Contrasting retrograde oxygen isotope exchange behaviour and implications: examples from the Langtang Valley, Nepal

Quantitative modelling of oxygen exchange by diffusion during slow cooling has been compared to the observed oxygen isotope distributions from high-grade metamorphic and granitic rocks of the High Himalayan Crystallines, Langtang Valley, central Nepal, in order to investigate the effect of retrograde diffusional exchange on the preservation of high-temperature, oxygen isotope systematics. Modelled fractionations, using water-present diffusion data reported in the literature, predict quartz-mica fractionations to be much larger than those at peak metamorphic and igneous conditions due to low closure temperatures for micas. Quartz-feldspar fractionations may be less than those at peak conditions, and in some samples may even be slightly negative. The observed oxygen isotope fractionations in the metamorphic rocks are small and largely appear to record equilibrations close to peak conditions determined by other methods. Hence these rocks clearly do not conform to predictions of fluid-present diffusional retrograde exchange. It is suggested that their retrograde history was therefore within an anhydrous closed system in which diffusion was slow and hence mineral closure temperatures were high. The granitic rocks record rather larger quartz-biotite fractionations, approaching those predicted by the diffusion modelling. However, quartz-feldspar fractionations are large and hence, although significant retrograde exchange has clearly occurred, simple diffusion alone is not sufficient to explain the observed data and open-system exchange may be required. The presence of fluids during the retrograde history of this part of the section is supported by petrographic evidence. The different retrograde oxygen exchange histories recorded between the regional metamorphic and magmatic regimes of the Langtang section would appear to support the importance of water on the kinetics of such exchange, and suggests that in its absence, diffusional exchange may become insignificant, allowing oxygen isotope thermometry to record meaningful high-temperature 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.     

Apparent oxygen isotope equilibrium during progressive foliation development and porphyroblast growth in metapelites: implications for stable isotope and conventional thermometry

The assumption of oxygen isotope and major element equilibrium during prograde metamorphism was tested using staurolite‐grade pelitic schists that have undergone sequential porphyroblast growth and multiple episodes of recrystallization of matrix minerals and foliation development. Textural relationships are used to infer a metamorphic history that involves garnet growth followed by staurolite growth, with each porphyroblast growth event followed by at least one period of recrystallization of matrix minerals. Conventional geothermobarometry using Qtz–Grt–Pl–Ms–Bt ± St equilibria yields peak P–T conditions of c. 625 °C at 9–11 kbar, consistent with KMnFMASH petrogenetic grid predictions for stability of the assemblage Grt + St + Bt. Qtz–Grt oxygen isotope fractionations yield apparent temperatures of c. 590 °C and Qtz–St fractionations yield an apparent temperature of c. 595 °C. Diffusional modelling indicates that quartz isotopic compositions were reset by c. 30 °C via retrograde isotopic diffusional exchange with micas. The isotopic temperatures appear to be in excellent agreement with one another, and suggest oxygen isotope equilibrium was attained between garnet and staurolite at c. 625 °C. However, the agreement of Qtz–Grt and Qtz–Str isotopic temperatures is not consistent with petrographic observations (garnet grew before staurolite) and petrogenetic grid constraints that predict that garnet grows over a temperature interval of c. 525–550 °C. Given that: (i) oxygen diffusion rates in staurolite and garnet are slow enough to render an individual porphyroblast effectively closed to exchange after it forms; and (ii) matrix minerals are able to exchange isotopes via recrystallization during each period of deformation; garnet and staurolite could not have simultaneously achieved oxygen isotope equilibrium with each other or with minerals in the recrystallized matrix. Thus, the Qtz–Grt fractionations, which yield apparent temperatures that are in apparent agreement with peak metamorphic temperature and apparent temperatures for Qtz–St fractionations, cannot be fractionations resulting from equilibrium isotopic exchange. Instead, they are apparent fractionations between porphyroblasts formed at different temperature and times in the prograde P–T–D path, and quartz that recrystallized and exchanged with micas and plagioclase during several phases of deformation.     

Hydrogen and oxygen isotope evidence for fluid–rock interactions in the stages of pre- and post-UHP metamorphism in the Dabie Mountains

Hydrogen and oxygen isotope studies were carried out on high and ultrahigh pressure metamorphic rocks in the eastern Dabie Mountains, China. The δ¹⁸O values of eclogites cover a wide range of −4.2 to +8.8‰, but the δD values of micas from the eclogites fall within a narrow range of −87 to −71‰. Both equilibrium and disequilibrium oxygen isotope fractionations were observed between quartz and the other minerals, with reversed fractionations between omphacite and garnet in some eclogite samples. The δ¹⁸O values of −4 to −1‰ for some of the eclogites represent the oxygen isotope compositions of their protoliths which underwent meteoric water–rock interaction before the high to ultrahigh pressure metamorphism. Heterogeneous δ¹⁸O values for the eclogite protoliths implies not only the varying degrees of the water–rock interaction before the metamorphism at different localities, but also the channelized flow of fluids during progressive metamorphism due to rapid plate subduction. Retrograde metamorphism caused oxygen and hydrogen isotope disequilibria between some of the minerals, but the fluid for retrograde reactions was internally buffered in the stable isotope compositions and could be derived from structural hydroxyls dissolved in nominally anhydrous minerals.     

Oxygen isotope salt effects at high pressure and high temperature and the calibration of oxygen isotope geothermometers

The influence of NaCl, CaCl₂, and dissolved minerals on the oxygen isotope fractionation in mineral-water systems at high pressure and high temperature was studied experimentally. The salt effects of NaCl (up to 37 molal) and 5-molal CaCl₂ on the oxygen isotope fractionation between quartz and water and between calcite and water were measured at 5 and 15 kbar at temperatures from 300 to 750°C. CaCl₂ has a larger influence than NaCl on the isotopic fractionation between quartz and water. Although NaCl systematically changes the isotopic fractionation between quartz and water, it has no influence on the isotopic fractionation between calcite and water. This difference in the apparent oxygen isotope salt effects of NaCl must relate to the use of different minerals as reference phases. The term oxygen isotope salt effect is expanded here to encompass the effects of dissolved minerals on the fractionations between minerals and aqueous fluids. The oxygen isotope salt effects of dissolved quartz, calcite, and phlogopite at 15 kbar and 750°C were measured in the three-phase systems quartz-calcite-water and phlogopite-calcite-water. Under these conditions, the oxygen isotope salt effects of the three dissolved minerals range from ∼0.7 to 2.1‰. In both three-phase hydrothermal systems, the equilibrium fractionation factors between the pairs of minerals are the same as those obtained by anhydrous direct exchange between each pair of minerals, proving that the use of carbonate as exchange medium provides correct isotopic fractionations for a mineral pair.When the oxygen isotope salt effects of two minerals are different, the use of water as an indirect exchange medium will give erroneous fractionations between the two minerals. The isotope salt effect of a dissolved mineral is also the main reason for the observation that the experimentally calibrated oxygen isotope fractionations between a mineral and water are systematically 1.5 to 2‰ more positive than the results of theoretical calculations. Dissolved minerals greatly affect the isotopic fractionation in mineral-water systems at high pressure and high temperature. If the presence of a solute changes the solubility of a mineral, the real oxygen isotope salt effect of the solute at high pressure and high temperature cannot be correctly derived by using the mineral as reference phase.     

Hydrogen and oxygen isotope evidence for fluid–rock interactions in the Menderes massif, western Turkey

The Menderes Massif comprises an inner crystalline core with gneissic rocks and an outer surrounding schist belt with predominantly metasedimentary rocks. Both units have a complex metamorphic history including a late Alpine overprint. Temperatures inferred from oxygen isotope compositions of coexisting minerals increase from 420 to 600°C from the rim to the center. More positive '¹⁸O values in all minerals from the schist belt may reflect a higher abundance of sedimentary precursor material, whereas biotites and muscovites in core and rim are indistinguishable in hydrogen isotope composition. 'D values of muscovites range from -35 to -60‰, whereas 'D values of biotites range from -65 to -125‰, indicating normal values for muscovite but anomalously negative values for some biotites. For muscovite the trend can be interpreted in terms of increasing loss of water with rising metamorphic temperature. For biotite the 'D values decrease with increasing H₂O content and decreasing Na₂O+K₂O content, which provides evidence for alteration processes or exchange of K and Na with water from interlayers of biotite forming hydro-biotite. The data suggest isotopic resetting of pre-Alpine characteristics during Alpine metamorphism. The hydrogen isotope composition of biotite was later disturbed, probably during extensional neotectonic movements in this region, as this allowed infiltration of and exchange with D-depleted meteoric water; however, the muscovites retained its Alpine characteristics.     

Metasomatic coronas around hornblendite xenoliths in granulite facies marble, Ivrea zone, N Italy. II: Oxygen isotope patterns

Up to 20-cm-wide metasomatic reaction bands formed coronas around hornblendite xenoliths in a marble matrix during high grade metamorphism in the Ivrea zone. The coronas are comprised of an innermost monomineralic clinopyroxene layer, a garnet-clinopyroxene layer and an outermost scapolite-clinopyroxene layer. The oxygen isotope composition of the original hornblendite core is 7‰ relative to V-SMOW and the oxygen isotope composition of the marble matrix is 19.7‰. The oxygen isotope transition across the corona is represented by a diffusion front with a step discontinuity at the inner margin of the corona. The systematics of the inter-mineral fractionations indicates preservation of the oxygen isotope compositions from high temperatures and maintenance of grain-scale oxygen isotope equilibrium during corona formation. The oxygen isotope pattern is interpreted in terms of a moving boundary diffusion problem. The growing reaction band and the reactant hornblendite and marble represent a total of five media with different transport properties and moving separation surfaces. Bulk oxygen diffusion was at least three orders of magnitude faster then expected from volume diffusion, suggesting that transport was enhanced by relatively fast diffusion along grain boundaries. Oxygen diffusivities in the individual layers correlate with the oxygen volume diffusivities in the major constituent minerals of the respective layers, suggesting mineralogical control on bulk oxygen diffusion.     

Hydrogen and oxygen isotope exchange reactions between clay minerals and water

The extent of hydrogen and oxygen isotope exchange between clay minerals and water has been measured in the temperature range 100–350° for bomb runs of up to almost 2 years. Hydrogen isotope exchange between water and the clays was demonstrable at 100°. Exchange rates were 3–5 times greater for montmorillonite than for kaolinite or illite and this is attributed to the presence of interlayer water in the montmorillonite structure.Negligible oxygen isotope exchange occurred at these low temperatures. The great disparity in D and O¹⁸ exchange rates observed in every experiment demonstrates that hydrogen isotope exchange occurred by a mechanism of proton exchange independent of the slower process of O¹⁸ exchange.At 350° kaolinite reacted to form pyrophyllite and diaspore. This was accompanied by essentially complete D exchange but minor O¹⁸ exchange and implies that intact structural units in the pyrophyllite were inherited from the kaolinite precursor.     

Oxygen and hydrogen isotope geochemistry of gneisses associated with ultrahigh pressure eclogites at Shuanghe in the Dabie Mountains

The oxygen and hydrogen isotope compositions of minerals and whole rock were determined for two types of gneiss (biotite gneiss and granitic gneiss) associated with ultrahigh pressure (UHP) eclogites in the Shuanghe district of the eastern Dabie Mountains. There are significant differences in δ¹⁸O between the two gneisses: the UHP biotite gneiss varying from −4.3‰ to 10.6‰ similar to the associated eclogites, whereas the non-UHP granitic gneiss ranges only from −3.8‰ to 1.2‰. The δD values are similar in the two gneisses with −37 to −64‰ for epidote/zoisite, −92 to −83‰ for amphibole, and −63 to −109‰ for biotite/phengite. Hydrogen isotope disequilibrium among the coexisting hydroxyl-bearing minerals is ascribed to retrograde exchange subsequent to amphibolite-facies metamorphism. Oxygen isotopic equilibrium has been preserved among various minerals in both gneisses regardless of the large variation in rock δ¹⁸O. Oxygen isotopic geothermometers yield different but regular temperatures corresponding to the closure temperatures of oxygen diffusion in the minerals. The metamorphic temperatures of both eclogite facies and amphibolite facies have been recovered in mineral pairs from the biotite gneiss. The isotopic temperatures for the granitic gneiss are mostly in accordance with amphibolite-facies metamorphism. However, high temperatures of 550 to 650 °C are obtained from those minerals resistant to retrograde oxygen isotope exchange, implying that the granitic gneiss may have experienced higher temperature metamorphism than expected from petrologic thermometers. The ¹⁸O-depletion of both gneisses is interpreted to result from meteoric-hydrothermal exchange before/during plate subduction. Therefore, the measured δ¹⁸O values of the gneisses reflect the oxygen isotope compositions of their protoliths prior to the UHP metamorphism. It is inferred that the UHP unit is in foreign contact with the non-UHP unit like a tectonic melange, but both of them experienced the two common stages of geodynamic evolution: (1) ¹⁸O-depletion prior to the UHP metamorphism, (2) uplifting since the amphibolite-facies metamorphism. Received: 5 May 1998 / Accepted: 27 August 1998     

A computer simulation approach to modelling the structure,thermodynamics and oxygen isotope equilibria of silicates

We use an atomistic model to simulate the structure, lattice dynamics and thermodynamics of silicate minerals. Our approach uses the Born model of a solid, in which the interaction between atoms is described by an interatomic pair potential. We have extended the study of thermodynamics to its very limit by looking at the subtle reaction of oxygen isotope exchange. We have modelled equilibria involving the important metamorphic minerals; albite, diopside, forsterite, pyrope, quartz and wollastonite. The predicted structural and thermodynamic data for these silicates are in very good agreement with the observed values. In addition, we predict not only the correct direction for the phase equilibria for oxygen isotope exchange, but also fractionation factors for the reaction to within a factor of two of the available experimental data. Hence, the potentials used in our approach have shown excellent transferability and have performed very well against the most stringent of tests.     

Oxygen isotope fractionation in zinc oxides and implications for zinc mineralization in the Sterling Hill deposit, USA

Oxygen isotope fractionation in the zinc oxides has been calculated by means of the modified increment method. The results suggest that zincite is slightly enriched in ¹⁸O relative to the franklinite of the spinel-type structure but considerably depleted in ¹⁸O relative to the franklinite of the inverse spinel-type structure. The zinc oxides are significantly depleted in ¹⁸O relative to water under hydrothermal and metamorphic conditions. The oxygen isotope analyses of mineral pairs including the zinc oxides and the common gangue minerals such as calcite and quartz can constitute a sensitive isotope geothermometer. Application of oxygen isotope geothermometry to natural assemblages is attempted for the calcite-zinc ore mineral pairs from the Sterling Hill deposit in USA. The results indicate that the temperature of the zinc mineralization may be in the range from 410° to 630 °C and thus lower than the metamorphic temperatures of granulite facies. A metamorphic fluid could have been involved in the formation of the zinc ore minerals. Franklinite would structurally be an inverse spinel in the infancy of its formation, and thus could have originally evolved from Zn^{2 +} substitution to Fe^{2 +} of magnetite at the high temperatures.     

矿物-水体系氢同位素平衡分馏和动力分馏的实验研究

矿物水体系氢同位素平衡分馏系数和动力分馏系数是同位素地球化学研究中的重要参数。这些参数大多由实验测定。氢同位素分馏的实验研究主要包括矿物水体系氢同位素交换实验,交换实验前后矿物、水的氢同位素分析及分馏机理、平衡分馏、动力分馏理论研究。为确保氢同位素分馏系数和一系列动力学参数的准确可靠,实验中防止氢透过容器壁扩散,避免空气中水汽污染样品,正确控制实验温度等都很重要。本研究以石英管代替前人常用的金（银、铂）管作反应容器,建立了一套实验研究羟基矿物水体系氢同位素平衡分馏和动力分馏的新方法,并开展了电气石水、黑柱石水体系氢同位素分馏的实验研究。所得一系列参数的精度明显好于国外报道的资料。此研究方法可广泛应用于羟基矿物水体系的氢同位素分馏的实验研究。     

质量传输和同位素交换:流动几何学和交换机制

耦合的质量传输和动力学限制的同位素交换模型综合考虑了平流、扩散、热液弥散 ,以及岩石与水之间的不平衡同位素交换等项因素。把耦合模型应用于 2个构造环境下的古热液系统 ,进而解释稳定同位素数据。对于造成环绕浅成侵入岩体分布的18O亏损环带的流体的流动几何学 ,以及浅部正断层流体流动的几何学 ,耦合模型提供了不同于单一同位素交换模型的解释。耦合模型也提供了关于同位素相对交换速率和同位素交换机制的信息。结果表明 ,断层带的动态重结晶促进了表面反应 ,进而便利了同位素交换 ;在化学不反应性和未变形的矿物中 ,同位素交换可能受制于固态条件下的扩散。     

On the Direction and Magnitude of Oxygen Isotope Fractionation Between Calcite and Aragonite at Thermodynamic Equilibrium

Oxygen isotope fractionation factors between calcium carbonates and water have been applied to ancient marine geochemistry principally for the purpose of geothermometry. The problem was encountered, however, with respect to the direction and magnitude of oxygen isotope fractionation between calcite and aragonite at thermodynamic equilibrium. This basically involves sound understanding of both thermodynamics and kinetics of oxygen isotope fractionation between inorganically precipitated carbonate and water at low temperatures. Thus the crucial issues are to acknowledge the processes of chemical reaction and isotopic exchange during precipitation of CaCO₃ minerals in solution, the kinetic mechanism of isotope equilibrium or disequilibrium, the effect of polymorphic transition from metastable aragonite to stable calcite under hydrous or anhydrous conditions, and the presence or absence of isotope salt effect on oxygen isotope exchange between carbonate and water in response to the hydrous or anhydrous conditions at thermodynamic equilibrium. Because good agreements exist in carbonate–water oxygen isotope fractionation factors between theoretical calculations and experimental determinations, it is encouraging to applying the thermodynamic and kinetic data to isotopic paleothermometry and geochemical tracing.     

Experimental studies of oxygen and hydrogen isotope fractionations between precipitated brucite and water at low temperatures

Oxygen and hydrogen isotope fractionation factors between brucite and water were experimentally determined by chemical synthesis techniques at low temperatures of 15° to 120°C. MgCl₂, Mg3N₂, and MgO were used as reactants, respectively, to produce brucite in aqueous solutions. All of the synthesis products were identified by x-ray diffraction (XRD) for crystal structure and by scanning electron microscope (SEM) for morphology. It is observed that oxygen isotope fractionations between brucite and water are temperature dependent regardless of variations in aging time, the chemical composition, and pH value of solutions. Brucites derived from three different starting materials yielded consistent fractionations with water at the same temperatures. These suggest that oxygen isotope equilibrium has been achieved between the synthesized brucite and water, resulting in the fractionation equation of 10³lnα=1.56×10⁶/T²−14.1. When the present results for the brucite–water system are compared with those for systems of gibbsite–water and goethite–water, it suggests the following sequence of ¹⁸O-enrichment in the M−OH bonds of hydroxides: Al³⁺ − OH > Fe³⁺ − OH > Mg²⁺ − OH.Hydrogen isotope fractionations between brucite and water obtained by the different synthesis methods have also achieved equilibrium, resulting in the fractionation equation of 10³lnα=−4.88×10⁶/T²−22.5. Because of the pressure effect on hydrogen isotope fractionations between minerals and water, the present calibrations at atmospheric pressure are systematically lower than fractionations extrapolated from hydrothermal exchange experiments at high temperatures of 510° to 100°C and high pressures of 1060 to 1000 bar. Comparison of the present results with existing calibrations involving other low-temperature minerals suggests the following sequence of D-enrichment in hydroxyl-bearing minerals: Al³⁺ − OH > Mg²⁺ − OH > Fe³⁺ − OH.     

On the oxygen isotope distribution among mineral triplets in igneous and metamorphic rocks

A compilation of ¹⁸O analyses of minerals separated from about 400 igneous and metamorphic rocks from published investigations reveals regularity in the fractionation of ¹⁸O among associated minerals, suggesting that an approach to isotopic equilibrium may be common. However, for only a minority of terrestrial rocks are these regularities sufficiently systematic to be compatible with the actual attainment and preservation of isotopic equilibrium among three minerals. Fractionations among triplets of quartz, calcite, feldspar, muscovite, and magnetite show some correspondence to those expected on the basis of experimental calibrations; however, there are also considerable deviations. The variability of natural data is such that less than half of the rocks analyzed to date would yield concordant ¹⁸O-derived temperatures. Of the additional 52 mineral triplets studied, plagioclase-pyrox-ene-ilmenite, plagioclase-pyroxene-magnetite, plagioclase-pyroxene-olivine, quartz-amphibole-garnet, pyroxene-ilmenite-magnetite, muscovite-biotite-magnetite, and quartz-muscovite-amphibole show the most systematic oxygen isotope fractionations. For 12 other mineral triplets a defined isotope fractionation relationship may be postulated to underlie the data; however for these a close approach to isotopic equilibrium is not commonly observed. For 33 of the mineral triplets an approach to isotopic equilibrium can be noted; however, the scatter of the available data is such that a systematic influence of a factor, such as temperature, on the size of the ¹⁸O fractionation could not be detected. In the past, regularities of oxygen isotope fractionations among three minerals have been used to establish secondary isotope geothermometers. Before this can be done with any reliability, however, the effects of possible retrograde isotope exchange and spurious correlation must be accounted for.     

Oxygen isotope exchange processes and disequilibrium between calcite and forsterite in an experimental C-O-H fluid

Oxygen isotope exchange between calcite and forsterite were investigated in the presence of a large amount of supercritical fluid. The experiments were conducted in standard cold-seal pressure vessels at 680°C and 500 MPa in the T-P-X_CO2 stability field of the calcite-forsterite assemblage for 2, 5, 10, 20, 40 and 80 days, respectively. The weight ratio of mineral to fluid in the starting mixture is 1.46; the fluid was a mixture of H₂O and CO₂ with the mole fraction of CO₂ being 0.1. The results show that the oxygen isotope exchange between the minerals was accomplished via mineral-fluid exchange by a dual-mechanism, i.e. initial rapid exchange due to Ostwald ripening of both calcite and forsterite, followed by a slower diffusion-controlled process. Furthermore, for the given fluid composition, calcite shows a greater rate of dissolution-recrystallization and oxygen isotope exchange with fluid than forsterite. As a result, oxygen isotope fractionations between calcite and forsterite and between the minerals and the fluid can simply pass the equilibrium fractionations with time and even lead to crossover behavior. Once diffusion becomes a primary mechanism for further isotope exchange in the three-phase system, the rate of oxygen diffusion in calcite is equal to, or slightly less than that in forsterite.     

Oxygen isotope exchange and closure temperatures in cooling rocks

Retrograde exchange of oxygen isotopes between minerals in igneous and metamorphic rocks by means of diffusion is explored using a finite difference computer model, which predicts both the zonation profile of δ¹⁸O within grains, and the bulk δ¹⁸O value of each mineral in the rock. Apparent oxygen isotope equilibrium temperatures that would be observed in these rocks are calculated from the δ¹⁸O values of each mineral pair within the rock. In systems which cool linearly from a sufficiently high temperature or at a low enough cooling rate, such that the final oxygen isotope values are not dependent upon the initial oxygen isotope values ('slow cooling'), the apparent oxygen isotope temperature derived for a rock composed of a single mineral pair can be shown to be simply related to the Dodson closure temperatures ( T _c) for the two phases and the mode of the rock. Adding a third phase into a system which undergoes 'slow' cooling will cause the apparent temperature derived for the two minerals already present to differ from the simple relationship for a two-phase system. In some systems oxygen isotope reversals can be developed. If cooling is not 'slow', then the mineral δ¹⁸O values resulting from cooling will be partly dependent upon the initial temperature of the system concerned. The model successfully simulates the mineral δ¹⁸O values that are often observed in granitic rocks. Application of the model will help in assessing the validity of oxygen isotope thermometry in different geological settings, and allows quantitative prediction of the oxygen isotope fractionations that are developed in cooling closed systems.     

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.     

西南大别榴辉岩和麻粒岩的氧同位素地球化学

报道了大别造山带西南部湖北红安榴辉岩和罗田麻粒岩的氧同位素组成，并讨论了氧扩散作用对矿物氧同位素平衡的影响，结果得到，红安榴辉岩的全岩δ^18O值为6．4－7．3‰，罗田黄土岭麻粒岩的全岩δ^18O值为6．6－7．8‰，罗田惠兰山麻粒岩的全岩δ^18O值为3．9‰，这些榴辉岩和麻粒岩全岩的氧同位素组成保持了峰期变质条件下的平衡分馏特征，得到的氧同位素温度对于红安榴辉岩425－620度，对于罗田麻粒岩为740－945度。根据快速颗粒边界扩散模型计算的矿物对氧同位素温度不仅与大多数实测氧同位素温度一致，而且与岩石学测温结果相吻合，因此，这些岩石与东大别榴辉岩一样在形成后经历了快速冷却过程，退变质反应过程中没有外来流体加入。