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.     

The role of the grain boundary at chemical and isotopic fronts in marble during contact metamorphism

Carbon and oxygen isotopic profiles around a low pressure metasomatic wollastonite reaction front in a marble of the Hida metamorphic terrain, central Japan, display typical metamorphic fluid-enhanced isotopic zonations. Isotopic profiles obtained from detailed microscale analyses perpendicular to the chemical reaction front in calcite marble show that diffusion-enhanced isotopic exchange may control these profiles. Carbon and oxygen isotopic behaviour in grain boundaries is remarkably different. Oxygen isotopic troughs (¹⁸O depleted rims) around the calcite-grain boundaries are widely observed in this contact aureole, demonstrating that diffusion of oxygen in calcite grain boundary dominates over lattice diffusion in calcite. In contrast, no difference is observed in carbon isotopic profiles obtained from grain cores and rims. There is thus no specific role of the grain boundary for diffusion of carbonic species in the metamorphic fluid during transportation. Carbon chemical species such as CO₂ and CO₃ ions in metamorphic fluid migrate mainly through lattice diffusion. The carbon and oxygen isotope profiles may be modelled by diffusion into a semi-infinite medium. Empirically lattice diffusion of oxygen isotopes is almost six times faster than that of carbon isotopes, and oxygen grain-boundary diffusion is ten times faster than oxygen lattice diffusion. Oxygen isotopic results around the wollastonite vein indicate that migration of the metamorphic fluid into calcite marble was small and was parallel to the aquifer. From the stability of wollastonite and the attainment of oxygen isotopic equilibrium, we suggest that diffusion of oxygen occurred through an aqueous fluid phase. The timescale of formation of the oxygen isotopic profile around the wollastonite vein is calculated to be about 0.76 × 10⁶ years using the experimentally determined diffusion constant. Received: 14 January 1997 / Accepted: 23 April 1998     

Local mineral equilibrium in metamorphism: development of D. Korzhinskii’s ideas (on 110th anniversary of D.S. Korzhinskii)

In 1950, D. Korzhinskii hypothesized that minerals in metamorphic reactions can be in local equilibrium. Proceeding from this idea, G. Fisher and R. Joesten later developed a realistic model of metamorphism kinetics. The model included diffusive mass transport in intergranular fluid controlled by the concentrations of components and chemical potential gradients, local-equilibrium reactions between minerals and pore fluid, mass balance of components, etc. The Korzhinskii–Fisher–Joesten model can provide clues to the duration of metamorphic events as inferred from mineral chemistry, free energy of phases, and rock textures and structures. The respective modeling of metamorphic reactions, with regard to spatial distribution of mineral grains, has implications for the transport and balance of chemical components. The balance of components (except volatiles) is restricted to domains of hundredth fractions of a cubic millimeter to several cubic meters. This may be the minimum size of an elementary domain in which minerals are in local equilibrium.     

矿物之间的元素和同位素平衡:地质测温和等时线定年的热力学和动力学控制

在特定的地质事件过程中,矿物等时线放射体系是否达到并且保持了平衡是变质岩Sm-Nd和Rb-Sr同位素年代学中的一个重要问题。在这个问题上矿物对O同位素测温与矿物等时线定年相似,因此两者之间可以相互制约。在岩浆岩和变质岩中,矿物中Sm-Nd、Sr和O之间的扩散速率在无水的条件下一般具有可比性,因此矿物之间O同位素的平衡状态可以用来对Sm-Nd和Rb-Sr定年的有效性进行检验。对大别-苏鲁造山带超高压变质岩的Sm-Nd和Rb-Sr等时线矿物进行O同位素测温,得到Sm-Nd等时线有时给出三叠纪年龄,有时给出非三叠纪年龄;对应的矿物O同位素分馏分别处于平衡和不平衡状态。对于引起非三叠纪等时线年龄的原因,一方面可以是由于榴辉岩相变质过程中同位素体系没有达到平衡,另一方面则可能角闪岩相退变质作用打破了平衡。等时线矿物中初始同位素比值的均一化速率主要受慢扩散矿物的影响,而矿物等时线时钟的启动主要受高母/子比值矿物控制。因此在变质作用过程中,只有当高母/子比值矿物同时具有快的放射成因同位素扩散速率,才可能得到有效的矿物等时线来用于变质年龄的测定。根据不同矿物中不同元素在扩散速率上的差异,能够定量估计大陆碰撞过程中榴辉岩相变质的持续时间。应用增量方法和离子孔隙度经验模型,不仅分别能够从理论上准确计算所有固体矿物的氧同位素分馏系数和获得不同矿物中元素的扩散参数,而且分别能够定量预测热力学平衡条件下共生矿物之间的¹⁸O富集顺序和相同条件下矿物中元素扩散速率的相对快慢。     

Oxygen isotope exchange and disequilibrium between calcite and tremolite in the absence and presence of an experimental C–O–H fluid

Oxygen isotope exchange between minerals during metamorphism can occur in either the presence or the absence of aqueous fluids. Oxygen isotope partitioning among minerals and fluid is governed by both chemical and isotopic equilibria during these processes, which progress by intragranular and intergranular diffusion as well as by surface reactions. We have carried out isotope exchange experiments in two- and three-phase systems, respectively, between calcite and tremolite at high temperatures and pressures. The two-phase system experiments were conducted without fluid either at 1 GPa and 680 °C for 7 days or at 500 MPa and 560 °C for 20 days. Extrapolated equilibrium fractionations between calcite and tremolite are significantly lower than existing empirical estimates and experimental determinations in the presence of small amounts of fluid, but closely match calculated fractionations by means of the increment method for framework oxygen in tremolite. The small fractionations measured in the direct calcite–tremolite exchange experiments are interpreted by different rates of oxygen isotope exchange between hydroxyl oxygen, framework oxygen and calcite during the solid–solid reactions where significant recrystallization occurs. The three-phase system experiments were accomplished in the presence of a large amount of fluid (CO₂+H₂O) at 500 MPa and 560 °C under conditions of phase equilibrium for 5, 10, 20, 40, 80, 120, 160, and 200 days. The results show that oxygen isotope exchange between minerals and fluid proceeds in two stages: first, through a mechanism of dissolution-recrystallization and very rapidly; second, through a mechanism of diffusion and very slowly. Synthetic calcite shows a greater rate of isotopic exchange with fluid than natural calcite in the first stage. The rate of oxygen diffusion in calcite is approximately equal to or slightly greater than that in tremolite in the second stage. A calculation using available diffusion coefficients for calcite suggests that grain boundary diffusion, rather than volume diffusion, has been the dominant mechanism of oxygen transport between the fluid and the mineral grains in the later stage.Editorial responsibility: T.L. Grove     

http://www.sciencedirect.com/science/article/pii/S1674987114000395

The study of fluid inclusions in high-grade rocks is especially challenging as the host minerals have been normally subjected to deformation, recrystallization and fluid-rock interaction so that primary in- clusions, formed at the peak of metamorphism are rare. The larger part of the fluid inclusions found in metamorphic minerals is typically modified during uplift. These late processes may strongly disguise the characteristics of the ＂original＂ peak metamorphic fluid. A detailed microstructural analysis of the host minerals, notably quartz, is therefore indispensable for a proper interpretation of fluid inclusions. Cathodoluminescence （CL） techniques combined with trace element analysis of quartz （EPMA, LA- [CPMS） have shown to be very helpful in deciphering the rock-fluid evolution. Whereas high-grade metamorphic quartz may have relatively high contents of trace elements like Ti and A1, low- temperature re-equilibrated quartz typically shows reduced trace element concentrations. The result- ing microstructures in CL can be basically distinguished in diffusion patterns （along microfractures and grain boundaries）, and secondary quartz formed by dissolution-reprecipitation. Most of these textures are formed during retrograde fluid-controlled processes between ca. 220 and 500 ℃, i.e. the range of semi-brittle deformation （greenschist-facies） and can be correlated with the fluid inclusions. In this way modified and re-trapped fluids can be identified, even when there are no optical features observed under the microscope.     

俯冲带中水流体的化学性质研究进展

俯冲带中的水在壳幔演化和物质交换中起重要作用。本文就俯冲带中水的物理化学性质、溶液中的离子缔合、混溶、主量元素与微量元素组成等方面进行了阐述。重点剖析:1)超临界态下温度压力条件的改变导致水微观结构与性质的变化,扩散系数、粘度等性质随之改变,进而对水岩反应产生影响;2)富水流体中离子缔合影响着金属配合物数量,很大程度制约流体中矿物的溶解行为;3)低Cl流体中微量元素配分模式与岛弧玄武岩类似,意味着富水贫氯碱性硅酸盐成分的流体在地幔楔元素运移中起关键作用。并展望了俯冲带中流体化学性质研究的新手段。     

Isotopic disequilibrium in ultrahigh-pressure and retrograde metamorphism of eclogite and gneiss from the Chinese Continental Scientific Drilling in the Sulu orogen, China: evidence from mineral Nd–Sr–O isotopic composition

Diffusion rates of Sr and O in minerals are often comparable while Nd has a lower diffusion rate during thermal overprint(s); thus, the O isotope systems between metamorphic minerals can serve as an indicator to evaluate whether equilibrium of Rb–Sr and Sm–Nd systems has been preserved in the metamorphic minerals that experienced retrograde metamorphism. This study presents a combination of investigation on Sm–Nd, Rb–Sr, and O isotopic compositions of minerals separated from ultrahigh-pressure eclogite and gneiss that were collected from the main hole of the Chinese Continental Scientific Drilling project located in the Sulu orogen, eastern China. Oxygen isotopic compositions of minerals from gneiss and eclogite yield two temperature groups of 620–740 and 460–590°C, representing diffusion cessation of isotopic exchange during the eclogite-facies recrystallization and later amphibolite-facies retrograde overprint. Rb–Sr mineral regressions of two eclogite samples give consistent Triassic ages of 244 Ma, corresponding to eclogite-facies metamorphism, while the same minerals do not yield meaningful Sm–Nd isochron ages. This phenomenon likely suggests that Rb–Sr isotopic equilibrium was achieved during eclogite-facies metamorphism and preserved during late amphibolite-facies retrogression. In contrast, Sm–Nd isotopic equilibrium between the minerals of eclogite was not achieved under UHP metamorphic conditions. Regressions of epidote and biotite of one gneiss sample give a Triassic Sm–Nd age of 243 ± 34 Ma, corresponding to the time of the eclogite-facies metamorphism, and a Jurassic mineral Rb–Sr age of 187.5 ± 1.8 Ma. These results imply that fluids have played an important role to achievement of the Sm–Nd isotopic equilibrium during eclogite-facies metamorphism and re-equilibration of the Rb–Sr isotopic system during later retrograde overprint.     

Dependence of reaction kinetics on H2O activity as inferred from rates of intergranular diffusion of aluminium

Quantitative constraints on the accelerative effects of H₂O on the kinetics of metamorphic reactions arise from a comparison of rates of intergranular diffusion of Al in natural systems that are fluid‐saturated, hydrous but fluid‐undersaturated, and nearly anhydrous. Widths of symplectitic reaction coronas around partially resorbed garnet crystals in the contact aureole of the Makhavinekh Lake Pluton, northern Labrador, combined with time–temperature histories from conductive thermal models, yield intergranular diffusivities for Al from ～700–900 °C under nearly anhydrous conditions. Those rates, when extrapolated down temperature, are approximately three orders of magnitude slower than rates derived from re‐analysis of garnet resorption coronas formed under hydrous but fluid‐undersaturated conditions near 575 °C in rocks of the Llano Uplift of central Texas, which are in turn approximately four orders of magnitude slower than rates at comparable temperatures derived from numerical simulations of prograde garnet growth in fluid‐saturated conditions in rocks from the Picuris Range of north‐central New Mexico. Thus, even at constant temperature, rates of intergranular diffusion of Al – and corresponding length scales and timescales of metamorphic reaction and equilibration – may vary by as much as seven orders of magnitude across the range of H₂O activities found in nature.     

地质速率计—矿物氧扩散的应用

概述了同位素封闭体系内的矿物氧扩散和同位素交换机制及其在地质速率计上的应用。火成岩从高温冷却或变质岩从高峰主质温度冷却过程中，由于冷却速度不同，扩散作用导致的矿物晶体内部及晶粒间氧同位素再平衡也有所不同。通过实测岩石中各组成矿物氧同位素比值，模式含量和颗粒半径，据矿物氧扩散和同位素交换模型，可以估算出岩石的冷却速率。     

Compositional changes of minerals associated with dynamic recrystallizatin

The rate of compositional and isotopic exchange between minerals may be enhanced significantly if the rock is deformed simultaneously. The enhanced exchange rate may result from a reduction in grain size (shorter distance for volume diffusion), dissolution and growth of grains by diffusion creep (pressure solution), or the movement of high-angle grain boundaries through strained grains during recrystallization in the dislocation creep regime. The migration of high-angle grain boundaries provides high diffusivity paths for the rapid exchange of components during recrystallization. The operation of the latter process has been demonstrated by deforming aggregates consisting of two plagioclases (An₁ and An₇₉) at 900°C, 1 GPa confining pressure, and a strain rate of ∼2x10^-6s^-1. The polygonal, recrystallized grains were analyzed using an analytical transmission electron microscope and have a variable but often intermediate composition. At the conditions of these experiments, the volume interdiffusion rate of NaSi/CaAl is too slow to produce any observable chemical change, and microstructural-chemical relations indicate that the contribution from diffusion creep was insignificant except for initially fine-grained (2–10 μm) aggregates. These results indicate that strain-induced recrystallization can be an effective mechanism for enhancing the kinetics of metamorphic reactions and for resetting the isotope systematics of minerals such as feldspars, pyroxenes, and amphiboles.     

Calculated phase equilibria involving chemical potentials to investigate the textural evolution of metamorphic rocks

Evolving pressure–temperature conditions during metamorphism drive changes in the stable mineral assemblage, mineral proportions and mineral compositions in rocks. These changes are achieved via the diffusion of components between minerals, fluid and melt, the driving force for diffusion being the gradients in chemical potential of the components developed spatially within the rock. This study utilises recent developments in the software thermocalc to investigate quantitatively chemical potential relationships in rocks, with the phases involved being (solid) solutions. Phase diagrams with chemical potentials as axes are used to understand better the spatial rearrangement of components during the metamorphic evolution of rocks and the metamorphic textures that result. In contrast to qualitative chemical potential diagrams, quantitative diagrams can be contoured for mineral composition, allowing consideration of chemical zoning in minerals. Furthermore, the amount of material required to diffuse to equalise chemical potentials can be calculated. We start by demonstrating the approach via an example of retrograde corona development in an ultra-high-temperature granulite. Whereas the use of chemical potentials to consider the retrograde development of corona textures is well known, they are also significant in considering the prograde history. The role of chemical potentials in prograde metamorphic textural evolution is highlighted in consideration of the consumption and growth of aluminosilicates during the kyanite-to-sillimanite reaction, and the growth of garnet porphyroblasts.     

Experimental hydrogen isotope studies III: Diffusion of hydrogen in hydrous minerals,and stable isotope exchange in metamorphic rocks

Diffusion parameters for hydrogen diffusion in epidote-group minerals and micas have been measured under hydrothermal conditions, or calculated from existing experimental data, for bulk hydrogen isotope exchange experiments between hydrous minerals and water. Activation energies in the range 14 to 31 kcals/g-atom H are comparable to those derived by application of kinetic theory to experimental hydrogen isotope exchange data, and to those for oxygen diffusion in minerals under hydrothermal conditions. Diffusion of hydrogen in epidote is about four orders of magnitude faster than in muscovite, and about two orders of magnitude faster than in zoisite. Hydrogen diffusion in micas is about five orders of magnitude faster than oxygen diffusion, and hydrogen transport occurs dominantly parallel to the layers rather than parallel to the c-axis as for oxygen.Rapid hydrogen transport in minerals may proceed by hydrolysis of Si-O and Al-O bonds, followed by exchange of hydrolyzed oxygens with slower-diffusing (OH) or H₂O. Water appears to be essential for stable isotope exchange between minerals in slowly cooling metamorphic rocks.Stable isotope data for regional metamorphic mineral assemblages suggests that water is usually present in small amounts during cooling of prograde regional metamorphic systems, and estimated closure temperatures for cessation of stable isotope exchange are often more comparable to those calculated from diffusion data than to likely temperatures of metamorphism.Alpine deformation of the Hercynian Monte Rose Granite (Frey et al. 1976) permitted access of water and initiated stable isotope exchange amongst coexisting minerals. The diffusional behaviour of species in relict Hercynian muscovites is consistent with available experimental diffusion data.     

Oxygen and hydrogen isotope study of minerals from metapelitic rocks, staurolite to sillimanite zones, Mica Creek, British Columbia

Abstract Oxygen and hydrogen isotope analyses have been made of coexisting quartz, ilmenite, muscovite, and biotite from Late Precambrian metapelitic rocks, staurolite-kyanite to K-feldspar-muscovite-sillimanite zones, from Mica Creek, British Columbia. The δ¹⁸O and †D values of these minerals are generally uniform and do not decrease significantly with increasing metamorphic grade. This implies that there has not been significant infiltration of deep crustal, possibly magmatic, fluids into the metapelites that has been suggested for other high-grade metamorphic terranes. The uniformity of oxygen isotope compositions of the Mica Creek metapelite rocks may reflect isotopic uniformity in the sedimentary protolith rather than widespread exchange with an isotopically homogeneous metamorphic pore fluid.
Temperature estimates based upon ¹⁸O exchange thermometry for samples below the sillimanite zone are in reasonable agreement with the results of garnet-biotite Fe–Mg exchange thermometry. In the higher grade rocks, the oxygen isotope and garnet-biotite thermometry yield results which disagree by about 100°C. The highest temperatures recorded by oxygen isotope thermometry, 595°C, are at least 60°C below the minimum temperatures required by phase equilibria. These discrepancies appear to result from pervasive equilibrium retrograde exchange of oxygen isotopes between coexisting minerals. In addition, there are problems with calibration of garnet-biotite thermometry at higher temperatures. Retrograde oxygen isotope exchange may be a general characteristic of high-grade metamorphic rocks and oxygen isotope thermometry may not usually record peak metamorphic temperatures if they significantly exceed 600°C.     

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

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

区域变质作用中的流体

区域变质条件下流体的流动有 4种标志 :( 1)细脉 ;( 2 )岩石学 ;( 3 )稳定同位素 ;( 4 )常量元素的交代作用。不同级别的区域变质作用中 ,流体影响着岩石的变质反应和变形 ;在高级变质的情况下甚至有熔体出现。在超高压变质条件下 ,流体量比地壳范围区域变质要少得多 ,从大别山超高压变质带的资料可知 ,流体的演化有明显的阶段性 ,局部曾发现熔融包裹体。水流体的介入 ,引起岩石的退变质和元素地球化学变异 ,是超高压变质岩抬升、进入中下地壳的产物。新近的实验岩石学成果说明 ,多硅白云母、角闪石等含羟基的矿物 ,在俯冲达 10 0km以下依然稳定 ,而一些花岗岩体系在超高压的条件下产生的超临界流体 ,乃是花岗岩、片麻岩只能部分保留超高压矿物组合的原因。     

Oxygen isotope fractionation and disequilibrium displayed by some granulite facies rocks from the Fraser Range,Western Australia

The granulites of the Fraser Range are assumed to have formed in a carbon-rich fluid, and are generally devoid of hornblende, and lack obvious hydrous retrograde features. In these granulites, pyroxene, garnet, plagioclase and quartz are the minerals most likely to retain the oxygen isotope ratios fixed at an early stage of initial granulite metamorphism. Temperature estimates using these minerals commonly suggest that oxygen isotopic exchange ceased in the range 600 to 680°C. The peak metamorphic temperature was probably ～ 850°C as based on the stability fields of the coexisting minerals and some cation temperatures from coexisting pyroxenes in these rocks. Ilmenite may be slightly out of isotopic equilibrium with the other minerals. Thus, grains of quartz, feldspar, pyroxene and ilmenite have suffered considerable oxygen isotopic exchange during the retrogressive phase of the metamorphism, in spite of the fact that very little water was present in these granulites. The observed deviation from the peak metamorphic temperatures can be explained by essentially closed system solid-state diffusion (on at least a scale of centimetres) during slow cooling of the rocks from ~850 to 650°C, followed by more rapid cooling down to ～ 300°C. Such an explanation is not at variance with the radiometric data available for rocks from the area, which suggest that the latter phase could have involved uplift rates of ?0.5 mm/yr for a period of about 40 Ma. Wholerock δ¹⁸O values on non-quartzose mafic granulites, about 7.2%., fall within the range of basalts affected by seafloor weathering.     

超高压变质矿物中的多相固体包裹体研究进展

大陆碰撞过程中熔/流体的组成和演化是研究大陆深俯冲动力学的重要内容,而超高压岩石记录了大陆俯冲和折返过程中的熔/流体-岩石相互作用,因而是研究大陆碰撞过程中熔/流体组成和演化的天然实验室。大陆俯冲带高压/超高压变质矿物中多相固体包裹体作为熔/流体活动的直接记录,为我们提供了揭示超高压变质过程中熔/流体演化的重要制约。近年来,围绕超高压岩石中多相固体包裹体的形成时间、演化过程及其所反映的俯冲带超高压变质熔/流体的组成和性质,进行了大量的研究工作。超高压岩石中多相固体包裹体的发现,为理解峰期超高压变质流体的组成和演化提供了重要制约,同时也为研究俯冲板片-地幔楔界面的熔/流体交代作用提供了新的途径。本文从多相固体包裹体形成机制、结构形态特征、矿物化学成分及其地质地球化学意义等方面,对于超高压变质岩中多相固体包裹体的研究现状和存在的问题进行系统地总结和探讨,以期促进多相固体包裹体的岩石学和地球化学研究。     

高压超高压变质作用中流体—熔体—岩石相互作用

在高压超高压变质作用过程中所释放的流体对俯冲板块的演化起着重要作用,与岛弧岩浆活动有着直接联系,随着温度和压力的增加,俯冲板片将发生高压到超高榴辉岩相转变,大量的水将通过含水矿物的消失反应释放出来,这些流体可引起上覆岩圈大规模水化,并促进地幔楔状体的部分熔融,同时,通过流体的向上迁移可将某些组分带入上覆岩石圈板块,并改变其总体组成,许多含水矿物,同变质脉体,高压自形晶体组成的布丁,原生液态包裹体和     

Timescales and mechanisms of fluid infiltration in a marble: an ion microprobe study

Using a recently developed ion microprobe technique, a detailed oxygen isotope map of calcite grains in a coarse-grained marble has been constructed, supported by trace element (Mn, Sr, Fe) analysis and cathodoluminescence (CL) imaging, in order to constrain scales of oxygen isotope equilibrium, timescales and mechanisms of metamorphic fluid infiltration, and fluid sources and pathways. Results are compared with a previous study of this sample (Wada 1988) carried out using a cryo-microtome technique and conventional oxygen isotope analysis. The marble, from the high temperature/low pressure Hida metamorphic belt in north-central Japan, underwent granulite facies followed by amphibolite facies metamorphic events, the latter associated with regional granite intrusion. The CL imaging indicates two types of calcite, a yellow luminescing (YLC) and a purple luminescing (PLC) variety. The YLC, which occupies grain boundaries, fractures, replacement patches, and most of the abundant deformation twin lamellae, post-dates the dominant PLC calcite and maps out fluid pathways. Systematic relationships were established between oxygen isotope and trace element composition, calcite type and texture, based on 74 ¹⁸O/¹⁶O and 17 trace element analyses with 20–30 μ m spatial resolution. The YLC is enriched in Mn and Fe, and depleted in ¹⁸O and Sr compared to PLC, and is much more ¹⁸O depleted than is indicated from conventional analyses. Results are interpreted to indicate infiltration of ¹⁸O-depleted (metamorphic or magmatic) fluid (initial δ¹⁸O = 9‰–10.5‰) along grain boundaries, fractures and deformation twin lamellae, depleting calcite grains in Sr and enriching them in Mn and Fe. The sample is characterised by gross isotopic and elemental disequilibrium, with important implications for the application of chromatographic theory to constrain fluid fluxes in metacarbonate rocks. Areas of PLC unaffected by “short-circuiting” fluid pathways contain oxygen diffusion profiles of ∼10‰/∼200 μm in grain boundary regions or adjacent to fractures/patches. When correction is made for estimated grain boundary/fracture and profile orientation in 3D, profiles are indistinguishable within error. Modelling of these profiles gives consistent estimates of Dt (where D is the diffusion coefficient and t is time) of ∼0.8 × 10⁻⁸ m², from which, using experimental data for oxygen diffusion in calcite, timescales of fluid transport along grain boundaries at amphibolite facies temperatures of ∼10³ to ∼10⁴ years are obtained. These short timescales, which are much shorter than plausible durations of metamorphism, imply that rock permeabilities may be transiently much higher during fluid flow than those calculated from time integrated fluid fluxes or predicted from laboratory measurements. The preservation of ¹⁸O/¹⁶O profiles requires either rapid cooling rates (∼100–600 °C/million years), or, more plausibly, loss of grain boundary fluid such that a dry cooling history followed the transient passage of fluid. The δ¹⁸O/trace element correlations are also consistent with volume diffusion-controlled transport in the PLC. Fluid transport and element exchange occurred by two inter-related mechanisms on short timescales and on different lengthscales – long-distance flow along cracks, grain boundaries and twin lamellae coupled to ∼200 μm-scale volume diffusion of oxygen. Received: 8 December 1997 / Accepted: 18 May 1998