Oxygen Isotopic Study on the Date‐Nagai Skarn‐Type Tungsten Deposit,Northeastern Japan

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.     

Fluid flow and mass transport at the Valentine wollastonite deposit, Adirondack Mountains, New York State

The Valentine wollastonite skarn in the north-west Adirondack Mountains, New York, is a seven million ton deposit which resulted from channellized infiltration of H₂O-rich, silica-bearing fluids. The wollastonite formed by reaction of these fluids with non-siliceous calcite marble. The skarn formed at the contact of the syenitic Diana Complex and was subsequently overprinted by Grenville-age granulite facies metamorphism and retrograde hydrothermal alteration during uplift. Calcite marbles adjacent to the deposit have generally high δ¹⁸O values (c. 21‰), typical of Grenville marbles which have not exchanged extensively with externally derived fluids. Carbon isotopic fractiona-tions between coexisting calcite and graphite in the marbles indicate equilibration at 675d? C, consistent with the conditions of regional metamorphism. Oxygen isotopic ratios from wollastonite skarn are lower than in the marbles and show a 14‰ variation (-1‰ to 13‰). Some isotopic heterogeneity is preserved from skarn formation, and some represents localized exchange with low-δ¹⁸O retrograde fluids. Detailed millimetre- to centimetre-scale isotopic profiles taken across skarn/marble contacts reveal steep δ¹⁸O gradients in the skarn, with values increasing towards the marble. The gradients reflect isotopic evolution of the fluid as it reacted with high δ¹⁸O calcite to form wollastonite. Calcite in the marble preserves high δ¹⁸O values to within <5 mm of the skarn contact. The preservation of high δ¹⁸O values in marbles at skarn contacts and the disequilibrium fractionation between wollastonite skarn and calcite marble across these contacts indicate that the marbles were not infiltrated with significant quantities of the fluid. Thus, the marbles were relatively impermeable during both the skarn formation and retrograde alteration. Skarn formation may have been episodic and fluid flow was either chaotic or dominantly parallel to lithological contacts. Although these steep isotope gradients resemble fluid infiltration fronts, they actually represent the sides of the major flow system. Because chromatographic infiltration models of mass transport require the assumption of pervasive fluid flow through a permeable rock, such models are not applicable to this hydrothermal system and, by extension, to many other metamorphic systems where low-permeability rocks restrict fluid migration pathways. Minimum time-integrated fluid fluxes have been calculated at the Valentine deposit using oxygen isotopic mass balance, reaction progress of fluid buffering reactions, and silica mass balance. All three approaches show that large volumes of fluid were necessary to produce the skarn, but silica mass balance calculations yield the largest minimum flux and are hence the most realistic.     

Geochemistry of major and rare earth elements in garnet of the Kal-e Kafi skarn,Anarak Area,Central Iran: Constraints on processes in a hydrothermal system

Grossular-andradite (grandite) garnets, precipitated from hydrothermal solutions is associated with contact metamorphism in the Kal-e Kafi skarn show complex oscillatory chemical zonation. These skarn garnets preserve the records of the temporal evolution of contact metasomatism. According to microscopic studies and microprobe analysis profiles, the studied garnet has two distinct parts: the intermediate (granditic) composition birefringent core that its andradite content based on microprobe analysis varies between 0.68–0.7. This part is superimposed with more andraditic composition, and the isotropic rim which its andradite content regarding microprobe analysis ranges between 0.83–0.99. Garnets in the studied sample are small (0.5–2 mm in diameter) and show complex oscillatory zoning. Electron microprobe analyses of the oscillatory zoning in grandite garnet of the Kal-e Kafi area showed a fluctuation in chemical composition. The grandite garnets normally display core with intermediate composition with oscillatory Fe-rich zones at the rim. Detailed study of oscillatory zoning in grandite garnet from Kal-e Kafi area suggests that the garnet has developed during early metasomatism involving monzonite to monzodiorite granitoid body intrusion into the Anarak schist- marble interlayers. During this metasomatic event, Al, Fe, and Si in the fluid have reacted with Ca in carbonate rocks to form grandite garnet. The first step of garnet growth has been coeval with intrusion of the Kal-e Kafi granitoid into the Anarak schist- marble interlayers. In this period of garnet growth, change in fluid composition may cause the garnet to stop growing temporarily or keep growing but in a much slower rate allowing Al to precipitate rather than Fe. The next step consists of pervasive infiltration of Fe rich fluids and Fe rich grandite garnets formation as the rim of previously formed more Al rich garnets. Oscillatory zoning in the garnet probably reflects an oscillatory change in the fluid composition which may be internally and/or externally controlled. The rare earth elements study of these garnets revealed enrichment in light REEs (LREE) with a maximum at Pr and Nd and a negative to no Eu anomaly. This pattern is resulted from the uptake of REE out of hydrothermal fluids by growing crystals of calcsilicate minerals principally andradite with amounts of LREE controlled by the difference in ionic radius between Ca⁺⁺ and REE³⁺ in garnet x site.     

Stable isotopic signatures of superposed fluid events in granulite facies marbles of the Rauer Group, East Antarctica

The role of volatiles in the stabilization of the lower (granulite facies) crust is contentious. Opposing models invoke infiltration of CO₂-rich fluids or generally vapour-absent conditions during granulite facies metamorphism. Stable isotope and petrological studies of granulite facies metacarbonates can provide constraints on these models. In this study data are presented from metre-scale forsteritic marble boudins within Archaean intermediate to felsic orthogneisses from the Rauer Group, East Antarctica. Forsteritic marble layers and associated calcsilicates preserve a range of ¹³C- and ¹⁸O-depleted calcite isotope values (δ¹³C= -9.9 to -3.0% PDB, δ¹⁸O = 4.0 to 12.1% SMOW). A coupled trend of ¹³C and ¹⁸O depletion (～2%, ～5%, respectively) from core to rim across one marble layer is inconsistent with pervasive CO₂ infiltration during granulite facies metamorphism, but does indicate localized fluid-rock interaction. At another locality, more pervasive fluid infiltration has resulted in calcite having uniformly low, carbonatite-like δ¹⁸O and δ¹³C values. A favoured mechanism for the low δ¹⁸O and δ¹³C values of the marbles is infiltration by fluids that were derived from, or equilibrated with, a magmatic source. It is likely that this fluid-rock interaction occurred prior to high-grade metamorphism; other fluid-rock histories are not, however, ruled out by the available data. Coupled trends of ¹³C and ¹⁸O depletion are modified to even lower values by the superposed development of small-scale metasomatic reaction zones between marbles and internally folded mafic (?) interlayers. The timing of development of these layers is uncertain, but may be related to Archaean high-temperature (>1000d?C) granulite facies metamorphism.     

δ18O and yttrium zoning in garnet: time markers for fluid flow?

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.     

Role of H2O in the formation of garnet coronas during near‐isobaric cooling of mafic granulites: the Tasiusarsuaq terrane,southern West Greenland

The Mesoarchaean Tasiusarsuaq terrane of southern West Greenland consists of Tonalite–trondhjemite–granodiorite gneisses and, locally, polymetamorphic mafic and ultramafic rocks. The terrane experienced medium‐pressure granulite facies conditions during M_1A in the Neoarchean, resulting in the development of two‐pyroxene melanosome assemblages in mafic granulites containing garnet‐bearing leucosome. Reworking of these rocks during retrogression introduced garnet to the melanosome in the form of overgrowths, coronas and grain necklaces that separate the mafic minerals from plagioclase. NCFMASHTO pseudosection modelling constrains the peak metamorphism during M_1A to ～850 °C and 7.5 kbar at fluid‐saturated conditions. Following M_1A, the rocks retained their M_1A H₂O content and became fluid‐undersaturated as they underwent near‐isobaric cooling to ～700 °C and 6.5–7 kbar, prior to reworking during M_1B. These low H₂O contents allowed for the formation of garnet overgrowths and coronas during M_1B. The stability of garnet is greatly increased to lower pressure and temperature in fluid‐absent, fluid‐undersaturated mafic rocks, indicating that fluid and melt loss during initial granulite facies metamorphism is essential for the introduction of garnet, and the formation of garnet coronas, during retrogression. The occurrence of garnet coronas is consistent with, but not unique to, near‐isobaric cooling paths.     

Constraints on the application of carbon isotope thermometry in high- to ultrahigh-temperature metamorphic terranes

Nine marble horizons from the granulite facies terrane of southern India were examined in detail for stable carbon and oxygen isotopes in calcite and carbon isotopes in graphite. The marbles in Trivandrum Block show coupled lowering of δ¹³C and δ¹⁸O values in calcite and heterogeneous single crystal δ¹³C values (? 1 to ? 10‰) for graphite indicating varying carbon isotope fractionation between calcite and graphite, despite the granulite facies regional metamorphic conditions. The stable isotope patterns suggest alteration of δ¹³C and δ¹⁸O values in marbles by infiltration of low δ¹³C–δ¹⁸O‐bearing fluids, the extent of alteration being a direct function of the fluid‐rock ratio. The carbon isotope zonation preserved in graphite suggests that the graphite crystals precipitated/recrystallized in the presence of an externally derived CO₂‐rich fluid, and that the infiltration had occurred under high temperature and low f_O2 conditions during metamorphism. The onset of graphite precipitation resulted in a depletion of the carbon isotope values of the remaining fluid+calcite carbon reservoir, following a Rayleigh‐type distillation process within fluid‐rich pockets/pathways in marbles resulting in the observed zonation. The results suggest that calcite–graphite thermometry cannot be applied in marbles that are affected by external carbonic fluid infiltration. However, marble horizons in the Madurai Block, where the effect of fluid infiltration is not detected, record clear imprints of ultrahigh temperature metamorphism (800–1000 °C), with fractionations reaching <2‰. Zonation studies on graphite show a nominal rimward lowering δ¹³C on the order of 1 to 2‰. The zonation carries the imprint of fluid deficient/absent UHT metamorphism. Commonly, calculated core temperatures are > 1000 °C and would be consistent with UHT metamorphism.     

Isotopic constraints on fluid infiltration from an eclogite facies shear zone, Holsenøy, Norway

Granulite facies anorthosites on Holsenøy Island in the Bergen Arcs region of western Norway are transected by shear zones 0.1–100 m wide characterized by eclogite facies assemblages. Eclogite formation is related to influx of fluid along the shears at temperatures of c. 700d?C and pressures in excess of 1.7 GPa. Combined carbon and nitrogen stable isotope, ⁴⁰Ar/³⁶Ar, trace-element and petrological data have been used to determine the nature and distribution of fluids across the anorthosite-eclogite transition. A metre-wide drilled section traverses the eclogitic centre of the shear into undeformed granulite facies garnet-clinopyroxene anorthosite. Clinozoisite occurs along grain boundaries and microcracks in undeformed anorthosite up to 1 m from the centre of the shear and clinozoisite increases in abundance as the edge of the shear zone is approached. The eclogite-granulite transition, marked by the appearance of sodic pyroxene and loss of albite, occurs within the most highly sheared section of the traverse. The jadeite-in reaction coincides with increased paragonite activity in mica. The separation between paragonite and clinozoisite reaction fronts can be semiquantitatively modelled assuming advective fluid flow perpendicular to the shear zone. The inner section of the traverse (0.25 m wide) is marked by retrogressive replacement of omphacite by plagioclase + paragonite accompanied by veins of quartz-phengite-plagioclase. C-N-Ar characteristics of fluid inclusions in garnet show that fluids associated with precursor granulite, eclogite and retrogressed eclogite are isotopically distinct. The granulite-eclogite transition coincides with a marked change in CO₂ abundance and δ¹³C (<36ppm, δ¹³C=-2% in the granulite; <180 ppm, δ¹³C=-10% in the eclogite). The distribution of Ar indicates mixing between influxed fluid (⁴⁰Ar/³⁶Ar > 25 times 10³) and pre-existing Ar in the granulite (⁴⁰Ar/³⁶Ar < 8 times 10³). δ¹⁵N values decrease from +6% in the anorthosite to +3% within the eclogite shear. The central zone of retrogressed eclogite post-dates shearing and is characterised by substantial enrichment of Si, K, Ba and Rb. Fluids are CO₂-rich (δ¹³C ～ -5%) with variable N₂ and Ar abundances and isotopic compositions. Both Ar and H₂O have penetrated the underformed granulite fabric more than 0.5m beyond the granulite/eclogite transition during eclogite formation. Argon isotopes show a mixing profile consistent with diffusion through an interconnecting H₂O-rich fluid network. In contrast, a carbon-isotope front coincides with the deformation boundary layer, indicating that the underformed anorthosite was impervious to CO₂-rich fluids. This is consistent with the high dihedral angle of carbonic fluids, and may be interpreted in terms of evolving fluid compositions within the shear zone.     

Oxygen isotope thermometry using quartz inclusions in garnet

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 (Alm_60–75) 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.     

Oxygen isotope speedometry in granulite facies garnet recording fluid/melt–rock interaction (Sør Rondane Mountains,East Antarctica)

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.     

江西永平铜矿矽卡岩矿物特征及其地质意义

永平铜矿含矿岩石主要为绿帘石透辉石石榴石矽卡岩,这种岩石类型是与斑岩体有关的矽卡岩铜矿的典型赋矿岩石。通过对这一主要赋矿矽卡岩的研究,我们发现石榴石生长分为两个阶段:(1)早期石榴石:主要分布在石榴石颗粒核部,XAdr=1.0,主要以钙铁榴石为主,说明早期流体中可能含有较多的铁,是在较氧化条件下形成的;(2)晚期石榴石,沿石榴石裂隙重新成核或者在靠近流体通道的早期石榴石表面生长,出现震荡环带,XAdr=0.46~0.99,为钙铁-钙铝石榴石系列。石榴石发生变化的期间也形成新的矿物,如绿帘石、萤石、方解石和石英等。共存石榴石和绿帘石矿物中存在Fe3+-Al3+之间的替代,说明流体的氧逸度、组分浓度或aFe3+/aAl3+可能发生了变化。金属矿物也可能是在这一阶段形成的。永平铜矿矽卡岩从接触带到大理岩空间上有分带现象。从岩体到围岩的变化趋势为:石榴石含量减少,颜色存在红棕色-棕色-棕绿色-黄绿色-浅黄色的变化趋势;矿石品位降低,这与石榴石中Al2O3含量的变化较一致。我们认为这种变化是含矿热液对早期矽卡岩进行再交代改造的结果,表现为石榴石和绿帘石中Fe3+-Al3+含量的变化,并将Cu等金属沉淀下来。根据矽卡岩矿物的这些特征,在矿床勘探时,可依据棕色石榴石来追踪主矿体的位置。     

Fluid heterogeneity during granulite facies metamorphism in the Adirondacks: stable isotope evidence

The preservation of premetamorphic, whole-rock oxygen isotope ratios in Adirondack metasediments shows that neither these rocks nor adjacent anorthosites and gneisses have been penetrated by large amounts of externally derived, hot CO₂-H₂O fluids during granulite facies metamorphism. This conclusion is supported by calculations of the effect of fluid volatilization and exchange and is also independently supported by petrologic and phase equilibria considerations. The data suggest that these rocks were not an open system during metamorphism; that fluid/rock ratios were in many instances between 0.0 and 0.1; that externally derived fluids, as well as fluids derived by metamorphic volatilization, rose along localized channels and were not pervasive; and thus that no single generalization can be applied to metamorphic fluid conditions in the Adirondacks.Analyses of 3 to 4 coexisting minerals from Adirondack marbles show that isotopic equilibrium was attained at the peak of granulite and upper amphibolite facies metamorphism. Thus the isotopic compositions of metamorphic fluids can be inferred from analyses of carbonates and fluid budgets can be constructed.Carbonates from the granulite facies are on average, isotopically similar to those from lower grade or unmetamorphosed limestones of the same age showing that no large isotopic shifts accompanied high grade metamorphism. Equilibrium calculations indicate that small decreases in ¹⁸O, averaging 1 permil, result from volatilization reactions for Adirondack rock compositions. Additional small differences between amphibolite and granulite facies marbles are due to systematic lithologie differences.The range of Adirondack carbonate ¹⁸O values (12.3 to 27.2) can be explained by the highly variable isotopic compositions of unmetamorphosed limestones in conjunction with minor ¹⁸O and ¹³C depletions caused by metamorphic volatilization suggesting that many (and possibly most) marbles have closely preserved their premetamorphic isotopic compositions. Such preservation is particularly evident in instances of high ¹⁸O calcites (25.0 to 27.2), low ¹⁸O wollastonites (–1.3 to 3.5), and sharp gradients in ¹⁸O (18 permil/15m between marble and anorthosite, 8 permil/25 m in metasediments, and 6 permil/1 m in skarn).Isotopic exchange is seen across marble-anorthosite and marble-granite contacts only at the scale of a few meters. Small (<5 m) marble xenoliths are in approximate exchange equilibrium with their hosts, but for larger xenoliths and layers of marble there is no evidence of exchange at distances greater than 10 m from meta-igneous contacts.     

Geochemical constraints of the eclogite and granulite facies metamorphism as recognized in the Raobazhai complex from North Dabie Shan,China

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 (δ¹⁸O_VSMOW = 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 ε_Nd(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.     

Origin and evolution of skarn fluids,Empire zinc skarns,Central Mining District,New Mexico,U.S.A.

Garnet-pyroxene-sphalerite skarns in the Empire Mine replace Paleozoic carbonates adjacent to the Tertiary Hanover-Fierro granodiorite. Skarn geometry suggests that fluids migrated up pre-ore dikes, faults and the igneous contact, and were deflected laterally into the permeable Tierra Blanca Limestone beneath the relatively impermeable Parting Shale.Silicates associated with propylitically altered pre-ore dikes are enriched in deuterium (D), and depleted in¹⁸O relative to the Hanover-Fierro pluton and post-ore igneous rocks. Early skarn silicates are also depleted in¹⁸O with respect to the pluton, while later skarn minerals are depleted in both D and¹⁸O. Variations in isotope composition of alteration and skarn minerals indicate isotope heterogeneities in mineralizing fluids, even at the small scale of centimeters. Isotope thermometry indicates that there is some degree of subsolidus re-equilibration of igneous and alteration minerals.Several possible fluid flow regimes may have operated to produce the fluids calculated to be in exchange equilibrium with the various rocks and minerals of the Empire skarn system, and mixing of end-member meteoric, formation and magmatic fluids in different proportions can produce observed δDδ¹⁸O trends. An end-member magmatic fluid could produce the D-enrichment observed for early skarn fluids, but this would require isolating magmatic fluids from external fluid sources during cooling of the system from magmatic temperatures of 700°C to skarn temperatures of the order of ≤ 400°C. The D-enrichment may also be explained by the mixing of magmatic and formation waters. Lower δD values, however, require that a large proportion of late-stage skarn fluids must be a D-depleted Tertiary meteoric water, and magmatic water is restricted to a relatively minor component.The end-member mixing approach indicates significant changes in fluid flow systematics over a relatively narrow range in temperature. Alternatively, observed trends in both δD and δ¹⁸O for skarn fluids can also be reproduced by interacting a D-depleted meteoric water with the Hanover-Fierro pluton at low and variable system water-rock ratios, and temperatures between 250 and 400°C. During migration along the long fluid flow paths implied by the low system water-rock ratios (≤0.1), the salinity of dilute meteoric waters could increase through interaction with minerals or leaking fluid inclusions in the country rock. Correlation of isotope depletions of the carbonate wallrocks with inferred fluid flow conduits, suggests significant amounts of fluid-rock exchange at relatively high local water-rock ratios during focusing of flow by critical structures. Although different C sources might require smaller values, it is clear that large (>1) local water-rock ratios are required to produce depletions observed in both¹⁸O and¹³C in hydrothermal calcites. Stable isotope evidence does not require the presence of a significant magmatic fluid component, and suggests that the bulk of the skarn fluids could instead be derived predominantly from a D-depleted meteoric water.     

Eclogite origin and timings in the North Qinling terrane,and their bearing on the amalgamation of the South and North China Blocks

The amalgamation of South (SCB) and North China Blocks (NCB) along the Qinling‐Dabie orogenic belt involved several stages of high pressure (HP)‐ultra high pressure (UHP) metamorphism. The new discovery of UHP metamorphic rocks in the North Qinling (NQ) terrane can provide valuable information on this process. However, no precise age for the UHP metamorphism in the NQ terrane has been documented yet, and thus hinders deciphering of the evolution of the whole Qinling‐Dabie‐Sulu orogenic belt. This article reports an integrated study of U–Pb age, trace element, mineral inclusion and Hf isotope composition of zircon from an eclogite, a quartz vein and a schist in the NQ terrane. The zircon cores in the eclogite are characterized by oscillatory zoning or weak zoning, high Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, pronounced Eu anomalies and steep heavy rare earth element (HREE) patterns. The zircon cores yield an age of 796 ± 13 Ma, which is taken as the protolith formation age of the eclogite, and implies that the NQ terrane may belong to the SCB before it collided with the NCB. The ?_Hf(t) values vary from ?11.3 to 3.2 and corresponding two‐stage Hf model ages are 2402 to 1495 Ma, suggesting the protolith was derived from an enriched mantle. In contrast, the metamorphic zircon rims show no zoning or weak zoning, very low Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, insignificant Eu anomalies and flat HREE patterns. They contain inclusions of garnet, omphacite and phengite, suggesting that the metamorphic zircon formed under eclogite facies metamorphic conditions, and their weighted mean ²⁰⁶Pb/²³⁸U age of 485.9 ± 3.8 Ma was interpreted to date the timing of the eclogite facies metamorphism. Zircon in the quartz vein is characterized by perfect euhedral habit, some oscillatory zoning, low Th/U ratios and variable HREE contents. It yields a weighted mean U–Pb age of 480.5 ± 2.5 Ma, which registers the age of fluid activity during exhumation. Zircon in the schist is mostly detrital and U–Pb age peaks at c. 1950 to 1850, 1800 to 1600, 1560 to 1460 and 1400 to 1260 Ma with an oldest grain of 2517 Ma, also suggesting that the NQ terrane may have an affinity to the SCB. Accordingly, the amalgamation between the SCB and the NCB is a multistage process that spans c. 300 Myr, which includes: the formation of the Erlangping intra‐oceanic arc zone onto the NCB before c. 490 Ma, the c. 485 Ma crustal subduction and UHP metamorphism of the NQ terrane, the c. 430 Ma arc‐continent collision and granulite facies metamorphism, the 420 to 400 Ma extension and rifting in relation to the opening of the Palaeo‐Tethyan ocean, the c. 310 Ma HP eclogite facies metamorphism of oceanic crust and associated continental basement, and the final 250 to 220 Ma continental subduction and HP–UHP metamorphism.     

Eclogite-facies fluid infiltration: constraints from δ18O zoning in garnet

In situ analysis reveals that eclogite-facies garnets are zoned in δ¹⁸O with lower values in the core and rims that are ~1.5 to 2.5 ‰ higher. This pattern is present in 9 out of 12 garnets analyzed by SIMS from four orogenic eclogite terranes, and correlates with an increase in the mole fraction of pyrope and Mg/Fe ratio from core to rim, indicating prograde garnet growth. At the maximum temperatures and the time-scales experienced by these garnets, calculated intragranular diffusion distances for oxygen are small (<5 μm), indicating that δ¹⁸O records primary growth zoning and not diffusive exchange. The oxygen isotope gradients are larger than could form due to temperature changes during closed-system mineral growth. Thus, gradients reflect the compositions of fluids infiltrating during prograde metamorphism. Values of δ¹⁸O in garnet cores range from ?1 to 15 ‰, likely preserving the composition of the eclogite protoliths. Two garnet cores from the Almenningen eclogite in the Western Gneiss Region, Norway, have δ¹⁸O ~?1 ‰ and are the first negative δ¹⁸O eclogites identified in the region. In contrast with orogenic eclogites, seven high δ¹⁸O garnets (>5 ‰) from two kimberlites are homogeneous in δ¹⁸O, possibly due to diffusive exchange, which is possible for prolonged periods at higher mantle temperatures. Homogeneity of δ¹⁸O in garnets outside the normal mantle range (5–6 ‰) may be common in kimberlitic samples.     

The stable isotope signature of kilometre-scale fracturedominated metamorphic fluid pathways, Mary Kathleen, Australia

Abstract Large calcite veins and pods in the Proterozoic Corella Formation of the Mount Isa Inlier provide evidence for kilometre-scale fluid transport during amphibolite facies metamorphism. These 10- to 100-m-scale podiform veins and their surrounding alteration zones have similar oxygen and carbon isotopic ratios throughout the 200 × 10-km Mary Kathleen Fold Belt, despite the isotopic heterogeneity of the surrounding wallrocks. The fluids that formed the pods and veins were not in isotopic equilibrium with the immediately adjacent rocks. The pods have δ¹³C_calcite values of –2 to –7% and δ¹⁸O_calcite values of 10.5 to 12.5%. Away from the pods, metadolerite wallrocks have δ¹⁸O_whole-rock values of 3.5 to 7%. and unaltered banded calc-silicate and marble wallrocks have δ¹³C_calcite of –1.6 to –0.6%, and δ¹⁸O_calcite of 18 to 21%. In the alteration zones adjacent to the pods, the δ¹⁸O values of both metadolerite and calc-silicate rocks approach those of the pods. Large calcite pods hosted entirely in calc-silicates show little difference in isotopic composition from pods hosted entirely in metadolerite. Thus, 100- to 500-m-scale isotopic exchange with the surrounding metadolerites and calc-silicates does not explain the observation that the δ¹⁸O values of the pods are intermediate between these two rock types. Pods hosted in felsic metavolcanics and metasiltstones are also isotopically indistinguishable from those hosted in the dominant metadolerites and calc-silicates. These data suggest the veins are the product of infiltration of isotopically homogeneous fluids that were not derived from within the Corella Formation at the presently exposed crustal level, although some of the spread in the data may be due to a relatively small contribution from devolatilization reactions in the calc-silicates, or thermal fluctuations attending deformation and metamorphism. The overall L-shaped trend of the data on plots of δ¹³C vs. δ¹⁸O is most consistent with mixing of large volumes of externally derived fluids with small volumes of locally derived fluid produced by devolatilization of calc-silicate rocks. Localization of the vein systems in dilatant sites around metadolerite/calc-silicate boundaries indicates a strong structural control on fluid flow, and the stable isotope data suggest fluid migration must have occurred at scales greater than at least 1 km. The ultimate source for the external fluid is uncertain, but is probably fluid released from crystallizing melts derived from the lower crust or upper mantle. Intrusion of magmas below the exposed crustal level would also explain the high geothermal gradient calculated for the regional metamorphism.     

Stable isotopic and petrological constraints on scapolitization of the Whitestone meta-anorthosite,Grenville Province,Ontario*

The Whitestone Anorthosite (WSA), located in the Central Gneiss Belt of the south-western Grenville Province, Ontario, exhibits a nearly concentric metamorphic envelope characterized by an increase in modal scapolite, hornblende, epidote and garnet, developed around a core of granulite facies clinopyroxene ± orthopyroxene ± garnet meta-anorthosite. Scapolite- and hornblende-bearing assemblages develop mainly at the expense of plagioclase and pyroxene within the envelope. Stable isotopic and petrological data for scapolite-bearing mineral assemblages within meta-anorthosite constrain the source of carbon responsible for CO₃-scapolite formation and the extent of fluid/rock interaction between the anorthosite and adjacent lithologies. Stable isotopic data indicate increasing δ¹⁸O and δ¹³C from core to margin of the meta-anorthosite and for samples from the southern extension of the WSA, where it is ductilely deformed within the Parry Sound Shear Zone (PSSZ). The average δ¹⁸O_SMOW value (whole rock) for the WSA core is 6.9‰, increasing to 11.5‰ where the WSA is in tectonic contact with marble breccia. The average δ¹³C_PBD value of scapolite in meta-anorthosite from the centre of the WSA is -3.4‰, increasing to -0.5‰ at the eastern (marble) contact. Average values of δ¹³C for scapolite and whole-rock δ¹⁸O for samples from the shear zone are -1.0 and 8.0‰, respectively. Marbles have average δ¹⁸O and δ¹³C values of 19.2 and -0.4‰, respectively. The sulphate content of texturally primary scapolite decreases from the core of the WSA (X_SO4= 0.48) to the eastern contact (≤0.05). Texturally late scapolite after plagioclase and garnet tends to be CO₃-rich relative to texturally primary scapolite, and some scapolite grains show zoning in the anion site with CO₃-enriched rims. Scapolite composition may vary at any scale from a single grain to outcrop. The pattern of isotopic enrichment in ¹³C and ¹⁸O preserved in the eastern margin of the WSA is consistent with marble as the major source of fluid contributing to the formation of the metamorphic envelope. The decrease in X_SO4 and increase in X_CO3 in scapolite toward the margin of the WSA indicate that the volatile content was reset by, or developed from, a CO₂-bearing fluid. Assuming derivation of fluid from marble, minimum fluid/rock values at the margin of the WSA range from 0.03 for the least enriched, to 0.30 for the most isotopically enriched samples. Although marble is not found in immediate contact with samples of sheared meta-anorthosite from the PSSZ, a marble source is also consistent with the C and O isotope composition and anion chemistry of scapolite within these samples.     

Fluids in granulites of the Southern Marginal Zone of the Limpopo Belt, South Africa

The Southern Marginal Zone of the Limpopo Belt in South Africa is characterised by a granulite and retrograde hydrated granulite terrane. The Southern Marginal Zone is, therefore, perfectly suitable to study fluids during and after granulite facies metamorphism by means of fluid inclusions and equilibrium calculations. Isolated and clustered high-salinity aqueous and CO₂(-CH₄) fluid inclusions within quartz inclusions in garnet in metapelites demonstrate that these immiscible low H₂O activity fluids were present under peak metamorphic conditions (800-850 °C, 7.5-8.5 kbar). The absence of widespread high-temperature metasomatic alteration indicates that the brine fluid was probably only locally present in small quantities. Thermocalc calculations demonstrate that the peak metamorphic mineral assemblage in mafic granulites was in equilibrium with a fluid with a low H₂O activity (0.2-0.3). The absence of water in CO₂-rich fluid inclusions is due to either observation difficulties or selective water leakage. The density of CO₂ inclusions in trails suggests a retrograde P-T path dominated by decompression at T<600 °C. Re-evaluation of previously published data demonstrates that retrograde hydration of the granulites at 600 °C occurred in the presence of H₂O and CO₂-rich fluids under P-T conditions of 5-6 kbar and ~600 °C. The different compositions of the hydrating fluid suggest more than one fluid source.     

Formation of wollastonite-bearing marbles during late regional metamorphic channelled fluid flow in the Upper Calcsilicate Unit of the Reynolds Range Group,central Australia*

Abstract Granulite facies marbles from the Upper Calcsilicate Unit of the Reynolds Range, central Australia, contain metre-scale wollastonite-bearing layers formed by infiltration of water-rich (X_CO2= 0.1–0.3) fluids close to the peak of regional metamorphism at c. 700° C. Within the wollastonite marbles, zones that contain <10% wollastonite alternate on a millimetre scale with zones containing up to 66% wollastonite. Adjacent wollastonite-free marbles contain up to 11% quartz that is uniformly distributed. This suggests that, although some wollastonite formed by the reaction calcite + quartz = wollastonite + CO₂, the wollastonite-rich zones also underwent silica metasomatism. Time-integrated fluid fluxes required to cause silica metasomatism are one to two orders of magnitude higher than those required to hydrate the rocks, implying that time-integrated fluid fluxes varied markedly on a millimetre scale. Interlayered millimetre -to centimetre-thick marls within the wollastonite marbles contain calcite + quartz without wollastonite. These marls were probably not infiltrated by significant volumes of water-rich fluids, providing further evidence of local fluid channelling. Zones dominated by grandite garnet at the margins of the marl layers and marbles in the wollastonite-bearing rocks probably formed by Fe metasomatism, and may record even higher fluid fluxes. The fluid flow also reset stable isotope ratios. The wollastonite marbles have average calcite (Cc) δ¹⁸O values of 15.4 ± 1.6% that are lower than the average δ¹⁸O(Cc) value of wollastonite-free marbles (c. 17.2 ± 1.2%). δ¹³C(Cc) values for the wollastonite marbles vary from 0.4% to as low as -5.3%, and correlations between δ¹⁸O(Cc) and δ¹³C(Cc) values probably result from the combination of fluid infiltration and devolatilization. Fluids were probably derived from aluminous pegmatites, and the pattern of mineralogical and stable isotope resetting implies that fluid flow was largely parallel to strike.