modelled as having formed mainly in the P–T conditions of lawsonite‐eclogite facies at the pre‐peak stage. Omphacite shows an increase in jadeite component as aegirine and also total FeO decrease in going from the inclusions in garnet to grains in the matrix, and from core to rim of zoned crystals, reflecting an increase in metamorphic P–T conditions. Glaucophane exhibits a compositional variation in X(gl) (= Fe²⁺/(Fe²⁺ + Mg)) and F(gl) (= Fe³⁺/(Fe³⁺ + Al) in M2 site), which decrease from the inclusions in garnet to crystals in the matrix, consistent with an increase in P–T conditions. However, for zoned matrix crystals, the X(gl) and F(gl) increase from core to rim, is interpreted to reflect a late‐stage decompression. Using composition isopleths for garnet rim and phengite in P–T pseudosections, peak P–T conditions for three samples Q5–45, Q5–01 and Q7–28 were estimated as 530–540 °C at 2.10–2.25 GPa, 580–590 °C at 2.30–2.45 GPa and 575–590 °C at 2.50–2.65 GPa, respectively, for the same assemblage garnet + omphacite + glaucophane + lawsonite (+ phengite + quartz + rutile) at the peak stage. The eclogites suggest similar P–T ranges to their surrounding felsic–pelitic schists. During post‐peak decompression of the eclogites, the most distinctive change involves the transformation of lawsonite to epidote, releasing large amount of water in the rock. The released fluid promoted further growth of glaucophane at the expense of omphacite and, in appropriate bulk‐rock compositions, paragonite formed. The decompression of eclogite did not lead to pronounced changes in garnet and phengite compositions. Peak P–T conditions of the North Qilian eclogite are well constrained using both the average P–T and pseudosection approaches in Thermocalc. Generally, the conventional garnet–clinopyroxene geothermometer is too sensitive to be used for constraining the temperature of low‐T eclogite because of the uncertainty in Fe³⁺ determination in omphacite and slight variations in mineral compositions because of incomplete equilibration.     

Effects of diffusional modification of garnet growth zoning on P-T path calculations

The effect of intragranular diffusion on chemical zoning in garnet and on P-T paths calculated from that zoning was evaluated using a numerical model of multicomponent diffusion in combination with simulations of garnet growth. Syn-and post-growth diffusion of Mg–Fe–Mn–Ca species in garnet was calculated for a model pelitic assemblage over a range of temperatures from 485 to 635°C. Compositions from zoned garnet, as modified by diffusion, hypothetical inclusions of plagioclase within garnet and matrix phases were used to reconstruct pressure-temperature (P-T) paths from isobaric and polybaric model histories. P-T path calculations, based on numerical simulations conducted over an input isobaric heating path that reached peak temperatures between 585 and 635°C, show that relaxation of garnet compositional gradients by diffusion can induce modest to appreciable curvature in the inferred paths. Retrieved paths also indicated somewhat smaller overall temperature changes relative to the actual temperature difference of the input path. The magnitude of these distortions is shown to depend upon the heating and cooling rate and garnet crystal size as well as the actual peak temperature condition. The effect of diffusion on path trajectories in simulations with thermal histories that also included cooling were comparable to heating-only models that reached peak temperatures approximately 15–30°C higher. Compositions of garnets with radii less than 1 mm, that reached actual peak temperatures of 605°C along temperature-time histories characteristic of regional metamorphism, experienced sufficient diffusional relaxation to introduce errors of hundreds of bars to in excess of one kilobar in path trajectories. Path distortions were significant at heating/cooling rates less than 10°C/Ma, but rapidly diminished for rates faster than this. In polybaric simulations diffusion effects were least noticeable when the actual pressure-temperature conditions changed in a clockwise sense (i.e., convex to higher P and higher T), but apprecciable modification was seen in path models that underwent counterclockwise changes in P and T. Reequilibration of garnet rim compositions occurred during cooling on all paths, and temperature maxima obtained from garnet-biotite geothermometry underestimated actual peak conditions by 40 to 70°C. Calculations suggest that P-T path trajectories calculated from garnets of at least 1 mm size, and that experienced actual thermal maxima below 585°C, are not likely to be distorted by diffusional effects during regional metamorphism. However, P-T path reconstructions based on garnet zonation with smaller grains or higher temperatures may lead to misinterpretation of crystallization history. The partitioning record of peak metamorphic temperatures may be destroyed by diffusional reequilibration of garnet rim compositions during cooling, seriously complicating the task of quantitatively estimating diffusion effects on path calculations.     

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.     

Details of the gabbro‐to‐eclogite transition determined from microtextures and calculated chemical potential relationships

Permian‐aged metagabbros from the eclogite type‐locality in the eastern European Alps were partially to completely transformed to eclogite during Eoalpine intracontinental subduction. Microtextures developed along a preserved fluid infiltration and reaction front in the gabbros record the incipient gabbro‐to‐eclogite transition, allowing the details of the eclogitization process to be investigated. Original, anorthite‐rich igneous plagioclase is pervasively replaced by fine‐grained intergrowths of clinozoisite, kyanite and Na‐rich plagioclase. Where plagioclase was in contact with igneous orthopyroxene, 100–200 μm thick bimineralic coronae of symplectic kyanite and diopsidic clinopyroxene form along the edges of the grains. The rims of igneous orthopyroxene develop a complementary bimineralic corona of diopsidic clinopyroxene and garnet. Igneous clinopyroxene does not show any breakdown textures; however, jadeite content gradually increases towards the rims. In addition, exsolution lamellae inherited from the igneous clinopyroxene become progressively more jadeitic as eclogitization proceeds. Given that the igneous plagioclase is pervasively replaced by clinozoisite, kyanite and Na‐rich plagioclase, whereas kyanite–diopside symplectites are confined to narrow rim zones, we suggest that the development of these textures was controlled by the (im)mobility of different elements on different length scales. The presence of hydrous minerals in the core of anhydrous plagioclase indicates that H₂O diffusivity occurred on a mm‐scale. By contrast, the size of the anhydrous diopside–kyanite and diopside–garnet symplectites indicate that Fe–Mg–Ca–Na diffusivity was limited to a 10s of μm scale. Chemical potential relations calculated in the idealized NCASH chemical system show that the clinozoisite–kyanite–albite intergrowths formed due to an increase of μH₂O to plagioclase, whereas all other elements remained effectively immobile on the scale of this texture. Fluid conditions indicated by this texture span from virtually dry conditions (0.15) to H₂O‐saturation, and therefore does not imply that the rocks were ever fluid‐saturated. Calculations in the CMAS and NCFMAS systems show that the gabbro‐to‐eclogite transition is characterized by the growth of garnet, diopsidic clinopyroxene and kyanite due to diffusion of Ca (+ Na) and Mg (+ Fe) along a μCaO (+ Na₂O)–μMgO (+ FeO) chemical potential gradient developed between orthopyroxene and plagioclase compositional domains. The anhydrous nature of the textures indicate that the gabbro‐to‐eclogite transition is not driven by hydration; however, increased μH₂O acts as a catalyst that increases diffusivity of all elements and rates of dissolution–precipitation, allowing the overstepped metamorphic reactions to occur. Our results show that crustal eclogite formation requires low H₂O content, confirming that true eclogites are dry rocks.     

Diffusion-controlled growth of wollastonite rims between quartz and calcite: comparison between nature and experiment

Growth rates of wollastonite reaction rims between quartz and calcite were experimentally determined at 0.1 and 1 GPa and temperatures from 850 to 1200 °C. Rim growth follows a parabolic rate law indicating that this reaction is diffusion‐controlled. From the rate constants, the D′δ‐values of the rate‐limiting species were derived, i.e. the product of grain boundary diffusion coefficient D′ and the effective grain boundary width, δ. In dry runs at 0.1 GPa, wollastonite grew exclusively on quartz surfaces. From volume considerations it is inferred that (D′_CaOδ)/(D′_SiO2δ)≥1.33, and that SiO₂ diffusion controls rim growth. D′_SiO2δ increases from about 10^?25 to 10^?23 m³ s^?1 as temperature increases from 850 to 1000 °C, yielding an apparent activation energy of 330±36 kJ mol^?1. In runs at 1 GPa, performed in a piston‐cylinder apparatus, there were always small amounts of water present. Here, wollastonite rims always overgrew calcite. Rims around calcite grains in quartz matrix are porous and their growth rates are controlled by a complex diffusion‐advection mechanism. Rim growth on matrix calcite around quartz grains is controlled by grain boundary diffusion, but it is not clear whether CaO or SiO₂ diffusion is rate‐limiting. D′δ increases from about 10^?21 to 10^?20 m³ s^?1 as temperature increases from 1100 to 1200 °C. D′_SiO2δ or D′_CaOδ in rims on calcite is c. 10 times larger than D′_SiO2δ in dry rims at the same temperature. Growth structures of the experimentally produced rims are very similar to contact‐metamorphic wollastonite rims between metachert bands and limestone in the Bufa del Diente aureole, Mexico, whereby noninfiltrated metacherts correspond to dry and brine‐infiltrated metacherts to water‐bearing experiments. However, the observed diffusivities were 4 to 5 orders of magnitude larger during contact‐metamorphism as compared to our experimental results.     

Grain‐scale dependency of metamorphic reaction on crystal plastic strain

The Breaksea Orthogneiss in Fiordland, New Zealand preserves water‐poor intermediate and mafic igneous rocks that were partially recrystallized to omphacite granulite and eclogite, respectively, at P ≈ 1.8 GPa and T ≈ 850°C. Metamorphic reaction consumed plagioclase and produced grossular‐rich garnet, jadeite‐rich omphacite, clinozoisite and kyanite. The extent of metamorphic reaction, identified by major and trace element composition and microstructural features, is patchy on the grain and outcrop scale. Domains of re‐equilibration coincide with areas that exhibit higher strain suggesting a causal link between crystal plastic strain and metamorphic reaction. Quantitative orientation analysis (EBSD) identifies gradual and stepped changes in crystal lattice orientations of igneous phenocrysts that are surrounded by homophase areas of neoblasts, characterized by high grain boundary to volume ratios and little to no internal lattice distortion. The narrow, peripheral compositional modification of less deformed garnet and omphacite phenocrysts reflects limited lattice diffusion in areas that lacked three‐dimensional networks of interconnected low‐angle boundaries. Low‐angle boundaries acted as elemental pathways (pipe diffusion) that enhanced in‐grain element diffusion. The scale of pipe diffusion is pronounced in garnet relatively to clinopyroxene. Strain‐induced mineral transformation largely controlled the extent of high‐T metamorphic reaction under relatively fluid‐poor conditions.     

Compositional controls on spinel clouding and garnet formation in plagioclase of olivine metagabbros,Adirondack Mountains,New York

Olivine metagabbros from the Adirondacks usually contain both clear and spinel-clouded plagioclase, as well as garnet. The latter occurs primarily as the outer rim of coronas surrounding olivine and pyroxene, and less commonly as lamellae or isolated grains within plagioclase. The formation of garnet and metamorphic spinel is dependent upon the anorthite content of the plagioclase. Plagioclase more sodic than An_38±2 does not exhibit spinel clouding, and garnet rarely occurs in contact with plagioclase more albitic than An_36±4. As a result of these compositional controls, the distribution of spinel and garnet mimics and visually enhances original igneous zoning in plagioclase. Most features of the arrangement of clear (unclouded) plagioclase, including the shells or moats of clear plagioclase which frequently occur inside the garnet rims of coronas, can be explained on the basis of igneous zoning. The form and distribution of the clear zones may also be affected by the metamorphic reactions which have produced the coronas, and by redistribution of plagioclase in response to local volume changes during metamorphism.Authors listed alphabeticallyPublished by permission of the Director, New York State Museum, Journal Series Number 299     

Constraining the prograde and retrograde P-T paths of granulites using decomposition of initially zoned garnets: an example from the Central Indian Tectonic Zone

The present study from the Sausar Mobile Belt (SMB) in the southern part of the Central Indian Tectonic zone (CITZ) demonstrates how microdomainal compositional variation of a single garnet porphyroblast in a metapelite granulite sample records the different segments of a near complete P-T path of metamorphic evolution. The microdomainal variation is ascribed to the preservation of growth zoning and heterogeneous distribution of diverse inclusion mineral assemblages. Subsequent mineral reactions under changing P/T conditions were controlled by this compositional heterogeneity. Four stages of metamorphic evolution have been deciphered. An early prograde stage (M_o) is implied by the rare presence of staurolite-biotite-quartz and in places of kyanite inclusion assemblages in other metapelite samples, together with the growth zoning preserved in garnet. The peak metamorphism (M₁) at ~9.5 kbar, ~850 °C is consistent with the biotite dehydration melting that produced garnet-K-feldspar and granitic leucosomes. This was followed by near isothermal decompression (M₂) at ~6 kbar, ~825 °C, during which different garnet segments behaved as separate microscale bulk compositions and decomposed both internally and externally to produce different retrograde mineral assemblages. In the quartz-bearing domain of almandine-rich and grossular-rich garnet core, grossular components in garnet reacted with included sillimanite and quartz to produce coronal plagioclase (X_An=0.90). By contrast, grossular-rich garnet in quartz-absent domain reacted with included sillimanite to produce layered spinel_ss {X_Mg (Mg/Mg+Fe²⁺) = 0.23–0.26}, X_Al (Al/Al+Fe³⁺)=0.71–0.81}-plagioclase (X_An=0.91)-cordierite {X_Mg (Mg/Mg+Fe²⁺) = 0.80–0.83} coronas both in the core and inner rim region of garnet. During post-decompression cooling, reactions occurred at about 600 °C (M₃), whereby quartz-bearing, sillimanite-absent microdomains of pyrope-rich, grossular-poor garnet outer rim decomposed to form relatively magnesian assemblages of cordierite-anthophyllite and cordierite-biotite-quartz. M₂ spinel_ss decomposed to polyphase domains of spinel-magnetite±högbomite at this stage. Collating the textural and geothermobarometric results, a clockwise P-T path has been deduced. The deduced P-T loop is consistent with a model of crustal thickening due to continental collision, followed by rapid vertical thinning, which appears to be the general feature of the Sausar Mobile Belt. Using model calculations of the preserved growth and diffusion zoning in garnet, we demonstrate rather short-lived nature of this collision orogeny (in the order of 40–60 Ma).Editorial responsibility: W. Schreyer