Causes of the uniformly high crystallinity of graphite in large epigenetic deposits

In low-pressure environments, precipitation of graphite is hindered at low to moderate temperatures by the high solubility of carbon in C-O-H fluids and by kinetic barriers to nucleation. Those low-temperature fluids that do attain saturation tend to precipitate graphite continuously during flow and cooling, thereby producing widely dispersed films of low-crystallinity graphite. In contrast, at high temperatures, particularly when combined with high pressures, the precipitation of graphite is enhanced by decreased solubility of carbon in C-O-H fluids and by improved nucleation under those conditions. The longevity of fluid systems in high-temperature, high-pressure terranes permits efficient, long-term scavenging of dispersed carbon from the crust. The latter may be redistributed in a much more concentrated form as fluids rise, cool and decompress, and as the carbon is finally precipitated as highly crystalline graphite in fracture systems. The combined effects of the thermochemical controls on carbon solubility and the geological controls on fluid generation, movement and P – T  pathways are the reason that large, epigenetic graphite deposits form dominantly at high temperatures and pressures. Those high-temperature, high-pressure conditions, in turn, account for the uniformly high crystallinity of the fluid-deposited graphite.     

Thermodynamic modelling of a cooling C–O–H fluid–graphite system: implications for hydrothermal graphite precipitation

Carbon-saturated crustal fluids in the C–O–H system comprise H₂O, CO₂ and CH₄ as the most important fluid species. Graphite precipitation from a cooling C–O–H is discussed for two different systems, namely for a fluid–rock system in which no transfer of atomic oxygen and hydrogen between the fluid and the rock is possible (closed fluid system), and for an open fluid system. Thermodynamic model calculations show that the graphite-forming reactions and the graphite precipitation potential are different for these two systems. Furthermore, the calculations demonstrate that for both systems, the following factors play a role in determining the graphite precipitation potential, i.e. (1) the redox state of the fluid, (2) the initial pressure and temperature conditions and (3) whether cooling is combined with decompression. Open and closed fluid system graphite precipitation can be distinguished from each other using fluid inclusion and stable carbon isotope studies. The results of this study provide insight in the formation of hydrothermal graphite deposits.     

http://www.sciencedirect.com/science/article/pii/S1674987111001083

Stable carbon isotope geochemistry provides important information for the recognition of fundamental isotope exchange processes related to the movement of carbon in the lithosphere and permits the elaboration of models for the global carbon cycle.Carbon isotope ratios in fluid-deposited graphite are powerful tools for unravelling the ultimate origin of carbon（organic matter,mantle,or carbonates） and help to constrain the fluid history and the mechanisms involved in graphite deposition.Graphite precipitation in fluid-deposited occurrences results from CO₂- and/or CH₄-bearing aqueous fluids.Fluid flow can be considered as both a closed（without replenishment of the fluid） or an open system（with renewal of the fluid by successive fluid batches）.In closed systems,carbon isotope systematics in graphite is mainly governed by Rayleigh precipitation and/or by changes in temperature affecting the fractionation factor between fluid and graphite.Such processes result in zoned graphite crystals or in successive graphite generations showing,in both cases, isotopic variation towards progressive ^l3C or ¹²C enrichment（depending upon the dominant carbon phase in the fluid.CO₂ or CH₄,respectively）.In open systems,in which carbon is episodically introduced along the fracture systems,the carbon systematics is more complex and individual graphite crystals may display oscillatory zoning because of Rayleigh precipitation or heterogeneous variations of 5’ C values when mixing of fluids or changes in the composition of the fluids are the mechanisms responsible for graphite precipitation.     

Graphite morphologies from the Borrowdale deposit (NW England,UK): Raman and SIMS data

Graphite in the Borrowdale (Cumbria, UK) deposit occurs as large masses within mineralized pipe-like bodies, in late graphite–chlorite veins, and disseminated through the volcanic host rocks. This occurrence shows the greatest variety of crystalline graphite morphologies recognized to date from a single deposit. These morphologies described herein include flakes, cryptocrystalline and spherulitic aggregates, and dish-like forms. Colloform textures, displayed by many of the cryptocrystalline aggregates, are reported here for the first time from any graphite deposit worldwide. Textural relationships indicate that spherulitic aggregates and colloform graphite formed earlier than flaky crystals. This sequence of crystallization is in agreement with the precipitation of graphite from fluids with progressively decreasing supersaturation. The structural characterization carried out by means of Raman spectroscopy shows that, with the exception of colloform graphite around silicate grains and pyrite within the host rocks, all graphite morphologies display very high crystallinity. The microscale SIMS study reveals light stable carbon isotope ratios for graphite (δ ¹³C = −34.5 to −30.2‰), which are compatible with the assimilation of carbon-bearing metapelites in the Borrowdale Volcanic Group magmas. Within the main mineralized breccia pipe-like bodies, the isotopic signatures (with cryptocrystalline graphite being lighter than flaky graphite) are consistent with the composition and evolution of the mineralizing fluids inferred from fluid inclusion data which indicate a progressive loss of CO₂. Late graphite–chlorite veins contain isotopically heavier spherulitic graphite than flaky graphite. This agrees with CH₄-enriched fluids at this stage of the mineralizing event, resulting in the successive precipitation of isotopically heavier graphite morphologies. The isotopic variations of the different graphite morphologies can be attributed therefore, to changes in the speciation of carbon in the fluids coupled with concomitant changes in the XH₂O during precipitation of graphite and associated hydrous minerals (mainly epidote and chlorite).     

Graphite precipitation in C—O—H fluid inclusions: closed system compositional and density changes,and thermobarometric implications

 Equilibrium C–O–H fluid speciation calculations predict that graphite will precipitate from initially graphite saturated fluid inclusions during cooling and exhumation of metamorphic rocks. In the case that no mass is gained or lost by the inclusions, the original X _O ratio [O/(O+H)] of the fluid phase must be maintained. Given this closed system constraint, the down-temperature progress of graphite precipitation can easily be monitored as a function of the varible X _O, and produces some effects that are of significance to fluid inclusion studies: 1. Variation of the H₂O : CO₂ : CH₄ relationship in the graphite-saturated COH fluid, namely increase of X _H2 ^O and decrease of the carbonic fraction; 2. Decrease of fluid density due to precipitation of graphite, which is denser than the residual fluid; 3. Alteration of the CO₂ : CH₄ ratio of the fluid, depending on the initial O : H ratio of the fluid: for X _O>1/3, fluids increase their CO₂ : CH₄ ratio with decreasing temperature, and vice-versa. This implies that the CO₂ : CH₄ ratio measured at room T will not represent the trapping value, which is in any case closer to unity. As a consequence of density reduction, isochores extrapolated from densities observed at room temperature do not pass through the pressure-temperature conditions at which the inclusion was trapped, with pressure underestimates of up to 2 kbar. Actual P-T trapping conditions are located along the equilibrium “bulk isochore” (curve of constant-X _O, constant-volume) of the fluid. Alteration of the CO₂ : CH₄ ratio is a mechanism by which a CO₂-rich or CH₄-rich carbonic phase can be formed from aqueous fluids that are slightly off the neutral X _O=1/3 value. Subsequent segregation of this phase from the aqueous counterpart may account for the formation of pure CO₂ and CH₄ fluids in the upper crust. Received: 15 March 1995 / Accepted: 1 June 1995     

Melting of albite and dehydration of brucite in H2O–NaCl fluids to 9 kbars and 700–900°C: implications for partial melting and water activities during high pressure metamorphism

 The melting reaction: albite_(solid)+ H₂O_(fluid) =albite-H₂O_(melt) has been determined in the presence of H₂O–NaCl fluids at 5 and 9.2 kbar, and results compared with those obtained in presence of H₂O–CO₂ fluids. To a good approximation, albite melts congruently at 9 kbar, indicating that the melting temperature at constant pressure is principally determined by water activity. At 5 kbar, the temperature (T)- mole fraction (X _(H2O) ) melting relations in the two systems are almost coincident. By contrast, H₂O–NaCl mixing at 9 kbar is quite non-ideal; albite melts ∼70 ^°C higher in H₂O–NaCl brines than in H₂O–CO₂ fluids for X _(H2O) =0.8 and ∼100 ^°C higher for X _(H2O) =0.5. The melting temperature of albite in H₂O–NaCl fluids of X _(H2O)=0.8 is ∼100 ^°C higher than in pure water. The P–T curves for albite melting at constant H₂O–NaCl show a temperature minimum at about 5 kbar. Water activities in H₂O–NaCl fluids calculated from these results, from new experimental data on the dehydration of brucite in presence of H₂O–NaCl fluid at 9 kbar, and from previously published experimental data, indicate a large decrease with increasing fluid pressure at pressures up to 10 kbar. Aqueous brines with dissolved chloride salt contents comparable to those of real crustal fluids provide a mechanism for reducing water activities, buffering and limiting crustal melting, and generating anhydrous mineral assemblages during deep crustal metamorphism in the granulite facies and in subduction-related metamorphism. Low water activity in high pressure-temperature metamorphic mineral assemblages is not necessarily a criterion of fluid absence or melting, but may be due to the presence of low a _(H2O) brines. Received: 17 March 1995/Accepted: 9 April 1996     

Fluid-present anatexis of metapelites at El Joyazo (SE Spain): constraints from Raman spectroscopy of graphite

The garnet-biotite-sillimanite anatectic xenoliths in the Neogene dacite dome of El Joyazo (also called Cerro de Hoyazo, SE Spain) contain four types of graphite (I to IV), distinguished on the basis of grain size and texture. Structural characterization of graphite by Laser Raman spectroscopy (LRS) shows systematic differences in the degree of ordering among the four types: only type III is fully consistent with the granulite-facies conditions reached by the xenoliths during partial melting, the others indicate metamorphic temperatures covering amphibolite-facies conditions, with only a few examples of granulite-grade crystallinity. All graphite crystallized before or during the anatectic event, indicating that a large fraction of the graphite did not equilibrate at peak temperatures. The mm-scale coexistence of different types and degrees of ordering in the graphite suggests different origins, i.e. of biogenic derivation and “fluid-deposited”, and is explained in terms of fluid-melt-graphite interaction during the anatectic event. Disequilibrium behaviour during high-temperature metamorphism and anatexis is typical of types I, II and particularly of IV, and is attributed to sluggish kinetics of solid-state graphitization, mainly owing to the limited time of the process and carbon saturation of the intergranular fluid. The coexisting, well-ordered type III graphite is the product of melting in the presence of a graphite-saturated fluid, a process that would account for the deposition of new graphite. The LRS results, together with petrologic observations, suggest that it is possible that high melt fractions can be generated by fluid-present melting of a metasedimentary protolith also in a closed system. Although this contradicts the commonly accepted hypothesis that, due to limited rock porosities, extensive fluid-present melting is precluded unless infiltration occurs, it is a possible end-member model in anatectic settings characterized by rapid heating rates and low-grade source rocks. Received: 14 July 1998 / Accepted: 16 November 1998     

Petrographic,fluid inclusion and isotopic study of the Dikulushi Cu–Ag deposit,Katanga (D.R.C.): implications for exploration

The Dikulushi Cu–Ag vein-type deposit is located on the Kundelungu Plateau, in the southeastern part of the Democratic Republic of Congo (D.R.C.). The Kundelungu Plateau is situated to the north of the Lufilian Arc that hosts the world-class stratiform Cu–Co deposits of the Central African Copperbelt. A combined petrographic, fluid inclusion and stable isotope study revealed that the mineralisation at Dikulushi developed during two spatially and temporally distinct mineralising episodes. An early Cu–Pb–Zn–Fe mineralisation took place during the Lufilian Orogeny in a zone of crosscutting EW- and NE-oriented faults and consists of a sequence of sulphides that precipitated from moderate-temperature, saline H₂O–NaCl–CaCl₂-rich fluids. These fluids interacted extensively with the country rocks. Sulphur was probably derived from thermochemical reduction of Neoproterozoic seawater sulphate. Undeformed, post-orogenic Cu–Ag mineralisation remobilised the upper part of the Cu–Pb–Zn–Fe mineralisation in an oxidising environment along reactivated and newly formed NE-oriented faults in the eastern part of the deposit. This mineralisation is dominated by massive Ag-rich chalcocite that precipitated from low-temperature H₂O–NaCl–KCl fluids, generated by mixing of moderate- and low-saline fluids. The same evolution in mineralisation assemblages and types of mineralising fluids is observed in three other Cu deposits on the Kundelungu Plateau. Therefore, the recognition of two distinct types of (vein-type) mineralisation in the study area has a profound impact on the exploration in the Kundelungu Plateau region. The identification of a Cu–Ag type mineralisation at the surface could imply the presence of a Cu–Pb–Zn–Fe mineralisation at depth.     

The dependence of the partitioning of iron and europium between plagioclase and hydrous tonalitic melt on oxygen fugacity

The dependence of iron and europium partitioning between plagioclase and melt on oxygen fugacity was studied in the system SiO₂(Qz)—NaAlSi₃O₈(Ab)—CaAl₂Si₂O₈(An)—H₂O. Experiments were performed at 500 MPa and 850 °C/750 °C under water saturated conditions. The oxygen fugacity was varied in the log f _O2-range from −7.27 to −15.78. To work at the most reducing conditions the classical double-capsule technique was modified. The sample and a C—O—H bearing sensor capsule were placed next to each other within a BN jacket to minimise loss of hydrogen to the vessel atmosphere. By this setup redox conditions slightly more reducing than the FeO—Fe₃O₄ buffer could be maintained even in 96 h runs. Raman spectra showed that the BN was modified by reaction with hydrogen resulting in a low hydrogen permeability. The partition coefficients determined for Eu at 850 °C and 500 MPa vary from 0.095 at conditions of the Cu—Cu₂O buffer to 1.81 at the most reducing conditions (C—O—H sensor). In the same f _O2 interval the partition coefficient for Fe varies from 0.55 at oxidising conditions to 0.08 at the most reducing conditions. The partitioning of Sm, which was added as a reference for a trivalent REE, does not vary with the oxygen fugacity, yielding an average value for D = 0.07. Lowering the temperature to 750 °C for a given f _O2 decreases the partition coefficient of Eu and increases that of Fe. Comparison with published data at 1 atm and at higher temperatures shows that both temperature and composition of the melt have strong effects on the partitioning behaviour. As the change of the partition coefficients in the geologically relevant f _O2 range is quite strong, element partitioning of Eu and Fe might be used to estimate redox conditions for the genesis of igneous rocks. Furthermore, by modelling the partitioning data it is possible to extract information about the redox state of the melt. Resulting ferric-ferrous ratios show significant differences from those predicted by empirical models. Received: 14 October 1998 / Received: 5 March 1999     

Fluid-assisted retrogression of garnet and P–T history of metapelites from HP/UHP metamorphic terrane (Pohorje Mountains, Eastern Alps)

Fluid inclusions in garnet combined with element X-ray mapping, phase equilibrium modelling and conventional thermobarometry have been used to constrain the metamorphic evolution of metapelitic gneiss from the HP/UHP metamorphic terrane of Pohorje Mountains in the Eastern Alps, Slovenia. Retrograde P–T trajectory from ~2.75 GPa and 780°C is constrained by the composition of matrix phengite (6.66 apfu Si) coexisting with garnet cores, kyanite and quartz. The intersection of the X _Prp = 0.25 isopleth for the garnet with the upper stability boundary for K-feldspar in the matrix indicates near-isothermal decompression to ~0.9 GPa at 720°C. Temperatures over 650°C during this stage are corroborated by the high degree of ordering of graphite inclusions associated with Zn, Mg-rich staurolite and phlogopite in the Mg-rich (X _Prp = 0.22–0.25) garnet cores. Majority of garnet porphyroblasts are depleted in Mg (down to X _Prp = 0.09) and enriched in Mn (up to X _Sps = 0.12) along cracks and at their margins. The associated retrograde mineral assemblage comprises Zn, Mg-poor staurolite, muscovite, biotite–siderophyllite, sillimanite and quartz. The onset of the retrogression and the compositional modification of the garnet porphyroblasts were accompanied by the addition of fluid-deposited graphite around older graphite inclusions, probably due to removal of water from a graphite-buffered COH fluid by dissolution in partial silicic melt. Instantaneous expulsion of water near the melt solidus (640°C, max. 0.45 GPa) caused dissolution of the graphite at redox conditions corresponding to 0.25–1.25 logfO₂ units below the QFM buffer, giving rise to a H₂O–CO₂–CH₄ fluid trapped in primary inclusions in Mn-rich, Mg-poor, almandine garnet that reprecipitated within the retrogressed domains. The absence of re-equilibration textures and consistent densities of the fluid inclusions reflect a near-isochoric cooling postdating the near-isothermal decompression. Bulk water content in the metapelite attained 2 wt% during this stage. The low-degree partial melting and extensive hydration due to the release of the internally derived, low-pressure aqueous fluids led to the reset of peak-pressure mineral assemblage.     

Fluids in low-pressure migmatites: a fluid inclusion study of rocks from the Gennargentu Igneous Complex (Sardinia, Italy)

Summary The low-pressure emplacement of a quartz diorite body in the metapelitic rocks of the Gennargentu Igneous Complex (Sardinia, Italy) produced a contact metamorphic aureole and resulted in migmatisation of part of the aureole through partial melting. The leucosome, formed by dehydration melting involving biotite, is characterised by granophyric intergrowth and abundant magnetite crystals. A large portion of the high temperature contact aureole shows petrographic features that are intermediate between quartz diorite and migmatite s.s. (i.e. hybrid rocks). A fluid inclusion study has been performed on quartz crystals from the quartz diorite and related contact aureole rocks, i.e. migmatite sensu stricto (s.s.) and hybrid rocks. Three types of fluid inclusions have been identified: I) monophase V inclusions, II) L + V, either L-rich or V-rich aqueous saline inclusions and III) multiphase V + L + S inclusions. Microthermometric data characterised the trapped fluid as a complex aqueous system varying from H₂O–NaCl–CaCl₂ in the quartz diorite to H₂O–NaCl–CaCl₂–FeCl₂ in the migmatite and hybrid rocks. Fluid salinities range from high saline fluids (50 wt% NaCl eq.) to almost pure aqueous fluid. Liquid-vapour homogenisation temperatures range from 100 to over 400 °C with an average peak around 300 °C. Temperatures of melting of daughter minerals are between 300 and 500 °C. Highly saline liquid- and vapour-rich inclusions coexist with melt inclusions and have been interpreted as brine exsolved from the crystallising magma. Fluid inclusion data indicate the formation of fluid of high iron activity during the low-pressure partial melting and a fluid mixing process in the hybrid rocks.     

Cu, Mn, and Ag mineralization in the Quebrada Marquesa Quadrangle, Chile: the Talcuna and Arqueros districts

The Quebrada Marquesa Quadrangle in Chile exhibits a series of mineralizations comprising manto-type manganese and copper deposits of Lower Cretaceous age, and copper and silver veins of Tertiary age. The deposits are hosted by volcanic and volcaniclastic units of the Arqueros (Hauterivian-Barremian) and Quebrada Marquesa (Barremian-Albian) Formations. Three episodes of manganese mineralization (Mn_1-3) are recognized within the study area. Hydrothermal activity leading to episodes 1 and 3 was of minor importance, while the second one (Mn₂) gave rise to major manto-type deposits of both manganese and copper in the Talcuna mining district. Extensional faulting during Tertiary time resulted in block faulting and the unroofing of the oldest andesitic volcanics and marine sediments (Arqueros Formation). This episode was accompanied by magmatic and hydrothermal activity leading to vein formation in the Arqueros (Ag) and Talcuna (Cu) districts. The latter veins cross-cut the previous manto-type copper deposits. Ore mineralogy is similar in both styles of mineralization (manto- and vein-type) and consists mainly of chalcopyrite and bornite, with variable amounts of galena, tetrahedrite (vein-related), chalcocite, sphalerite, pyrite, hematite, digenite and covellite. Alteration processes at Talcuna can be divided into two categories, those related to the Lower Cretaceous manto-type episode (LK alteration: chlorite-epidote-calcite-albite, prehnite, zeolite), and those associated with the locally mineralized normal faults of Tertiary age (Tt alteration: chlorite-calcite, sericite). The Arqueros silver veins display an ore mineralogy consisting of arquerite, argentite, native silver, polybasite, cerargyrite and pyrargyrite-proustite; associated alteration includes strong chloritization of the country rock. The manto-type deposits formed from fluids of salinity between 11 and 19 wt.% NaCl equivalent and temperatures between 120 and 205 °C. Mineralizing fluids during the vein-type stage circulated at lower temperatures, between 70 and 170 °C, with salinity values in a wide range from 3 to 27 wt.% NaCl equivalent. This distribution of salinities is interpreted as the result of the complex interplay of two different processes: boiling and fluid mixing; the former is considered to control the major mineralogical, textural and fluid inclusion features of the vein-type deposits. We suggest that the Lower Cretaceous mineralization (manto-type stage) developed in response to widespread hydrothermal activity (geothermal field-type) involving basinal brines. Received: 18 July 1997 / Accepted: 28 January 1998     

Vein graphite deposits: geological settings,origin, and economic significance

Graphite deposits result from the metamorphism of sedimentary rocks rich in carbonaceous matter or from precipitation from carbon-bearing fluids (or melts). The latter process forms vein deposits which are structurally controlled and usually occur in granulites or igneous rocks. The origin of carbon, the mechanisms of transport, and the factors controlling graphite deposition are discussed in relation to their geological settings. Carbon in granulite-hosted graphite veins derives from sublithospheric sources or from decarbonation reactions of carbonate-bearing lithologies, and it is transported mainly in CO₂-rich fluids from which it can precipitate. Graphite precipitation can occur by cooling, water removal by retrograde hydration reactions, or reduction when the CO₂-rich fluid passes through relatively low-fO₂ rocks. In igneous settings, carbon is derived from assimilation of crustal materials rich in organic matter, which causes immiscibility and the formation of carbon-rich fluids or melts. Carbon in these igneous-hosted deposits is transported as CO₂ and/or CH₄ and eventually precipitates as graphite by cooling and/or by hydration reactions affecting the host rock. Independently of the geological setting, vein graphite is characterized by its high purity and crystallinity, which are required for applications in advanced technologies. In addition, recent discovery of highly crystalline graphite precipitation from carbon-bearing fluids at moderate temperatures in vein deposits might provide an alternative method for the manufacture of synthetic graphite suitable for these new applications.     

A preliminary stable isotope study on Mogok Ruby, Myanmar

The primary occurrence of ruby in the Mogok area, northern Myanmar is exclusively found in marble along with spinel–forsterite-bearing marble and phlogopite–graphite marble. These marble units are enclosed within banded biotite–garnet–sillimanite–oligoclase gneisses. Samples of these marbles collected for C–O stable isotope analysis show two trends of δ¹³C–δ¹⁸O variation resulting most likely from fluid–rock interactions. Ruby-bearing marble and phlogopite–graphite marble follow a trend with coupled C–O depletion, whereas spinel–forsterite-bearing marble follows a δ¹⁸O depletion trend with relatively constant δ¹³C values. Ruby formation might have resulted from CO₂-rich fluid–rock interaction, while spinel–forsterite-bearing marble was genetically related to CO₂-poor fluid–rock interaction. Both fluids may have arisen from external sources. Based on graphite Raman spectral thermometry, the estimated temperature for phlogopite–graphite marble, and probably ruby-bearing marble, was lower than 607 °C, and for spinel–forsterite-bearing marble, lower than 710 °C. Contrasting C/O diffusion between graphite/ruby/spinel/forsterite and calcite, local variations of isotopic compositions of newly formed minerals as a result of non-pervasive fluid infiltration, and open-system isotopic disturbance during cooling may have affected C-/O-isotopic fractionations between minerals. The estimated high formation temperatures for ruby and spinel/forsterite imply that the parental fluids may have been related to nearby igneous intrusions and/or metamorphic processes. Whether these two types of fluid were genetically related is unclear based on the present data.     

Multiple Dolomitization and Fluid Flow Events in the Precambrian Dengying Formation of Sichuan Basin,Southwestern China

The Precambrian Dengying Formation is a set of large-scale, extensively dolomitized, carbonate reservoirs occurring within the Sichuan Basin. Petrographic and geochemical studies reveal dolomitization was a direct result of precipitation by chemically distinct fluids occurring at different times and at different intensities. Based on this evidence, dolomitization and multiple fluid flow events are analyzed, and three types of fluid evolution models are proposed. Results of analysis show that Precambrian Dengying Formation carbonates were deposited in a restricted peritidal environment(630–542 Ma). A high temperature and high Mg~(2+) concentration seawater was a direct result of dolomitization for the micrite matrix, and for fibrous aragonite in primary pores. Geochemical evidence shows low δ~(18)O values of micritic dolomite varying from-1.29‰ to-4.52‰ PDB, abundant light rare earth elements(REEs), and low dolomite order degrees. Microbes and meteoric water significantly altered dolomite original chemical signatures, resulting in algal micritic dolomite and the fine-grained, granular, dolosparite dolomite having very negative δ~(18)O values. Finely crystalline cement dolomite(536.3–280 Ma) and coarsely crystalline cement dolomite have a higher crystallization degree and higher order degree. The diagenetic sequence and fluid inclusion evidence imply a linear correlation between their burial depth and homogenization temperatures, which closely resemble the temperature of generated hydrocarbon. Compared with finely crystalline dolomite, precipitation of coarsely crystalline dolomite was more affected by restricted basinal fluids. In addition, there is a trend toward a more negative δ~(18)O value, higher salinity, higher Fe and Mn concentrations, REE-rich. Two periods of hydrothermal fluids are identified, as the exceptionally high temperatures as opposed to the temperatures of burial history, in addition to the presence of high salinity fluid inclusions. The early hydrothermal fluid flow event was characterized by hot magnesium-and silicon-rich fluids, as demonstrated by the recrystallized matrix dolomite that is intimately associated with flint, opal, and microcrystalline quartz in intergranular or intercrystalline pores. This event was likely the result of a seafloor hydrothermal chimney eruption during Episode I of the Tongwan Movement(536.3±5.5 Ma). In contrast, later hydrothermal fluids, which caused precipitation of saddle dolomite, were characterized by high salinity(15–16.05 wt% NaCl equivalent) and homogenization temperatures(250 to 265°C), δ~(18)O values that were more enriched, and REE signatures. Geochemical data and the paragenetic sequence indicate that this hydrothermal fluid was related to extensive Permian large igneous province activity(360–280 Ma). This study demonstrates the presence of complicated dolomitization processes occurring during various paleoclimates, tectonic cycles, and basinal fluids flow; results are a useful reference for these dolomitized Precambrian carbonates reservoirs.     

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.     

Fluid Inclusions in the Gold—Bearing Quartz Veins at Um Rus Area,Eastern Desert,Egypt

Fluid inclusions in the gold-bearing quartz veins at the Um Rus area are of three types: H₂O, H₂O−CO₂ and CO₂ inclusions. H₂O inclusions are the most abundant, they include two phases which exhibit low and high homogenization temperatures ranging from 150 to 200°C and 175 to 250°C, respectively. The salinity of aqueous inclusions, based on ice melting, varies between 6.1 and 8 equiv. wt% NaCl. On the other hand, H₂O−CO₂ fluid inclusions include three phases. Their total homogenization temperatures range from 270 to 325°C, and their salinity, based on clathrate melting, ranges between 0.8 and 3.8 equiv. wt% NaCl. CO₂ fluid inclusions homogenize to a liquid phase and exhibit a low density range from 0.52 to 0.66 g/cm³. The partial mixing of H₂O−CO₂ and salt H₂O−NaCl fluid inclusions is the main source of fluids from which the other types of inclusions were derived. The gold-bearing quartz veins are believed to be of medium temperature hydrothermal convective origin.     

The stability of sapphirine-quartz and hypersthene-sillimanite-quartz assemblages: an experimental investigation in the system FeO−MgO−Al2O3−SiO2 under H2O and CO2 conditions

Phase relations and mineral chemistry involving the phases garnet (Gt), spinel (Sp), hypersthene (Hy), sapphirine (Sa), cordierite (Cd), sillimanite (Sil) and quartz (Qz) have been experimentally determined in the system FMAS (FeO−MgO−Al₂O₂−SiO₂) under low fO₂ and for various H₂O/CO₂ conditions. Several compositions were studied with 100 (Mg/Mg+Fe) ratio ranging from 64 to 87 with excess quartz and sillimanite. Our data do not show any differences in Gt−Cd stability and composition as a function of H₂O, CO₂ and H₂O−CO₂ (±CH₄) content, in good agreement with a previous experimental study at lower temperature (Aranovich and Podlesskii 1983). At 1,000° C and 11 kbar, under CO₂-saturated conditions, cordierite grew from a crystalline mix unseeded with cordierite. Thus, under water-absent conditions, cordierite will have a high-P stability field in the presence of CO₂. If water has a pressure stabilizing effect on cordierite, then our results would indicate that the effects of H₂O and CO₂ are of the same magnitude at high temperature. Our data support the theoretical P-T grid proposed by Hensen (1986) for high-T metapelites and are largely consistent with the high-temperature experimental data of Hensen and Green (1973). The univariant boundary Gt+Cd=Hy+Sil+Qz, which marks the disappearance of Hy−Sil−Qz assemblages, has a negative dP/dT slope above 1,000° C and a positive one below this temperature. Extrapolation of our data to iron-free systems shows that the high-P breakdown limit of Mg-cordierite has a negative slope in the range 1,025–1,300° C and probably positive below 1,000° C. This indicates a maximum of stability for Mg-cordierite at around 1,000° C and 13 kbar. Because of the curvature of the univariant reactions En+Sil=Py+Qz, Mg−Cd=En+Sil+Qz and Gt+Cd=Hy+Sil+Qz, the iron-free invariant point involving the phases Py, En, Cd, Sil and Qz probably does not exist. Sapphirine—Qz-bearing assemblages are stable only at temperatures above 1,050° C. At 1,075° C, the joint Gt−Sa is stable up to 11 kbar. At higher pressure, garnet, sapphirine and quartz react according to the reaction Gt+Sa+Qz=Hy+Sil. Reequilibrated sapphirines are more aluminous than the theoretical endmember Mg₂Al₄SiO₁₀ due to AlAl=MgSi substitutions [100(Al₂O₃/Al₂O₃+FeO+MgO) in experimental sapphirines ranges from 50.5 to 52.2]. Sapphirine in the assemblage Sa−Cd−Sil−Qz shows a decrease in Al content with decreasing temperature and pressure, such that the alumina isopleths for sapphirine have a slight negative dP/dT slope. A similar decrease in Al content of sapphirine with temperature is also observed in Sa−Sil−Qz assemblages.     

The effect of fluid salinity on infiltration-driven contact metamorphism of carbonate rocks

Calculated phase equilibria involving minerals and H₂O–CO₂–NaCl fluid lead to predictions of how infiltration of rock by H₂O–NaCl fluids with X _NaCl in the range 0–0.3 (0–58 wt% NaCl) drives the reactions calcite + quartz = wollastonite + CO₂ and dolomite = periclase + calcite + CO₂. Calculations focus on metamorphism in four aureoles that together are representative of the normal P–T conditions and processes of infiltration-driven contact metamorphic reactions. The effect of salinity on the spatial extent of oxygen isotope alteration was also computed. The time-integrated input fluid flux (q°) that displaces the mineral reaction front an increment of distance along the flow path always increases with increasing X _NaCl. For input fluids with salinity up to approximately five times that of seawater (X _NaCl ≤ 0.05), values of q° required to explain the spatial extent of decarbonation reaction are no more than 1.1–1.5 times that computed assuming the input fluid was pure H₂O. For more saline fluids, values of q° may be up to 1.4–7.9 times that for pure H₂O. Except for reaction in the presence of halite and vapor (V), infiltration of H₂O–NaCl fluids expands the region of oxygen isotope alteration relative to the size of the region of mineral reaction. The expansion is significant only for saline fluids with X _NaCl ≥ ~0.1. Immiscible fluid phase separation and differential loss of the liquid (L) or V phase from the mineral reaction site increases the amount of reactive fluid required to advance the mineral reaction front compared to conditions under which equilibration of minerals and fluid is attained with no loss of L or V. Decarbonation reactions driven by infiltration of fluids with even modest seawater-like salinity can explain the occurrence of salt-saturated fluid and solid halide inclusions in contact metamorphosed carbonate rocks.     

Origin of the Zálesí U–Ni–Co–As–Ag/Bi deposit,Bohemian Massif,Czech Republic: fluid inclusion and stable isotope constraints

The Zálesí vein-type deposit is hosted by Early Paleozoic high-grade metamorphic rocks on the northern margin of the Bohemian Massif. The mineralization is composed of three main stages: uraninite, arsenide, and sulfide. The mineral assemblages formed at low temperatures (~80 to 130°C, locally even lower) and low pressures (<100 bars). The salinity of the aqueous hydrothermal fluids (0 to 27 wt.% salts) and their chemical composition vary significantly. Early fluids of the oldest uraninite stage contain a small admixture of a clathrate-forming gas, possibly CO₂. Salinity correlates with oxygen isotope signature of the fluid and suggests mixing of brines [δ ¹⁸O around +2‰ relative to standard mean ocean water (SMOW)] with meteoric waters (δ ¹⁸O around −4‰ SMOW). The fluid is characterized by highly variable halogen ratios (molar Br/Cl = 0.8 × 10⁻³ to 5.3 × 10⁻³; molar I/Cl = 5.7 × 10⁻⁶ to 891 × 10⁻⁶) indicating a dominantly external origin for the brines, i.e., from evaporated seawater, which mixed with iodine-enriched halite dissolution brine. The cationic composition of these fluids indicates extensive interaction of the initial brines with their country rocks, likely associated with leaching of sulfur, carbon, and metals. The brines possibly originated from Permian–Triassic evaporites in the neighboring Polish Basin, infiltrated into the basement during post-Variscan extension and were finally expelled along faults giving rise to the vein-type mineralization. Cenozoic reactivation by low-salinity, low-δ ¹⁸O (around −10‰ SMOW) fluids of mainly meteoric origin resulted in partial replacement of primary uraninite by coffinite-like mineral aggregates.