Thermodynamic and kinetic aspects of formation of bauxites

Experiments in which cleavage nepheline samples were reacted with aqueous solutions at fixed pH's and temperature were carried out in the laboratory. The chemistry of the solution as a function of time was monitored, as well as the chemistry of the nepheline surfaces.

At 25°C, Al derived from the nepheline stays in solution due to slow precipitation kinetics of Al(OH)₃. At 60° and 80°C, precipitation of Al(OH)₃ is so rapid that Al concentration in solution is below 0.05 ppm. This indicates that precipitation kinetics favour the formation of bauxite deposits in tropical regions (i.e. T25°C), but not in temperate regions.

Precipitation products on the surface of the nepheline fragments at 60° and 80°C depend on the pH. At pH 3.0, an amorphous aluminium silicate (proto-kaolinite?) is formed. At pH>7.0, the precipitated phase contains, in addition to Al and Si, high amounts of Na and K (proto-muscovite?). The optimum pH for the formation of bauxite is in the range 5–7. These results are in agreement with thermodynamic calculations.     

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.     

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.     

Compositional zoning in garnet and kinetics of metamorphic crystallization

The kinetics of zoned garnet porphyroblast growth is exemplified in a sample of garnet-staurolite-biotite schist from the northern Ladoga region. The diffusion-controlled porphyroblast growth was accompanied by a decrease in the kinetic coefficient during phase reactions. Even at insignificant (1–2°C) thermal overstepping, the leading role of diffusion as a factor that controls kinetics of porphyroblast growth in medium-grade metapelites is consistent with the parameters of metamorphic crystallization: T = 500–650°C, t = 1 Ma; D _A1 ^app = 10^?14 cm²/s, L = 0.2–0.6 cm, r = 1–3 mm, ΔC _Al = 1.5 × 10^?4–1.5 × 10^?3 mol/cm³.     

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.     

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.     

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.     

Modeling of retrograde diffusion zoning in garnet: evidence for slow cooling of granulites from the Highland Complex of Sri Lanka

Summary ?Diffusion modeling of zoning profiles in garnet rims from mafic granulites is used to estimate cooling rates in the Proterozoic basement of Sri Lanka, which represents a small, but important fragment of the Gondwana super-continent. Metamorphic peak temperatures and pressures, estimated with two-pyroxene thermometry and garnet–clinopyroxene–plagioclase–quartz (GADS) barometry, yield 875±20 °C and 9.0±0.1 kbar. These peak metamorphic conditions are slightly higher than results obtained by garnet-biotite Fe–Mg exchange thermometry of 820±20 °C. Reset flat zoning profiles were observed in most garnets. Only narrow garnet rims touching biotite exhibit retrograde zoning in terms of Fe and Mg exchange. The garnet zoning observed requires a slow cooling history. Equilibrium was achieved along grain boundaries during or close to peak metamorphism. During subsequent cooling to lower temperatures, only local exchange between garnet and biotite occurred. A cooling rate of 1–5 °C/Ma is estimated. The estimated temperature-time history from garnet profiles is in good agreement with the cooling history inferred from mineral radiogenic ages in the literature. Received December 11, 2001; revised version accepted August 28, 2002     

Thermodynamic modelling of diffusion-controlled garnet growth

Numerical thermodynamic modelling of mineral composition and modes for specified pressure-temperature paths reveals the strong influence of fractional garnet crystallisation, as well as water fractionation, on garnet growth histories in high pressure rocks. Disequilibrium element incorporation in garnet due to the development of chemical inhomogeneities around porphyroblasts leads to pronounced episodic growth and may even cause growth interruptions. Discontinuous growth, together with pressure- and temperature-dependent changes in garnet chemistry, cause zonation patterns that are indicative of different degrees of disequilibrium element incorporation. Chemical inhomogeneities in the matrix surrounding garnet porphyroblasts strongly affect garnet growth and lead to compositional discontinuities and steep compositional gradients in the garnet zonation pattern. Further, intergranular diffusion-controlled calcium incorporation can lead to a characteristic rise in grossular and spessartine contents at lower metamorphic conditions. The observation that garnet zonation patterns diagnostic of large and small fractionation effects coexist within the same sample suggests that garnet growth is often controlled by small-scale variations in the bulk rock chemistry. Therefore, the spatial distribution of garnet grains and their zonation patterns, together with numerical growth models of garnet zonation patterns, yield information about the processes limiting garnet growth. These processes include intercrystalline element transport and dissolution of pre-existing grains. Discontinuities in garnet growth induced by limited element supply can mask traces of the thermobarometric history of the rock. Therefore, thermodynamic modelling that considers fractional disequilibrium crystallisation is required to interpret compositional garnet zonation in terms of a quantitative pressure and temperature path of the host rock.     

Thermodynamic analysis of garnet growth zoning in eclogite facies granodiorite from M. Mucrone, Sesia Zone, Western Italian Alps

Samples of the metagranodiorite from M.  Mucrone (Sesia zone, Western Alps) show pseudomorphic and coronitic textures where the igneous minerals were partially replaced by high-pressure metamorphic assemblages. The original magmatic paragenesis consisted of quartz, plagioclase, K-feldspar, biotite and minor phases. During the eclogitic event the original plagioclase was fully replaced by zoisite, jadeite and quartz ± K-feldspar pseudomorphic symplectites and the biotite was in part replaced by phengitic mica. Moreover, a composite corona often developed around the biotite. This corona consists of a layer of phengite I and garnet and, where the igneous biotite and feldspars were in contact, of an outer layer of phengite II intergrown with quartz. Biotite, phengite and K-feldspar are homogeneous while garnet shows a strong composition zoning recording the kinetics of the metamorphic reactions. A numerical simulation of the observed garnet zoning is performed assuming that intercrystalline diffusion and plagioclase resorption were the slowest rate-determining processes during the prograde P-T path. The metamorphic paragenesis constrains the P-T path chosen in the simulation. The comparison between measured and calculated garnet zoning permits evaluation of the relative weights of interface kinetics, grain-boundary and lattice diffusion. Received: 26 November 1997 / Accepted: 6 August 1999     

Thermodynamic properties of almandine-grossular garnet solid solutions

The mixing properties of Fe₃Al₂Si₃O₁₂-Ca₃Al₂Si₃O₁₂ garnet solid solutions have been studied in the temperature range 850–1100° C. The experimental method involves measuring the composition of garnet in equilibrium with an assemblage in which the activity of the Ca₃Al₂Si₃O₁₂ component is fixed. Experiments on the assemblage garnet solid solution, anorthite, Al₂SiO₅ polymorph and quartz at known pressure and temperature fix the activity of the Ca₃Al₂Si₃O₁₂ component through the equilibrium: 1 $$\begin{gathered} {\text{3CaAl}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{8}} \rightleftarrows {\text{Ca}}_{\text{3}} {\text{Al}}_{\text{2}} {\text{Si}}_{\text{3}} {\text{O}}_{{\text{12}}} \hfill \\ {\text{Anorthite garnet}} \hfill \\ {\text{ + 2Al}}_{\text{2}} {\text{SiO}}_{\text{5}} {\text{ + SiO}}_{\text{2}} \hfill \\ {\text{ sillimanite/kyanite quartz}}{\text{.}} \hfill \\ \end{gathered}$$ This equilibrium, with either sillimanite or kyanite as the aluminosilicate mineral, was used to control \({\text{a}}_{{\text{Ca}}_{\text{3}} {\text{Al}}_{\text{2}} {\text{Si}}_{\text{3}} {\text{O}}_{{\text{12}}} }^{{\text{gt}}} \) . The compositions of the garnet solutions produced were determined by measurement of their unit cell edges. At 1 bar Fe₃Al₂Si₃O₁₂-Ca₃Al₂Si₃O₁₂ garnets exhibit negative deviations from ideality at the Fe-rich end of the series and positive deviations at the calcium end. With increasing pressure the activity coefficients for the Ca₃Al₂Si₃O₁₂ component increase because the partial molar volume of this component is greater than the molar volume of pure grossular. Previous studies indicate that the activity coefficients for the Ca₃Al₂Si₃O₁₂ component also increase with increasing (Mg/Mg+Fe) ratio of the garnet. The region of negative deviation from ideality implies a tendency towards formation of a stable Fe-Ca garnet component. Evidence in support of this conclusion has been found in a natural Fe-rich garnet which was found to contain two different garnet phases of distinctly different compositions.     

Vertical zoning of oil and gas formation: historico-genetic aspects

Considerable variations in depth zoning of dispersed organic matter (DOM) catagenesis are caused by various physical and geological factors. The evolution of a sedimentary basin (SB) implies successive changes in organization levels of this system. In the process of evolution the system structure is determined by the interaction of its subsystems. Any parameter of an SB (physical properties of rocks, degree of OM catagenesis, temperature, formation pressure, phase ratio of hydrocarbons) is governed by the processes running in the system. Variations of these parameters in space and time characterize the structure of the changing system. The intensity of lithification of terrigenous rocks, OM catagenesis, and HC generation in time is approximated by a curvilinear relation, which becomes asympthotic at a particular stage. In other words, these processes drastically decay 150 ± 50 Myr after the main sedimentation had completed. For an SB system with a natural set of main subsystems (mineral, water, organic, hydrocarbon), the age is less important (at least throughout the Phanerozoic) than the duration of the process. Analysis is given to the formation of vertical HC zoning, which includes all the processes observable within an SB. The relationship of events and qualitative temporal and spatial changes during these processes is considered.     

Two zoning patterns in tin deposits

Two zoning patterns in tin deposits are proposed according to geochemical environments.

1. Acidic zoning pattern is characteristic of tin deposits associated with sialic rocks and tin-bearing veins in carbonate rocks. Six zones may be recognized from the granite mass outwards: (1) Nb?Ta?(Li?Be?Mo), (2) Sn, (3) W?(Sn), (4) Cu?Pb?Zn?(Bi), (5) Sb?Hg, and (6) Au?Ag. This kind of zoning is related with the temperature difference involved in the deposition of various ore minerals in an acidic (or neutral) geochemical enviroment. From the granite outwards, the temperature decreases gradually with increasing distance from the heat source.
2. Alkaline zoning pattern is typical of tin deposits occurring in calcareous and magnesian carbonate rocks. Three zones can be recognized from the granite mass outwards: (1) Cu?Zn?Bi, (2) Sn, and (3) Fe?Pb?Zn?Cu. A calcium-and magnesium-rich alkaline environment is responsible for this zoning pattern. In this case the normal sequence of mineral formation will be greatly changed owing to neutralization when an acidic ore-forming solution enters the alkaline environment.

Zoning structure in tin deposits is very complex and highly variable, depending on: (1) the geochemical environment in which the deposits are formed, (2) the type of shield beds, and (3) the character of ore-forming solutions. However, there are some known examples showing similar zoning patterns for the deposits that are similar in these three aspects.     

Kinetic aspects of sector zoning in arsenopyrite: A case study

Summary A simple quartz-arsenopyrite vein assemblage formed at temperatures of 280–200°C occurs in the Madan lead-zinc ore district, Bulgaria. Spear-shaped arsenopyrite is bounded by {101}, {010} and {210}; compositionally it is pure FeAs_1-xS_1+X of variable x. The BSE image of an oriented (001) section reveals a pronounced sector zoning defined solely by differences in the S/As ratio. The boundary between the (210) and (010) growth sectors reflects the changes of their growth rates V⁰¹⁰ and V²¹⁰ in perfect correlation with zonal S/As oscillations. The V°10/V²¹⁰ ratios determined in 20 zones range from 0.1 to 2.4, and correspond to S variations from 39 to 34 at.% derived from 7 microprobe point analyses. The S content in the (010) sector is on average 1.5 at.% lower than in the (210) one, the difference decreasing from about 2.5 to less than 0.33 at.% with the decreasing V⁰¹⁰/V²¹⁰. The rate/composition relationship obeys the following rules: the higher the S/As the lower the V⁰¹⁰/V²¹⁰, and the slower the (010) growth. The phenomenon is interpreted in terms of crystal growth theory of a solid solution analyzing the arsenopyrite growth history on hand specimen, microscopic and structural scales. Sector zoning in this particular case is explained by processes taking place very close to the growing crystal surface which are superimposed on those produced by larger-scale variations in the hydrothermal environment.

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Kinetische Aspekte des sektoriellen Zonenbaues von Arsenkies: Untersuchung eines Wachstumsphdnomens

Zusammenfassung Eine gewöhnliche Quarz-Arsenkies Paragenese im Blei-Zink Erzgebiet von Madan, Bulgarien, bildete sich im Temperatur-Intervall von 280-200°C. Speerförmiger Arsenkies ist begrenzt von den Flächenformen 11011, {010} und {210}, wobei das Mineral der Zusammensetzung FeAs_1-xS_1+X mit variierendem x entspricht. Die Rückstreuelektronenabbildung eines (001)-orientierten Querschnittes zeigt einen deutlichen Sektorzon-enbau, der ausschließlich durch Unterschiede im S/As-Verhaltnis bestimmt wird. Die Grenze zwischen den Wachstumssektoren (210) und (010) spiegelt Veränderungen in ihren Wachstumsgeschwindigkeiten V⁰¹⁰ und V²¹⁰ wieder, die mit den zonenkorrelierten S/As Schwankungen variieren. Die Verhdltnisse V⁰¹⁰/V^21O wurden in 20 Zonen des Kristalls bestimmt; she variieren zwischen 0.1 und 2.4 und entsprechen einer Variation von 39 bis 34 At.% S, die durch 7 Elektronenstrahlmikrosondenanalysen bestimmt wurden. Der S-Gehalt im Sektor (010) ist durchschnittlich mit 1.5 At.% niedriger als im Sektor (210); der entsprechende Unterschied nimmt von ungefdhr 2.5 bis 0.33 At.% mit der Verringerung von V⁰¹⁰/V² ab. Die Beziehung Wachstumsgeschwindigkeit/ Element unterliegt der Regel: je hoher das Verhaltnis S/As; desto niedriger ist V⁰¹⁰/V²¹⁰ und desto langsamer ist das Wachstum von (010). Diese Erscheinung wird im Rahmen der Kristallwachstumstheorie einer festen Lösung gedeutet, wobei die Wachstumsgeschichte des Arsenkieses makroskopisch, mikroskopisch und strukturell analysiert wurde. Auf these Weise wird der Sektorzonenbau als ein Resultat von Prozessen interpretiert, die ganz nah der wachsenden Kristalloberfldche ablaufen und die die Veränderungen des hydrothermalen Milieus überlagern.

     

Statistical microanalysis applied to garnet growth zoning and to cordierite fluid content

An analytical study to evaluate quantitatively weak zoning of a garnet from a high-grade kinzigite has been performed with an electron microprobe. The technique consists of the reconstruction of a profile step-by-step by successive analyses performed during relatively long counting times (30 s), along a radial profile of 2,500 μm length. The successive analytical data along this profile are statistically treated by Fisher's test and compared with the χ² values (Pearson's law). These statistical tests were applied to assess microprobe stability and analysis homogeneity, and as a consequence to assure high credibility of the radial variations of the garnet. From core to rim, and for each element, zoning appears as the radial juxtaposition of stationary Poissonian samples. These samples being associated, the garnet appears to be constituted of successive concentric domains with stationary compositions. Different substitutions between Mg, Fe, Mn and Ca are evidenced. Such an analytical approach to chemical zoning can be useful for understanding growth mechanisms, and the possible diffusion reactions with the environment at each growth step. In addition, such a procedure can be used to evaluate accurately the fluid content of cordierite, and to appreciate the nature of the fluids concerned. As an example, the fluid content of a cordierite from a similar high-grade kinzigite has been evaluated.     

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.     

高压-超高压变质岩石中石榴石的环带和成因

在俯冲带变质过程中,石榴石是高压-超高压变质榴辉岩和片麻岩的常见变质矿物。由于石榴石具有难熔和流体中的低溶解能力的特点,通常可以很好地保存下来,并且能够保留复杂的化学成分环带,以及不同类型的矿物或流体包裹体,为解释石榴石寄主岩石经历的变质演化历史提供了重要信息。石榴子石的主微量元素成分受控于很多因素,如全岩成分、变质的温压条件、控制石榴子石形成的相关变质反应、与石榴子石共生的矿物种类和成分等。因此,在利用石榴石探讨超高压变质的演化历史时,对石榴石进行系统的主要元素、微量元素、氧同位素以及矿物包裹体分析,以及相互间的成因关系。同时,对石榴石中的锆石或独居石包裹体并进行原位U-Pb定年和微量元素分析,可以为变质石榴石的形成时代提供直接的时间制约。深入研究超高压变质岩中石榴石的生长阶段,不仅可以为含石榴石寄主岩石的变质过程提供岩石学和地球化学证据,而且对于理解石榴石的形成机制、生长规律及其变质化学动力学过程具有重要的科学意义。     

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

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

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

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