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.     

A garnet population in Yellowknife schist, Canada

Abstract Data are presented on a garnet population in a specimen of garnet-biotite-plagioclase-quartz schist from the cordierite zone of an Archaean thermal dome in the Southern Slave Province of the Canadian Shield. Garnet crystals are bounded by planar dodecahedral faces and by trapezohedral faces which on the 10-μm scale are corrugated. Crystal distribution, as revealed by dissection of a small cubic volume of rock, is random. The size distribution is normal, with a mean diameter of 0.81 mm and a standard deviation of 0.32 mm. In the largest crystal of the population (mean radius 0.83 mm), [Mn] = 100 Mn/(Fe + Mg + Mn + Ca) decreases from 14.5 at the centre to 7.5 and then increases in the outer margin to 8.5; [Fe] increases continuously from 67 at the centre to 77 at the surface; [Mg] increases from 12.5 to 13.5 and then falls sharply to 11; [Ca] remains unchanged at 4.0 and then drops to 3.3. Progressively smaller crystals have progressively lower [Mn] and higher [Fe] concentrations at their centres, while all crystals have the same margin composition. Growth vectors extending from given concentration contours to crystal surfaces are of equal length regardless of the size of the crystal in which the vector is located. A garnet-forming model is presented in which reaction was initiated by a rise in temperature. Nucleation sites were randomly selected. The nucleation rate increased with time and then declined. Crystal faces advanced at a constant linear rate, which implies an increase in volume proportional to surface area. Initially, the composition of garnet deposited on crystal surfaces was determined by van Laar equations of equilibrium, which demanded the withdrawal of Mn and Fe from within chlorite crystals. This transfer reaction was then accompanied by an ion exchange reaction which moved Mn and Fe to garnet surfaces from biotite, in exchange for Mg. The exchange reaction provides an explanation for the high overall concentration of Mn and Fe in garnet and for the observed Mn and Mg reversals in the margins of crystals. The increase of garnet volume in the garnet population is found to be parabolic, i.e. Vαα⁵.     

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.     

Ca distribution between almandine-rich garnet and plagioclase in pelitic and psammitic schists from the metamorphic basement of North-Eastern Sardinia

Garnet and plagioclase pairs from fourteen selected samples, from garnet to sillimanite zones, collected along a NS traverse throughout the metamorphic basement of NE Sardinia, have been analyzed by microprobe.Beyond the garnet isograd, plagioclase has albitic composition and the garnet (a Ca-rich almandine) shows Ca/ Ca+Mg+Fe ratios of about 0.35–0.30, fairly constant from core to rim.Towards the North, still in the garnet zone, when on the large albitic core of plagioclase a thin and discontinuous oligoclasic rim (An₂₂–An₁₈) formed, we observe in the garnet edge an abrupt decrease of the Ca/Ca+Mg+Fe ratio (0.27–0.16).In the staurolite and sillimanite zones garnet does not show significant Ca-zoning and it is characterized by low Ca content (Ca/Ca+Mg+Fe<0.1); the coexisting plagioclase has oligoclasic (An₁₆–An₂₇) composition.The chemical data and the microstructural evidence on growth time indicate that the garnet and plagioclase had a strong mutual interference in determining the relative Ca distribution.The most relevant reactions are discussed and, in particular, the antipathetical Ca-zoning, recorded by garnet and plagioclase in the garnet zone, is considered as the evidence of temperature increase during growth of the two minerals. It is also suggested that the sharp variation of Ca content at the garnet edge was controlled by the discontinuous nature of plagioclase solid solution in the peristeritic range.The order of appearance of garnet and oligoclase in the basement of NE Sardinia is also discussed in comparison with other well known metamorphic sequence (Vermont, New Zealand and Dalradian). It is concluded that the different order of appearance is controlled other than the different nature of the calcic phases in the lower grade zones also by the in the fluid phase.     

Biotite and garnet compositional variation and mineral equilibria in Grenville gneisses of the Otter Lake area, Quebec

Garnet-biotite gneisses, some of which contain sillimanite or hornblende, are widespread within the Otter Lake terrain, a portion of the Grenville Province of the Canadian Shield. The metamorphic grade is upper amphibolite to, locally, lower granulite facies. The atomic ratio Fe²⁺/(Fe²⁺+ Fe³⁺) in biotite ranges from 0.79 to 0.89 (ferrous iron determinations in 10 highly pure separates), with a mean of 0.86. Mg and Fe²⁺ atoms occupy 67–78% of the octahedral sites, the remainder are occupied by Fe³⁺, Ti, and Al, and some are vacant. Mg/(Mg + Fe²⁺), denoted X, in the analysed samples ranges from 0.32 to 0.65. Garnet contains 1–24% grossular, 1–12% spessartine and X ranges from 0.07 to 0.34. Compositional variation in biotite and garnet is examined in relation to three mineral equilibria: (I) biotite + sillimanite + quartz = garnet + K-feldspar + H₂O; (II) pyrope + annite = almandine + phlogopite; (III) anorthite = grossular + sillimanite + quartz. Measurements of X (biotite) and X (garnet) are used to construct an illustrative model for equilibrium (I) which relates the observed variation in X to a temperature range of 70°C or a range in H₂O activity of 0.6; the latter interpretation is preferred. In sillimanite-free gneisses, the distribution of Mg and Fe²⁺ between garnet (low in Ca and Mn) and biotite is adequately described by a distribution coefficient (KD) of 4.1 (equilibrium II). The observed increase in the distribution coefficient with increasing Ca in garnet is ln K_D= 1.3 + 2.5 × 10^?2 [Ca] where [Ca] = 100 Ca/(Mg + Fe²⁺+ Mn + Ca). The distribution coefficient is apparently unaffected by the presence of up to 12% spessartine in garnet. In several specimens of garnet-sillimanite-plagioclase gneiss, the Ca contents of garnet and of plagioclase increase in unison, as required by equilibrium (III). The mean pressure calculated from these data (n= 17) is 5.9 kbar, and the 95% confidence limits are ±0.5 kbar.     

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.     

Diffusion-controlled corona reaction and overstepping of equilibrium in a garnet granulite, Yenisey Ridge, Siberia

Diffusion modelling is applied to layered garnet–pyroxene–quartz coronas, formed by a pressure-induced reaction between plagioclase and primary pyroxene in a metabasic granulite. The reconstructed reaction involves some change in composition of reactant minerals. The distribution of minerals between layers is satisfactorily explained by diffusion-controlled reaction with local equilibrium, in which the diffusion coefficient for Al was smaller than those for Fe, Mg and Ca by a factor of approximately four. Diffusion of Mg towards plagioclase implies a chemical-potential gradient for MgO component in a direction opposite to the changing Mg content of garnet; this is explained by the influence of Al₂O₃ on the chemical potential of the pyrope end-member. Grain-boundary diffusion is suggested to have operated, possibly with composition gradients different from those in the bulk minerals. Chemical-potential differences across the corona are estimated from the variation in garnet composition, enabling affinity (the free energy change driving the reaction) to be estimated as 6.9±1.8  kJ per 24-oxygen mole of garnet produced. This implies that the pressure for equilibrium among the minerals was overstepped by 1.4±0.4  kbar. The probable P–T conditions of reaction were in the range 650–790  °C, 8–10  kbar. Assuming a timescale of reaction between 10⁶ and 10⁸ years, estimated diffusion coefficients for Fe, Mg and Ca are in the range 9×10⁻²³ to 5×10⁻²⁰ m² s⁻¹. These are consistent with experimental values in the literature for solid-state diffusion, including grain-boundary diffusion.     

Experimental investigation of the origin of majoritic garnet inclusions in diamonds

 Multianvil experiments were carried out at 10–15 GPa and 1600–1700 °C to match the compositions of majoritic garnet inclusions from diamonds, and to determine the compositions of other phases potentially coexisting with these inclusions in the source. Most experiments produced coexisting majoritic garnet, diopsidic clinopyroxene, one or more (Mg,Fe)₂SiO₄ polymorphs, and quenched carbonatic melt. The experimental garnets had relatively high Ca and Fe contents similar to the observed Ca and Fe contents of the inclusions. The resulting Si contents confirmed that the depth of origin of the inclusion with the highest Si content did not exceed 410 km, thus none of the majoritic garnet inclusions found so far originated in the transition zone (410–660 km). The evidence from inclusions and experiments is consistent with the presence of an eclogite layer occurring globally between 200 and 410 km. Compositional variations observed among more than 100 majoritic garnet inclusions with their Si content, which is a measure of pressure and depth, are consistent with the origin of the eclogite layer by crystal fractionation in a magma ocean. The compositions of olivine coexisting with majoritic garnet in the experimental products had the average Fe/(Fe + Mg) ratios between 0.16 and 0.28. Inclusions with such high Fe contents have not been found; the Fe/(Fe + Mg) ratio of the olivine inclusions in diamonds usually varies between 0.05 and 0.09. Hence, the mantle between 200 and 410 km may not contain olivine. In the absence of olivine, the discontinuity at 410 km is most likely a chemical boundary between the 200-km-thick eclogite layer and a more mafic transition zone. Received: 15 March 2001 / Accepted: 14 September 2001     

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.     

Ultrahigh-pressure garnet peridotites from the devolatilization of sea-floor hydrated ultramafic rocks

Garnet peridotites occur in quartzofeldspathic gneisses in the Northern Qaidam Mountains, western China. They are rich in Mg and Cr, with mineral compositions similar to those in mantle peridotites found in other orogenic belts and as xenoliths in kimberlite. Garnet‐bearing lherzolites interlayered with dunite display oriented ilmenite and chromite lamellae in olivine and pyroxene lamellae in garnet that have been interpreted to indicate pressures in excess of 6 GPa. However, some garnet porphyroblasts include hornblende, chlorite and spinel + orthopyroxene symplectite after garnet; some clinopyroxene porphyroblasts include abundant actinolite/edenite, calcite and lizardite in the lherzolite; some olivine porphyroblasts (Fo₉₂) include an earlier generation Mg‐rich olivine (Fo_95–99), F‐rich clinohumite, pyroxene, chromite, anthophyllite/cummingtonite, Cl‐rich lizardite, carbonates and a new type of brittle mica, here termed ‘Ca‐phlogopite’, in the associated dunite. The pyrope content of garnet increases from core to rim, reaching the pyrope content (72 mol.%) of garnet typically found in the xenoliths in kimberlite. The simplest interpretation of these observations is that the rock association was formerly mantle peridotite emplaced into the oceanic crust that was subjected to serpentinization by seawater‐derived fluids near the sea floor. Dehydration during subduction to 3.0–3.5 GPa and 700 °C transformed these serpentinites into garnet lherzolite and dunite, depending on their Al and Ca contents. Pseudosection modelling using thermocalc shows that dehydration of the serpentinites is progressive, and involved three stages for Al‐rich and two stages for Al‐poor serpentinites, corresponding to the breakdown of the key hydrous minerals. Static burial and exhumation make olivine a pressure vessel for the pre‐subduction mineral inclusions during ultrahigh‐pressure (UHP) metamorphism. The time span of the UHP event is constrained by the clear interface between the two generations of olivine to be very short, implying rapid subduction and exhumation.     

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.     

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。     

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.     

Geospeedometry of metamorphic rocks: examples in the Rantasalmi-Sulkava and Kiuruvesi areas, eastern Finland. Biotite–garnet diffusion couples

Compositional zoning in biotite–garnet pairs in metamorphic rocks from eastern Finland has been studied. The Mg profiles in the garnet side of biotite–garnet crystal pairs have been interpreted by means of Lasaga's theory (geospeedometry). However, the binary interdiffusion equations are first reformulated by starting from a ternary system and using the lattice fixed frame of reference. This frame of reference gives the fluxes directly by means of the numbers of diffusing ions, which helps to check the 1-dimensionality of the analysis assumed in Lasaga's theory. It is also shown that the recently argued effect of the third cation Ca is negligible in our samples. We were able to investigate satisfactory profiles in three samples from different areas. The values for the cooling rate are a few degrees per million years if the diffusion data obtained by Freer are adopted. The cooling rates are in agreement with recent estimates based on the K–Ar ages on biotite in the same areas.     

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.     

Effects of cation substitutions in garnet and pyroxene on equilibrium oxygen isotope fractionations

High-grade metamorphic rocks were used to explore oxygen isotope fractionations between pyroxene and garnet, and to investigate the effects on fractionation factors of the cation substitutions Fe³⁺Al_?1 and Ca(Fe,Mg)_?1. Recrystallized, granulite facies (725 °C) wollastonite ores from the northern Adirondack highlands contain essentially only the minerals clinopyroxene (a Di–Hd solid solution)+garnet (a Grs–Adr solid solution)±wollastonite, and exhibit a systematic dependence of measured fractionations on the Fe³⁺ content of calcic garnet: Δ(Cpx–CaGrt)=(0.14±0.12)+(0.78±0.20)X_Adr and Δ(Wo–CaGrt)=(0.15±0.22)+(0.57±0.33)X_Adr. In eclogites formed at T ≤650 °C, measured compositions of Ca-poor garnet and omphacite combined with experimental data indicate that Ca-poor, Fe-rich garnet is enriched in ¹⁸O compared to both diopside and grossular: extrapolating to 1000 K, Δ(Alm–Di)≈c. 0.2 and Δ(Alm–Grs)≈c. 0.5. Orthopyroxene and clinopyroxene from Gore Mountain, New York, show a constant fractionation that is independent of rock type, as expected if they have the same closure temperature. These data imply Δ(Opx-Cpx)≈c. 0.7 at 1000 K. Measured fractionations among Ca-poor garnet, orthopyroxene, clinopyroxene and hornblende in the Gore Mountain rocks further indicate an ¹⁸O enrichment in Ca-poor garnet over Grs (≈c. 0.5 at 1000 K). The new measurements are indistinguishable from expected equilibrium values based on experiments for the minerals enstatite, diopside, grossular, wollastonite and feldspar, but consistently indicate a significant isotope effect for the simple octahedral cation substitutions Fe³⁺Al_?1 (Grs vs. Adr) and Ca(Fe,Mg)_?1 (Ca-poor garnet vs. Grs; Opx vs. Cpx). Neither cation substitution has been directly investigated for its effect on ¹⁸O/¹⁶O fractionation with experiments in silicates. Chemical characterization of minerals is required prior to petrological interpretation of oxygen isotope trends.     

Zoning patterns in orthopyroxene and garnet in granulites: implications for geothermometry

Compositional maps of orthopyroxene and garnet of contrasting grain size and in contact with different minerals were made from two paragneiss granulites from the Minto terrane of northern Quebec. The compositional maps provide clear evidence of late exchange of Fe/(Fe + Mg) after Ca in garnet and Al in orthopyroxene had been quenched-in. The extent of late Fe-Mg exchange was controlled by neighbouring minerals, with negligible Fe-Mg gradients against plagioclase and quartz, and substantial gradients against exchangeable Fe-Mg minerals. Cores of grains in contact with exchangeable Fe-Mg neighbours are progressively more reset in Fe/(Fe + Mg) as grain size decreases, whereas cores of even small grains surrounded by only plagioclase and quartz are not significantly different in Fe/(Fe + Mg) than cores of the largest grains. Gradients of Ca in garnet and of Al in orthopyroxene in grains of uniform Fe/(Fe + Mg) preserve a high-temperature retrograde history during which intergranular exchange effected compositional uniformity of mineral rims and intragranular Fe-Mg diffusion in garnet and orthopyroxene was rapid enough to homogenize Fe/(Fe + Mg). The transition from efficient intergranular exchange at relatively high temperatures to local Fe-Mg exchange at lower temperatures may have been controlled by loss of an intergranular exchange medium in the rock, possibly an internally generated dehydration melt phase. Implications for geothermometry of granulites include the following (numerical values are particular to this study): (1) core compositions of garnet and orthopyroxene grains in contact with exchangeable neighbours may be reset in Fe/(Fe + Mg) relative to the most refractory compositions by an amount equivalent to 120d? C; (2) Fe-Mg exchange thermometry using even the most refractory Fe/(Fe + Mg) compositions may not record peak granulite conditions, possibly recording instead the temperature at which an intergranular exchange medium was lost from the rock; and (3) temperature-sensitive net transfer equilibria involving Al solubility in orthopyroxene yield temperatures up to 150d? C higher than maximum Fe-Mg exchange temperatures, even in grains with flat Fe/(Fe - Mg) compositional profiles, making them a better means of estimating peak granulite temperatures than Fe-Mg exchange thermometry.     

Some models for the rate of crystallization of garnet in metamorphic rocks

Information on the form of the equation for the rate of crystallization of garnet in metamorphic rocks may be obtained by combining an expression for the rate of crystal growth, obtained from data on compositional zoning, with an expression for the rate of nucleation, obtained from the crystal-size distribution.Three models for the rate of crystal growth and four for the rate of nucleation are formulated, and these, in different combinations, give rise to ten models for the rate of crystallization. Considerable variation in the form of the growth and nucleation equations produces a relatively small variation in the form of the equation for the rate of crystallization. In the favoured crystallization models, the volume of garnet produced in unit volume of rock is a function of time raised to the power m, where m lies between 3.5 and 5.     

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.     

Zoned minerals in garnet peridotite nodules from the Colorado Plateau: implications for mantle metasomatism and kinetics

Some garnet peridotite nodules from The Thumb, a minette neck on the Colorado Plateau in the southwestern United States, contain zoned minerals. Zoning does not exceed 1.5 wt.% for any oxide, but some relative changes are large: in one garnet TiO₂ and Cr₂O₃ ranges are 0.05–0.65 and 3.5–5.0 wt.%, respectively. In two porphyroclastic nodules, garnet rims are depleted in Mg and enriched in Fe, Ti, and Na compared to cores, and one garnet is irregularly zoned in Ti and Cr. Olivine crystals in these rocks are unzoned, and pyroxene zoning is slight, yet matrix olivine and pyroxene contain more Fe and Ti and less Mg and Cr than inclusions of these phases in garnet. In three coarse nodules, garnet rims are Ti-rich compared to cores, and Ca, Fe, Mg, and Cr zoning patterns are complex. Several nodules appear to have partially equilibrated near 1200° C and 35 kb, and under these conditions cation mobility in pyroxene was greater than in garnet. The zoning partly reflects Fe and Ti metasomatism in the mantle. Calculations indicate that Fe-Mg gradients in garnet could have persisted for only a short time in the mantle, perhaps thousands of years or less, so the metasomatism occurred shortly before eruption. The minette host, a likely source of the Fe and Ti, is rich in light rare earth elements: since the nodules are much poorer in these elements, little or no infiltrated minette was trapped in them. Diffusion is a possible mechanism for nodule metasomatism. Some fertile peridotite nodules from kimberlites may have been affected by similar events. Compositional differences between inclusions in garnet and matrix phases are intriguingly similar to some of the differences between most peridotite inclusions in diamonds and common lherzolite phases.