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1.
The analysis of texture, major element and oxygen isotope compositions of cloudy garnet crystals from a metapelite sampled on Ikaria Island (Greece) is used to assess the model of growth and re‐equilibration of these garnet crystals and to reconstruct the pressure–temperature–fluid history of the sample. Garnet crystals show complex textural and chemical zoning. Garnet cores (100–200 μm) are devoid of fluid inclusions. They are characterized by growth zoning demonstrated by a bell‐shaped profile of spessartine component (7–3 mol.%), an increase in grossular from 14 to 22 mol.% and δ18O values between 9.5 ± 0.3‰ and 10.4 ± 0.2‰. Garnet inner rims (90–130 μm) are fluid inclusion‐rich and show a decreasing grossular component from 22 to 5 mol.%. The trend of the spessartine component observed in the inner rim allows two domains to be distinguished. In contrast to domain I, where the spessartine content shows the same trend as in the core, the spessartine content of domain II increases outwards from 2 to 14 mol.%. The δ18O values decrease towards the margins of the crystals to a lowest value of 7.4 ± 0.2‰. The outer rims (<10 μm) are devoid of fluid inclusions and have the same chemical composition as the outermost part of domain II of the inner rim. Garnet crystals underwent a four‐stage history. Stage 1: garnet growth during the prograde path in a closed system for oxygen. Garnet cores are remnants of this growth stage. Stage 2: garnet re‐equilibration by coupled dissolution–reprecipitation at the temperature peak (630 < T < 650 °C). This causes the creation of porosity as the coupled dissolution–reprecipitation process allows chemical (Ca) and isotopic (O) exchange between garnet inner rims and the matrix. The formation of the outer rim is related to the closure of porosity. Stage 3: garnet mode decreases during the early retrograde path, but garnet is still a stable phase. The resulting garnet composition is characterized by an increasing Mn content in the inner rim’s domain II caused by intracrystalline diffusion. Stage 4: dissolution of garnet during the late retrograde path as garnet is not a stable phase anymore. This last stage forms corroded garnet. This study shows that coupled dissolution–reprecipitation is a possible re‐equilibration process for garnet in metamorphic rocks and that intra‐mineral porosity is an efficient pathway for chemical and isotopic exchange between garnet and the matrix, even for otherwise slow diffusing elements.  相似文献   

2.
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.  相似文献   

3.
The skarn‐type tungsten deposit of the Date‐Nagai mine is genetically related to the granodiorite batholith of the Iidateyama body. Skarn is developed along the contact between pelitic hornfels and marble that remains as a small roof pendant body directly above the granodiorite batholith. Zonal arrangement of minerals is observed in skarn. The zonation consists of wollastonite, garnet, garnet‐epidote, and vesuvianite‐garnet zones, from marble to hornfels. Sheelite is included in garnet, garnet‐epidote, and vesuvianite‐garnet zones. The oxygen isotope values of skarn minerals were obtained as δ18O = 4.2–7.7‰ for garnet, 5.9–6.9‰ for vesuvianite, ?0.3–3.4‰ for scheelite, 6.0–10.9‰ for quartz, and 8.2‰ for muscovite. The temperature of skarn‐formation was calculated from oxygen isotopic values of scheelite‐quartz pairs to be 288°C. Calculated oxygen isotope values of fluid responsible for skarn minerals were 6.1–9.5‰ for garnet, 1.2–4.8‰ for scheelite, ?1.3‐3.6‰ for quartz, and 4.5‰ for muscovite. Garnet precipitated from the fluids of different δ18O values from scheelite, quartz, and muscovite. These δ18O values suggest that the origin of fluid responsible for garnet was magmatic water, while evidence for the presence of a meteoric component in the fluids responsible for middle to later stages minerals was confirmed.  相似文献   

4.
Polymetamorphic metapelites and embedded eclogites share a complex, episodic interplay of dehydration and fluid infiltration at the eclogite type‐locality (Saualpe–Koralpe, Eastern Alps, Austria). The metapelites inherited a fluid content (i.e. mineral‐bound OH expressed in terms of mol.% H2O) of ～6–7 mol.% H2O from high‐T–low‐P metamorphism experienced during the Permian. At or near Pmax of the subsequent Eoalpine event (～20 kbar and 680°C), the breakdown of paragonite to Na‐rich clinopyroxene and kyanite in metapelites released a discrete pulse of hydrous fluid. Prior to the dehydration event, the rocks were largely fluid absent, allowing only limited re‐equilibration during the prograde Eoalpine evolution. Similarly, Permian‐aged gabbros have persisted metastably due to the absence of a catalyst prior to fluid‐induced re‐equilibration. The fluid triggered partial to complete eclogitization along a fluid infiltration front partially preserved in metagabbro. Near‐isothermal decompression to ～7.5–10 kbar and 670–690°C took place under fluid‐absent conditions. After decompression, a second breakdown of phengitic white mica and garnet produced muscovite, biotite, plagioclase and ～0.1–0.7 mol.% H2O that enhanced extensive fluid‐aided re‐equilibration of the metapelites. Potential relicts of high‐P assemblages were largely obliterated and replaced by the recurrent amphibolite facies assemblage garnet+biotite+staurolite+kyanite+muscovite+plagioclase+ilmenite+quartz. The hydrous fluid originating from the metapelites infiltrated the embedded eclogites at these P–T conditions and induced the local breakdown of the peak assemblage omphacite and garnet to fine‐grained symplectites of diopside and plagioclase. Further fluid infiltration led to the formation of hornblende–quartz poikiloblasts at the expense of the symplectites. The metapelites re‐equilibrated until the growth of retrograde staurolite consumed any remaining free fluid, thereby terminating the process. Further re‐equilibration is inhibited by both the lack of a catalytic fluid and H2O as a reactant essential for rehydration reactions. The interplay between fluid sources and fluid sinks describes a closed cycle for the rocks at the eclogite type‐locality. Final, near‐isobaric cooling is indicated by a slight increase of XFe in garnet rims. Post‐decompression dehydration and fluid‐aided re‐equilibration arrested by the introduction of staurolite might explain the apparently homogeneous retrogression conditions as well as the notorious absence of diagnostic high‐P assemblages in metapelites at the eclogite type‐locality.  相似文献   

5.
A combined study of major and trace elements, fluid inclusions and oxygen isotopes has been carried out on garnet pyroxenite from the Raobazhai complex in the North Dabie Terrane (NDT). Well‐preserved compositional zoning with Na decreasing and Ca and Mg increasing from the core to rim of pyroxene in the garnet pyroxenite indicates eclogite facies metamorphism at the peak metamorphic stage and subsequent granulite facies metamorphism during uplift. A P–T path with substantial heating (from c. 750 to 900 °C) after the maximum pressure reveals a different uplift history compared with most other eclogites in the South Dabie Terrane (SDT). Fluid inclusion data can be correlated with the metamorphic grade: the fluid regime during the peak metamorphism (eclogite facies) was dominated by N2‐bearing NaCl‐rich solutions, whereas it changed into CO2‐dominated fluids during the granulite facies retrograde metamorphism. At a late retrograde metamorphic stage, probably after amphibolite facies metamorphism, some external low‐salinity fluids were involved. In situ UV‐laser oxygen isotope analysis was undertaken on a 7 mm garnet, and impure pyroxene, amphibole and plagioclase. The nearly homogeneous oxygen isotopic composition (δ18OVSMOW = c. 6.7‰) in the garnet porphyroblast indicates closed fluid system conditions during garnet growth. However, isotopic fractionations between retrograde phases (amphibole and plagioclase) and garnet show an oxygen isotopic disequilibrium, indicating retrograde fluid–rock interactions. Unusual MORB‐like rare earth element (REE) patterns for whole rock of the garnet pyroxenite contrast with most ultra‐high‐pressure (UHP) eclogites in the Dabie‐Sulu area. However, the age‐corrected initial εNd(t) is ? 2.9, which indicates that the protolith of the garnet pyroxenite was derived from an enriched mantle rather than from a MORB source. Combined with the present data of oxygen isotopic compositions and the characteristic N2 content in the fluid inclusions, we suggest that the protolith of the garnet pyroxenite from Raobazhai formed in an enriched mantle fragment, which has been exposed to the surface prior to the Triassic metamorphism.  相似文献   

6.
Oxygen isotopic compositions of silicates in eclogites and whiteschists from the Kokchetav massif were analyzed by whole‐grain CO2‐laser fluorination methods. Systematic analyses yield extremely low δ18O for eclogites, as low as ?3.9‰ for garnet; these values are comparable with those reported for the Dabie‐Sulu UHP eclogites. Oxygen isotopic compositions are heterogeneous in samples of eclogite, even on an outcrop scale. Schists have rather uniform oxygen isotope values compared to eclogites, and low δ18O is not observed. Isotope thermometry indicates that both eclogites and schists achieved high‐temperature isotopic equilibration at 500–800 °C. This implies that retrograde metamorphic recrystallization barely modified the peak‐metamorphic oxygen isotopic signatures. A possible geological environment to account for the low‐δ18O basaltic protolith is a continental rift, most likely subjected to the conditions of a cold climate. After the basalt interacted with low δ18O meteoric water, it was tectonically inserted into the surrounding sedimentary units prior to, or during subduction and UHP metamorphism.  相似文献   

7.
The Mt. Emilius klippe (Western Alps, Italy) corresponds to a segment of the stretched Adriatic continental margin metamorphosed at granulite facies during Permian. This slice was subducted during the early Cenozoic Alpine subduction with the underlying eclogite facies remnants of the Tethyan seafloor (Zermatt‐Saas zone). Near the base of the Mt. Emilius massif, there is a shear zone with eclogite facies hydrofracture systems associated with deformation‐induced re‐equilibration of granulites during high‐P metamorphism. In the basal part of the massif, a pluri‐hectometre domain of sheared mafic boudins is hosted in the granulitic paragneiss. In these mafic boudins, there are garnetites, garnet veins and clinopyroxenites, as well as clinozoisite and calcite veins. These features record multiple events of fracture opening, brecciation, boudinage and parallelization of structures coevally with fluid–rock interaction, metasomatism and volume change. This integrated petrological, micro‐textural and geochemical investigation illustrates the multiplicity and the chemical variability of fluid sources during prograde to peak metamorphic evolution in the lawsonite–eclogite‐facies field (at ~2.15–2.4 GPa, 500–550 °C) during subduction of the Mt. Emilius slice. The calcite veins crosscutting the garnetites have relatively low δ18OVSMOW values (～+6.5‰) near those for marble layers (and nearby calcsilicates) embedded within the metasomatized granulites (+8 to +10‰). It is proposed that infiltration of externally‐derived H2O‐rich fluids derived from the plate interface flushed the marbles, promoting decarbonation followed by short‐distance transport and re‐precipitation along garnetite fractures. This study highlights the importance of inherited structural heterogeneities (such as mafic bodies or sills) in localizing deformation, draining fluids from the downgoing plate and creating long‐lasting mechanical instabilities during subduction zone deformation.  相似文献   

8.
It is generally thought that garnet in metapelites is produced by continuous reactions involving chlorite or chloritoid. Recent publications have suggested that the equilibrium temperatures of garnet‐in reactions may be significantly overstepped in regionally metamorphosed terranes. The growth of small spessartine–almandine garnet crystals on Mn‐siderite at the garnet isograd in graphitic metapelites in the Proterozoic Black Hills orogen, South Dakota, demonstrates that Mn‐siderite was the principal reactant that produced the initial garnet in the schists. Moreover, the positions of garnet compositions in isobaric, T–(C/H) pseudosections for the schists show that the temperature of the garnet‐in reaction from Mn‐siderite was overstepped minimally at the most. In the Black Hills, garnet was initially produced during regional metamorphism beginning at c. 1755 Ma due to the collision of Wyoming and Superior cratons, and was subsequently partially or fully re‐equilibrated at more elevated temperatures and pressures during intrusion of the Harney Peak Granite (HPG) at c. 1715 Ma. Garnet occurs in graphitic schists in garnet, staurolite and sillimanite zones, the latter being a product of contact metamorphism by HPG. During metamorphism, coexisting fluid contained both CO2 and CH4. In the garnet zone, garnet crystals contain petrographically distinct cores with inclusions of quartz, graphite and other minerals. Centres of the cores have distinctly elevated Y concentrations that mark the positions of garnet nucleation. The elevated Y is thought to have come from the Mn‐siderite onto which Y was probably absorbed during precipitation in an ocean. In the upper garnet and staurolite zones, the cores were overgrown by inclusion‐poor mantles. Mantles are highly zoned and have more elevated Fe and Mg and lower Mn and Ca than cores. The growth of mantles is attributed to late‐orogenic heating by leucogranite magmas and attendant influx of H2O that caused consumption of graphite in rock matrices. A portion of the Proterozoic terrane that includes the HPG is surrounded by four large faults. In this ‘HPG block’, garnet is inclusion‐poor and its composition does not preserve its early growth history. This garnet appears to have re‐equilibrated by internal diffusion of its major components and/or recrystallization of an earlier inclusion‐rich garnet. It has equilibrated within the kyanite stability range, and together with remnant kyanite in the high‐strain aureole of the HPG, indicates that the HPG block had a ≥6 kbar history. The HPG block has undergone decompression during emplacement of the HPG. The decompression is evident in occurrences of retrograde andalusite and cordierite in the thermal aureole of the HPG. The data support a polybaric metamorphic history of the Black Hills orogen with different segments of the orogen having their own clockwise P–T–t paths.  相似文献   

9.
We report technical and data treatment methods for making accurate, high‐precision measurements of 18O/16O in Ca–Mg–Fe garnet utilising the Cameca IMS 1280 multi‐collector ion microprobe. Matrix effects were similar to those shown by previous work, whereby Ca abundance is correlated with instrumental mass fractionation (IMF). After correction for this effect, there appeared to be no significant secondary effect associated with Mg/Fe2+ for routine operational conditions. In contrast, investigation of the IMF associated with Mn‐ or Cr‐rich garnet showed that these substitutions are significant and require a more complex calibration scheme. The Ca‐related calibration applied to low‐Cr, low‐Mn garnet was reproducible across different sample mounts and under a range of instrument settings and therefore should be applicable to similar instruments of this type. The repeatability of the measurements was often better than ± 0.2‰ (2s), a precision that is similar to the repeatability of bulk techniques. At this precision, the uncertainties due to spot‐to‐spot repeatability were at the same magnitude as those associated with matrix corrections (± 0.1–0.3‰) and the uncertainties in reference materials (± 0.1–0.2‰). Therefore, it is necessary to accurately estimate and propagate uncertainties associated with these parameters – in some cases, uncertainties in reference materials or matrix corrections dominate the uncertainty budget.  相似文献   

10.
The relative timing of two discrete pulses of metamorphic fluid flow is constrained based on chemical zoning in several garnet crystals from Kvaløya, Troms, northern Norway. The garnet crystals measured 1–2 cm in diameter and were contained within c. 1.6 Ga, staurolite grade metasediments. Major element zoning indicates that garnet grew under normal prograde conditions in the garnet and/or staurolite zones. Timing constraints are based on comparisons between major and trace element chemical zoning, oxygen isotope (δ18O) zoning and deformational (inclusion trail) zoning in one of the garnet. We interpret at least two pulses of metamorphic fluid flow. The first pulse occurred during the syn‐tectonic growth interval. The δ18O zoning was reversed relative to ‘normal’ prograde zoning and the δ18O maximum was located within the syn‐tectonic growth zone, displaced 3–4 mm from the garnet core. The fluid might have been sourced in neighbouring calcareous pelites and may also have caused formation of an Y ring. The second (and subsequent) pulse(s) occurred during/after the post‐tectonic growth interval. δ18O was locally increased at the garnet rim, particularly where the rim was sheared. The incomplete rim was also enriched in calcium. Transport of oxygen and calcium by metamorphic fluids is well documented. Transport of Y is both problematic and poorly understood, but might have been facilitated by complexing with F and/or CO2.  相似文献   

11.
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.  相似文献   

12.
In situ analysis of a garnet porphyroblast from a granulite facies gneiss from Sør Rondane Mountains, East Antarctica, reveals discontinuous step‐wise zoning in phosphorus and large δ18O variations from the phosphorus‐rich core to the phosphorus‐poor rim. The gradually decreasing profile of oxygen isotope from the core (δ18O = ~15‰) to the rim (δ18O = ~11‰) suggests that the 18O/16O zoning was originally step‐wise, and modified by diffusion after the garnet rim formation at ~800°C and 0.8 GPa. Fitting of the 18O/16O data to the diffusion equation constrains a duration of the high‐T event (~800°C) to c. 0.5–40 Ma after the garnet rim formation. The low δ18O value of the garnet rim, together with the previously reported low δ18O values in metacarbonates, indicates regional infiltration, probably along a detachment fault, of low δ18O fluid/melt possibly derived from meta‐mafic to ultramafic rocks.  相似文献   

13.
A combined oxygen‐isotope and fluid‐inclusion study has been carried out on high‐ and ultrahigh‐pressure metamorphic (HP/UHPM) eclogites and garnet clinopyroxenite from the Dabie‐Sulu terranes in eastern China. Coesite‐bearing eclogites/garnet clinopyroxenite and quartz eclogites have a wide range in whole‐rock δ18OVSMOW, from 0 to 11‰. The high‐T oxygen‐isotope fractionations preserved between quartz and garnet preclude significant retrograde isotope exchange during exhumation, and the wide range in whole‐rock oxygen‐isotope composition is thought to be a presubduction signature of the precursors. Aqueous fluids with variable salinities and gas species (N2‐, CO2‐, or CH4‐rich), are trapped as primary inclusions in garnet, omphacite and epidote, and in quartz blebs enclosed within eclogitic minerals. In high‐δ18O HP/UHPM rocks from Hujialin and Shima, high‐salinity brine and/or N2 inclusions occur in garnet porphyroblasts, which also contain inclusions of coesite, Cl‐rich blue amphibole and dolomite. In contrast, in low‐δ18O eclogites from Qinglongshan and Huangzhen, the Cl concentrations in amphibole are very low, < 0.2 wt.%, and low‐salinity aqueous inclusions occur in quartz inclusions in epidote porphyroblasts and in epidote cores. These low‐salinity fluid inclusions are believed to be remnants of meteoric water, although the fluid composition was modified during pre‐ and syn‐peak HP/UHPM. Eclogites at Houshuichegou and Hetang contain CH4‐rich fluid inclusions, coexisting with high‐salinity brine inclusions. Methane was probably formed under the influence of CO2‐rich aqueous fluids during serpentinisation of mantle‐derived peridotites prior to or during plate subduction. Remnants of premetamorphic low‐ to high‐salinity aqueous fluid with minor N2 and/or other gas species preserved in the Dabie‐Sulu HP/UHPM eclogites and garnet clinopyroxenite indicate a great diversity of initial fluid composition in the precursors, implying very limited fluid–rock interaction during syn‐ and post‐peak HP/UHPM.  相似文献   

14.
The large range of stable oxygen isotope values of phosphate‐bearing minerals and dissolved phosphate of inorganic or organic origin requires the availability of in‐house produced calibrated silver phosphate of which isotopic ratios must closely bracket those of studied samples. We propose a simple protocol to synthesise Ag3PO4 in a wide range of oxygen isotope compositions based on the equilibrium isotopic fractionation factor and the kinetics and temperature of isotopic exchange in the phosphate–water system. Ag3PO4 crystals were obtained from KH2PO4 that was dissolved in water of known oxygen isotope composition. Isotopic exchange between dissolved phosphate and water took place at a desired and constant temperature into PYREX? tubes that were placed in a high precision oven for defined run‐times. Samples were withdrawn at desired times, quenched in cold water and precipitated as Ag3PO4. We provide a calculation sheet that computes the δ18O of precipitated Ag3PO4 as a function of time, temperature and δ18O of both reactants KH2PO4 and H2O at t = 0. Predicted oxygen isotope compositions of synthesised silver phosphate range from ?7 to +31‰ VSMOW for a temperature range comprised between 110 and 130 °C and a range of water δ18O from ?20 to +15‰ VSMOW.  相似文献   

15.
Oscillatory zoning in low δ18O skarn garnet from the Willsboro wollastonite deposit, NE Adirondack Mts, NY, USA, preserves a record of the temporal evolution of mixing hydrothermal fluids from different sources. Garnet with oscillatory zoning are large (1–3 cm diameter) euhedral crystals that grew in formerly fluid filled cavities. They contain millimetre‐scale oscillatory zoning of varying grossular–andradite composition (XAdr = 0.13–0.36). The δ18O values of the garnet zones vary from 0.80 to 6.26‰ VSMOW and correlate with XAdr. The shape, pattern and number of garnet zones varies from crystal to crystal, as does the magnitude of the correlated chemistry changes, suggesting fluid system variability, temporal and/or spatial, over the time of garnet growth. The zones of correlated Fe content and δ18O indicate that a high Fe3+/Al, high δ18O fluid mixed with a lower Fe3+/Al and δ18O fluid. The high δ18O, Fe enriched fluids were likely magmatic fluids expelled from crystallizing anorthosite. The low δ18O fluids were meteoric in origin. These are the first skarn garnet with oscillatory zoning reported from granulite facies rocks. Geochronologic, stable isotope, petrologic and field evidence indicates that the Adirondacks are a polymetamorphic terrane, where localized contact metamorphism around shallowly intruded anorthosite was followed by a regional granulite facies overprint. The growth of these garnet in equilibrium with meteoric and magmatic fluids indicates an origin in the shallow contact aureole of the anorthosite prior to regional metamorphism. The zoning was preserved due to the slow diffusion of oxygen and cations in the large garnet and protection from deformation and recrystallization in zones of low strain in thick, rigid, garnetite layers. The garnet provide new information about the hydrothermal system adjacent to the shallowly intruded massif anorthosite that predates regional metamorphism in this geologically complex, polymetamorphic terrane.  相似文献   

16.
Oxygen isotope ratios of quartz inclusions (QI) within garnet from granulite and amphibolite facies gneisses in the Adirondack Mountains, NY were analysed and used to determine metamorphic temperatures. Primary QI for eight of 12 samples have δ18O values significantly lower than matrix quartz (MQ). The primary QI retain δ18O values representative of thermal conditions during garnet crystallization, whereas the δ18O values of MQ were raised by diffusive exchange with other matrix minerals (e.g. mica and feldspar) during cooling. The δ18O differences between QI and MQ show that garnet (a mineral with slow diffusion of oxygen) can armour QI from isotopic exchange with surrounding matrix, even during slow cooling. These differences between δ18O in MQ and QI can further be used to test cooling rates by Fast Grain Boundary diffusion modelling. Criteria for identifying QI that preserve primary compositions and are suitable for thermometry were developed based on comparative tests. Relations between δ18O and inclusion size, distance of inclusion to host–garnet rim, core–rim zonation of individual inclusions, and presence or absence of petrological features (healed cracks in QI, inclusions in contact with garnet cracks lined by secondary minerals, and secondary minerals along the inclusion grain boundary) were investigated. In this study, 61% of QI preserve primary δ18O and 39% were associated with features that were linked to reset δ18O values. If δ18O in garnet is homogeneous and inclusions are removed, laser‐fluorination δ18O values of bulk garnet are more precise, more accurate, and best for thermometry. Intragrain δ18O(Grt) profiles measured in situ by ion microprobe show no δ18O zonation. Almandine–rich garnet (Alm60–75) from each sample was measured by laser‐fluorination mass‐spectrometry (LF‐MS) for δ18O and compared with ion microprobe measurements of δ18O in QI for thermometry. The Δ18O(Qz–Grt) values for Adirondack samples range from 2.66 to 3.24‰, corresponding to temperatures of 640–740 °C (A[Qz–Alm] = 2.71). Out of 12 samples that were used for thermometry, nine are consistent with previous estimates of peak temperature (625–800 °C) based on petrological and carbon–isotope thermometry for regional granulite and upper amphibolite facies metamorphism. The three samples that disagree with independent thermometry for peak metamorphism are from the anorthosite–mangerite–charnockite–granite suite in the central Adirondacks and yield temperatures of 640–665 °C, ~100 °C lower than previous estimates. These low temperatures could be interpreted as thermal conditions during late (post‐peak) crystallization of garnet on the retrograde path.  相似文献   

17.
Palaeotemperature estimates from the oxygen‐isotope compositions of belemnites have been hampered by not knowing ancient seawater isotope compositions well enough. We have tackled this problem using Mg/Ca as a proxy for temperature and here, we present a ~2 Ma record of paired Mg/Ca and δ18O measurements of Jurassic (Early Pliensbachian) belemnites from the Asturian basin as a palaeo‐proxy of seawater oxygen‐isotope composition. From the combined use of the two approaches, we suggest a δ18Ow composition of about ?0.1‰ for the Jamesoni–Ibex zones. This value may have been increased by about 0.6‰ during the Davoei Zone due to the effect of waters with a different δ18Ow composition. These findings illustrate the inaccuracy of using a globally homogeneous ice‐free value of δ18Ow = ?1‰ for δ18Ocarb‐based palaeotemperature reconstructions. Our data suggest that previous palaeotemperatures calculated in the region from δ18O values of belemnites may have been underestimated as the seawater oxygen isotopic composition could have been higher.  相似文献   

18.
The a–x relations recently presented in White et al. ( 2014 , Journal of Metamorphic Geology, 32, 261–286) are extended to include MnO. This provides a set of internally consistent a–x relations for metapelitic rocks in the MnO–Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–O2 (MnNCKFMASHTO) system. The mixing parameters for the Mn‐bearing minerals were estimated using the micro‐? approach of Powell et al. ( 2014 , Journal of Metamorphic Geology, 32, 245–260). Then the Mn‐end‐member thermodynamic properties were calibrated using a database of co‐existing minerals involving literature data from rocks and from experiments on natural materials. Mn‐end‐members were calibrated for orthopyroxene, cordierite, staurolite, chloritoid, chlorite, biotite, ilmenite and hematite, assuming known properties for the garnet end‐member spessartine. The addition of MnO to phase diagram calculations results in a marked expansion of the stability of garnet‐bearing assemblages. At greenschist facies conditions garnet stability is extended down temperature. At amphibolite facies conditions, the garnet‐in boundary shifts to lower pressure. While the addition of MnO greatly influences the stability of garnet, it has relatively little effect on the stability of other common metapelitic minerals, with the resultant diagrams being topologically very similar to those calculated without MnO. Furthermore, the addition of MnO in the amounts measured in most metapelites has only a small effect on the mode of garnet, with calculated garnet modes remaining smaller than 1% in the P–T range outside its predicted Mn‐free P–T range.  相似文献   

19.
Caledonian eclogite-facies metamorphism partially reworking Grenvillian granulite-facies anorthosite allows us to study the processes of garnet reequilibration at high pressure and to reconstruct the evolution of the unit near metamorphic peak conditions. Our results indicate that eclogite-facies metamorphism happened in two successive phases: first, inherited granulitic garnet was fractured and reequilibrated from their boundaries (crystal or fracture rims); then eclogite-facies minerals were crystallised in the fractures as overgrowths on inherited garnets. The reequilibration of inherited garnets is achieved through Fe2+Mg−1 exchange, whereas eclogite-facies garnets crystallised during the subsequent phase are notably richer in Ca than un- and re-equilibrated granulitic garnet. Pseudosection construction shows that this lack in Ca reequilibration cannot be related to variations in thermodynamic conditions (a H2O, reacting system composition) between the two phases. From the compilation of the available data, the reequilibration of granulitic garnet seems to be controlled by the inefficient intra- and inter-granular transport properties of Ca compared to Fe2+ and Mg. While these kinetic factors confine garnet reequilibration to Fe2+Mg−1 exchange, the extent of reequilibration along this exchange vector is controlled by partitioning with adjacent omphacite. On the contrary to the diffusional reequilibration of granulitic garnet that lasted for several My according to our modelling of the diffusional relaxation, the strong compositional gradients between eclogite-facies and reequilibrated garnets, which are almost unaffected by diffusional reequilibration, provide evidence that rapid exhumation followed the crystallisation of eclogite-facies minerals. We propose that the movement reversal itself, from burial to exhumation, and associated deformation and fluid flow, triggered this crystallisation event. The resulting evolution near metamorphic peak conditions is therefore strongly asymmetrical: on the one hand, the prograde diffusional relaxation profiles indicate slow movement during the last stages of burial, whereas the unaffected retrograde overgrowth indicates fast exhumation rates.  相似文献   

20.
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.  相似文献   

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