H2O NaCl Fluids Research Articles

Small-scale transport of trace elements Nb and Cr during growth of titanite: an experimental study at 600 °C, 0.4 GPa

Trace element distribution in titanite overgrowths on rutile has been investigated experimentally at 600 °C, 400 MPa and fO2 near NiNiO buffer. Compositionally homogenous Cr- or Nb-doped synthetic rutile single crystals or Nb-containing natural rutile crystals were the source of Cr, Nb and Ti to synthesize titanite using the double-capsule technique. All element exchange with the source of Si, Ca and Al occurred via a NaCl–H2O fluid. Titanite forms quickly and exclusively around the rutile crystals. The titanite overgrowth separates rutile from the bulk fluid, and all elements from rutile dissolution have to pass through the titanite rim. Trace element concentrations in titanite show a considerable scatter in experiments with and without Al, although the average concentrations of Cr or Nb of titanite around compositionally homogeneous synthetic rutile approach the expected values for closed system conditions. Variability of Al with Cr or Nb in the titanite is not correlated. The Al zoning is irregular and patchy, and also the distribution of trace elements does not show systematic trends in the spatial distribution. In experiments using zoned natural rutile, the concentrations of Nb in titanite are related to the Nb zoning in rutile, but the contents also vary unsystematically. Under the controlled conditions of the experiment, the explanation for the strongly irregular spatial distribution is most likely due to variations in elemental concentrations during transport from the rutile along the titanite grain boundaries. The transport pathway is complex because grain boundary migration is important during titanite growth. Such irregular element distribution is also found in a natural sample of titanite overgrowth on rutile from an eclogite with retrograde overprint in the amphibolite facies. Transport of Ti and trace elements was focused on grain boundaries and shielded from the rutile as a source of these elements. We conclude that this type of zoning is not related to changes in P–T or composition in an open system, but solely controlled by transport in and through the titanite rim.

Fluid evolution of the Yuchiling porphyry Mo deposit, East Qinling, China

The Yuchiling Mo deposit, East Qinling, China, belongs to a typical porphyry Mo system associated with high-K calc-alkaline intrusions. The pure CO2 (PC), CO2-bearing (C), aqueous H2O-NaCl (W), and daughter mineral-bearing (S) fluid inclusions were observed in the hydrothermal quartz. Based on field investigations, petrographic, microthermometric and LA-ICP-MS studies of fluid inclusions, we develop a five-stage fluid evolution model to understand the ore-forming processes of the Yuchiling deposit. The earliest barren quartz±potassic feldspar veins, developed in intensively potassic alteration, were crystallized from carbonic-dominant fluids at high temperature (>416°C) and high pressure (>133MPa). Following the barren quartz±potassic feldspar veins are quartz-pyrite veins occasionally containing minor K-feldspar and molybdenite, which were formed by immiscible fluids at pressures of 47–159MPa and temperatures of 360–400°C. The fluids were characterized by high CO2 contents (approximately 8mol%) and variable salinities, as well as the highest Mo contents that resulted in the development of quartz-molybdenite veins. The quartz-molybdenite veins, accounting for >90% Mo in the orebody, were also formed by immiscible fluids with lower salinity and lower CO2 content of 7mol%, at temperatures of 340–380°C and pressures of 39–137MPa, as constrained by fluid inclusion assemblages. After the main Mo-mineralization, the uneconomic Cu-Pb-Zn mineralization occurred, as represented by quartz-polymetallic sulfides veins consisting of pyrite, molybdenite, chalcopyrite, digenite, galena, sphalerite and quartz. The quartz-polymetallic sulfide veins were formed by fluids containing 5mol% CO2, with minimum pressures of 32–110MPa and temperatures of 260–300°C. Finally, the fluids became dilute (5wt.% NaCl equiv) and CO2-poor, which caused the formation of late barren quartz±carbonate±fluorite veins at 140–180°C and 18–82MPa.It is clear that the fluids became more dilute, CO2-poor, and less fertile, with decreasing temperature and pressure from quartz-pyrite to late barren veins. Molybdenite and other sulfides can only be observed in the middle three stages, i.e., quartz-pyrite, quartz-molybdenite and quartz-polymetallic sulfide veins. These three kinds of veins are generally hosted in potassic altered rocks with remarkable K-feldspathization, but always partly overprinted by phyllic alteration. The traditional porphyry-style potassic–phyllic–propylitic alteration zoning is not conspicuous at Yuchiling, which may be related to, and characteristic of, the CO2-rich fluids derived from the magmas generated in intercontinental collision orogens.Among the fluid inclusions at Yuchiling, only the C-type contains maximum detectable Mo that gradationally decreases from 73ppm in quartz-pyrite veins, through 19ppm in quartz-molybdenite veins, and to 13ppm in quartz-polymetallic sulfide veins, coinciding well with the decreasing CO2 contents from 8mol%, through 7mol%, to 5mol%, respectively. Hence it is suggested that decreasing CO2 possibly results in decreasing Mo concentration in the fluids, as well as the precipitation of molybdenite from the fluids. This direct relationship might be a common characteristic for other porphyry Mo systems in the world.The Yuchiling Mo deposit represents a new type Mo mineralization, with features of collision-related setting, high-K calc-alkaline intrusion, CO2-rich fluid, and unique wall-rock alterations characterized by strong K-feldspathization and fluoritization.

Fluid inclusion study of the Nannihu giant porphyry Mo–W deposit, Henan Province, China: Implications for the nature of porphyry ore-fluid systems formed in a continental collision setting

The Nannihu Mo–W deposit, located in the Henan Province of China, is a giant porphyry deposit formed in the Qinling Orogen during the Jurassic continental collision between the North China and Yangtze Cratons. Mo–W mineralization is associated with the Nannihu porphyritic monzogranite, occurring as numerous stockwork veinlets in the altered wallrocks and the causative porphyry. Both the porphyry stock and wallrocks underwent intense hydrothermal alteration, ranging outwardly from potassic to phyllic alteration, and to carbonation zones with increasing distance from the intrusion. The hydrothermal ore-forming process can be divided into four stages characterized by veinlets, from early to late: (1) quartz+potassic feldspar±molybdenite±pyrite; (2) quartz+molybdenite veins containing minor pyrite and chalcopyrite; (3) quartz+polymetal sulfide; and (4) quartz+carbonate+fluorite. Most of the ores are formed during stages 2 and 3.Four types of fluid inclusions (FIs) are distinguished in this study based on petrographic and microthermometric criteria, i.e. pure CO2, NaCl–H2O, CO2–H2O and daughter mineral-bearing fluid inclusions. All of the four types of FIs can be observed in the hydrothermal quartz formed in stages 1, 2 and 3; while the stage 4 minerals contain only NaCl–H2O fluid inclusions. Fluid inclusions of stage 1 are mainly homogenized between 350 and 460°C, with salinities ranging from 5.7 to 17.9wt.% NaCl equiv. The stage 2 FIs yield homogeneous temperatures of 300–380°C and salinities of 3.5–16.9wt.% NaCl equiv. FIs of stage 3 are homogenized between 250 and 370°C, with salinities of 1.8–14.3 and 28.6–39.1wt.% NaCl equiv. FIs of stage 4 are homogenized at temperatures of 115 to 265°C, yielding salinities of 0.5 to 1.2wt.% NaCl equiv. Daughter minerals, such as halite, chalcopyrite and some unknown minerals, are frequently present in stage 3 FIs, which probably represent a reducing and oversaturated fluid-system resulting from fluid-boiling. The daughter mineral-bearing FIs coexist with vapor- and liquid-rich NaCl–H2O FIs that have contrasting salinities. These FIs are homogenized in divergent ways at similar temperatures, suggesting that fluid boiling took place in stages 2 and 3. The estimated pressures range from 70 to 270MPa in stage 1, through 30–150MPa in stage 2, to 30–85MPa in stage 3, corresponding to a depth of no less than 3km. In other words, the ore-forming fluids are characterized by high temperature, high salinity, high fO2 and high CO2 content; and fluid-boiling resulted in CO2 release, fO2 decrease and ore mineral precipitation. We suggest that the CO2-rich fluid is a distinctive feature of porphyry systems developed in continental collision setting, in transitional compressional to extensional regime, contrasting to the CO2-poor NaCl–H2O fluids observed in volcanic arcs.

A model for single-phase PVTx properties of CO2–CH4–C2H6–N2–H2O–NaCl fluid mixtures from 273 to 1273 K and from 1 to 5000 bar

A thermodynamic model explicit in Helmholtz free energy is constructed to calculate the single-phase PVTx properties of the CO2–CH4–C2H6–N2–H2O fluid mixtures. Parameters of the binary CO2–H2O, CH4–H2O, C2H6–H2O and N2–H2O mixtures are regressed from assessed experimental data. On the basis of the binary mixture parameters, the model can be used to predict the single-phase volumes of the CO2–CH4–C2H6–N2–H2O–NaCl fluid mixtures with a simple approach. Comparison with a large number of experimental data shows that the model can reproduce the single-phase PVTx properties of the CO2–CH4–C2H6–N2–H2O–NaCl fluid mixtures from 273 to 1273K and from 1 to 5000bar, with or close to experimental accuracy. Online calculations can be made on the website: www.geochem-model.org/.

Modification of fluid inclusions in quartz by deviatoric stress. II: experimentally induced changes in inclusion volume and composition

Fluid inclusions in quartz are known to modify their densities during shear deformation. Modifications of chemical composition are also suspected. However, such changes have not been experimentally demonstrated, their mechanisms remain unexplained, and no criteria are available to assess whether deformed inclusions preserve information on paleofluid properties. To address these issues, quartz crystals containing natural CO2–H2O–NaCl fluid inclusions have been experimentally subjected to compressive deviatoric stresses of 90–250 MPa at 700°C and ~600 MPa confining pressure. The resulting microcracking of the inclusions leads to expansion by up to 20%, producing low fluid densities that bear no relation to physical conditions outside the sample. Nevertheless, the chemical composition of the precursor inclusions is preserved. With time the microcracks heal and form swarms of tiny satellite inclusions with a wide range of densities, the highest reflecting the value of the maximum principle stress, σ 1. These new inclusions lose H2O via diffusion, thereby passively increasing their salt and gas contents, and triggering plastic deformation of the surrounding quartz via H2O-weakening. Using microstructural criteria to identify the characteristic types of modified inclusions, both the pre-deformation fluid composition and syn-deformation maximum stress on the host mineral can be derived from microthermometric analysis and thermodynamic modelling.

Mineralogical, fluid inclusion, and stable isotope constraints on mechanisms of ore deposition at the Samgwang mine (Republic of Korea)—a mesothermal, vein-hosted gold–silver deposit

The Samgwang mine is located in the Cheongyang gold district (Cheonan Metallogenic Province) of the Republic of Korea. It consists of eight massive, gold-bearing quartz veins that filled NE- and NW-striking fractures along fault zones in Precambrian granitic gneiss of the Gyeonggi massif. Their mineralogy and paragenesis allow two separate vein-forming episodes to be recognized, temporally separated by a major faulting event. The ore minerals occur in quartz and calcite of stage I, associated with fracturing and healing of veins. Hydrothermal wall-rock alteration minerals of stage I include Fe-rich chlorite (Fe/(Fe+Mg) ratios 0.74-0.81), muscovite, illite, K-feldspar, and minor arsenopyrite, pyrite, and carbonates. Sulfide minerals deposited along with electrum during this stage include arsenopyrite, pyrite, pyrrhotite, sphalerite, marcasite, chalcopyrite, galena, argentite, pyrargyrite, and argentian tetrahedrite. Only calcite was deposited during stage II. Fluid inclusions in quartz contain three main types of C–O–H fluids: CO2-rich, CO2–H2O, and aqueous inclusions. Quartz veins related to early sulfides in stage I were deposited from H2O–NaCl–CO2 fluids (1,500–5,000 bar, average 3,200) with T htotal values of 200°C to 383°C and salinities less than about 7 wt.% NaCl equiv. Late sulfide deposition was related to H2O–NaCl fluids (140–1,300 bar, average 700) with T htotal values of 110°C to 385°C and salinities less than about 11 wt.% NaCl equiv. These fluids either evolved through immiscibility of H2O–NaCl–CO2 fluids as a result of a decrease in fluid pressure, or through mixing with deeply circulated meteoric waters as a result of uplift or unloading during mineralization, or both. Measured and calculated sulfur isotope compositions (δ34SH2S = 1.5 to 4.8‰) of hydrothermal fluids from the stage I quartz veins indicate that ore sulfur was derived mainly from a magmatic source. The calculated and measured oxygen and hydrogen isotope compositions (δ18OH2O = −5.9‰ to 10.9‰, δD = −102‰ to −87‰) of the ore-forming fluids indicate that the fluids were derived from magmatic sources and evolved by mixing with local meteoric water by limited water–rock exchange and by partly degassing in uplift zones during mineralization. While most features of the Samgwang mine are consistent with classification as an orogenic gold deposit, isotopic and fluid chemistry indicate that the veins were genetically related to intrusions emplaced during the Jurassic to Cretaceous Daebo orogeny.

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 XNaCl 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 XNaCl. For input fluids with salinity up to approximately five times that of seawater (XNaCl ≤ 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 XNaCl ≥ ~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.

Postorogenic Origin of the Stratiform Cu Mineralization at Lufukwe, Lufilian Foreland, Democratic Republic of Congo

The Central African Copperbelt, which stretches across the border between Zambia and the Democratic Republic of Congo, is one of the largest sediment-hosted stratiform Cu-Co provinces in the world. The triangular-shaped Lufilian foreland is located to the northeast of the Copperbelt. Recently sediment-hosted stratiform copper occurrences have been explored in the foreland, including the Kinkumbi prospect in the Lufukwe anticline. Although the stratiform copper mineralization in the Copperbelt is mainly concentrated in the Roan Group sedimentary rocks, where it is commonly associated with cobalt, the Lufilian foreland copper mineralization occurs in sedimentary rock units of the Nguba and Kundelungu Groups where it is mainly associated with silver. This paper examines the metallogenesis of the stratiform copper mineralization at Lufukwe. The Lufukwe anticline is situated in the eastern part of the Lufilian foreland and is composed of Neoproterozoic sedimentary rocks belonging to the Katanga Supergroup. The Kinkumbi prospect, a sediment-hosted stratiform copper-silver occurrence, is located in the northern part of the western flank of the anticline. This part of the anticline is characterized by disseminated copper-silver mineralization hosted in the lower 10 to 15 m of the Monwezi Sandstone (Nguba Group). A comparison between the location of high copper grades in surface samples and boreholes and the location of structural lineaments visible on ASTER images indicates that the mineralization is spatially related to northeast-southwest to east-northeast‐west-southwest strike-slip faults. These faults are nearly perpendicular to the strike of the host rock and postdate both the Lufilian folding and deposition of the entire Katanga Supergroup. The Monwezi Sandstone was subjected to strong compaction and silica cementation (authigenic quartz overgrowths), followed by intense feldspar dissolution, which resulted in a well-developed secondary porosity represented by dissolution cavities. Copper sulfides are mainly concentrated in these cavities and partially replace the detrital grains. The copper mineralization is both hypogene (chalcopyrite, bornite, and chalcocite) and supergene (digenite, covellite, and minor native copper), with malachite and chrysocolla as the main oxidation products. Point counting and grain size measurements demonstrate that the sandstone horizons with high copper content (>1.25% Cu) are those with a detrital grain size larger than 175 µm, more than 35 percent altered feldspars and little or no fine-grained matrix. Microthermometry of fluid inclusions indicates that the authigenic quartz overgrowths precipitated from a moderate-temperature (80°‐130°C), high-salinity (18.8‐23.4 wt % CaCl2 equiv) H2O-NaCl-CaCl2 fluid. The hypogene copper-silver mineralization was deposited from a hot (120°‐180°C) and low- to moderate-salinity (1.9‐7.7 wt % NaCl equiv) H2O-NaCl fluid with a general trend of increasing homogenization temperatures with increasing salinities. The interpretation of the available structural, stratigraphic, petrographic, and fluid inclusion microthermometric data constrain the timing of the mineralization to a time after the Lufilian folding and deposition of the entire Katanga Supergroup. The data presented support a postorogenic fluid-mixing model in which the mineralization is related to the mixing of a copper-rich mineralizing fluid with a temperature ≥180°C and salinity ≥7.7 wt percent NaCl equiv, likely migrating upward along northeast-southwest‐ to east-northeast‐west-southwest‐oriented strike-slip faults, with a colder, low-salinity, reducing fluid in the Monwezi Sandstone. The location and distance between the northeast-southwest to east-northeast‐west-southwest faults strongly influenced the spatial distribution of the copper mineralization in the anticline, and the variability in grain size and composition of the Monwezi Sandstone caused the preferential lateral migration of the mineralizing fluid through the lower 10 to 15 m. Copper precipitation was possibly induced by reduction by preexisting noncopper sulfides (pyrite and arsenopyrite) and hydrocarbons and by the drop in fluid temperature and salinity. Based on this research the areas with dominant northeast-southwest to east-northeast‐west-southwest structural lineaments are considered favorable sites for further copper exploration in the Lufilian foreland, especially where these lineaments cut previously deformed Katanga sediments. Coarse-grained sandstones with no fine matrix that underwent intense feldspar dissolution are the most promising host rocks for the late disseminated stratiform copper mineralization in the Lufilian foreland. Airborne gamma-ray spectrometric surveys could be used as a powerful exploration tool for targeting ore-related, K-depleted zones in these sandstones.

Synthetic Fluid Inclusions. XVII. PVTX Properties of High Salinity H2O-NaCl Solutions (>30 wt % NaCl): Application to Fluid Inclusions that Homogenize by Halite Disappearance from Porphyry Copper and Other Hydrothermal Ore Deposits

Fluid inclusions that homogenize by disappearance of the halite crystal after the vapor bubble has disappeared have been reported from a wide range of ore-forming systems. While this inclusion type is most commonly observed in porphyry copper and similar magmatichydrothermal ore deposits, they have also been reported from iron oxide copper-gold (IOCG), Mississippi Valley-type, orogenic (lode, greenstone) gold, massive sulfide, unconformity U, and mantotype deposits, as well as from non-ore associated granitoids and oceanic crust. The lack of experimental data to interpret microthermometric data from these inclusions, combined with poor petrographic characterization of inclusion origin, has led to a wide range of inferred PT trapping conditions for the inclusions. The relationship between liquid-vapor homogenization temperature (ThL-V), halite dissolution temperature (Tmhalite) and pressure has been determined using synthetic H2O-NaCl fluid inclusions that homogenize by halite disappearance. The experimental data cover the range ThL-V ≈ 150° to 500°C and Tmhalite ≈ 275° to 550°C. An empirical equation describing the relationship between pressure, ThL-V, and Tmhalite has been developed to estimate formation pressures from microthermometric data and is valid from pressures along the liquid + vapor + halite curve to 300 MPa. A detailed literature review reveals that the results of this study cannot be applied retroactively to estimate pressures of previously reported inclusions that homogenize by halite dissolution for several reasons. First, most workers have not collected and reported the data in a manner that allows one to determine if the inclusions have trapped a single, homogeneous phase and have not leaked or changed volume following trapping. Thus, it is not possible to determine if the inclusions show consistent microthermometric behavior within a group of coeval inclusions. Additionally, many published studies provide only summaries of results from numerous samples or present the data graphically, precluding application of our results to individual inclusions. However, based on our review, it appears that much of the published data for inclusions that homogenize by halite dissolution represent inclusions that have either trapped a halite crystal along with the liquid or have reequilibrated by necking and/or stretching. Results from this study have been used to estimate minimum formation pressures for inclusions from the Ditrau Alkaline Massif, Transylvania, Romania, the Musoshi stratiform copper deposit, Zaire, the Bismark skarn deposit, northern Mexico, the Naica chimneymanto deposit, Mexico, the Questa porphyry molybdenum deposit, New Mexico, and the Bingham Canyon porphyry Cu-Mo deposit, Utah. In each case, pressures estimated using results from the present study are in good agreement with previous pressure estimates. However, in some cases estimated pressures (both our estimates as well as those of other authors) appear to be unreasonably high, based on the geologic setting at the time of formation. These results highlight the currently limited understanding concerning pressures (depths) of ore formation.

Experimental calibration of the vapour–liquid phase relations and lithium isotope fractionation in the system H2O–LiCl at 400°C/20–28 MPa

AbstractWe experimentally determined the vapour–liquid two‐phase field and the vapour–liquid fractionation of the lithium isotopes in the system H2O–LiCl along the 400°C isotherm at 20–28 MPa. The critical point of the 400°C isotherm is at 27.6 MPa/750 mmol kg−1 LiCl, i.e. at slightly lower pressure but higher salt concentration than in the H2O–NaCl system. At a given pressure, the vapour in the H2O–LiCl system has higher salt concentrations compared to the vapour in the H2O–NaCl system whereas salt concentrations in coexisting liquid are comparable in both systems. The vapour–liquid two‐phase field in the H2O–LiCl system therefore opens less with decreasing pressure. The available data indicate that adding LiCl to a predominantly H2O–NaCl fluid may notably increase salt concentrations in the vapour. The lithium isotope fractionation between vapour and liquid is only minor with a slight preference of 7Li for the liquid. The data do not allow quantifying Δ7Livapour‐liquid precisely, but they suggest Δ7Livapour‐liquid ≤ −0.5‰. Even for extreme Rayleigh fractionation in an open system the lithium isotopic signature of vapour, liquid, and bulk system will not be altered by more than 1‰. The lithium isotopes are a conservative tracer during aqueous fluid phase separation and lithium isotope fractionation observed in natural hydrothermal systems reflects the combined effects of source reservoir and fluid–mineral interactions.

Immiscibility of high salinity fluids in volcanic rocks and the mechanism of magma degassing in the Dongying sag, eastern China

Fluid inclusions that bear halite daughter minerals were discovered in volcanic rocks at Pingnan area in the Dongying sag. The samples of the fluid inclusions collected from the BGX-15 well drill cores are hosted in quartz of diorite-porphyrite. The daughter minerals are identified as NaCl crystals after being observed under a microscope and analyzed by in situ Raman spectroscopy at −185°C. The results of micro-thermal analysis show that the homogenization temperatures of primary fluid inclusions are between 359 and 496°C, and the salinities of fluid inclusions are from 43.26 to 54.51 wt-%. All fluid inclusions in the studied samples can be divided into five types including primary fluid inclusions and secondary fluid inclusions. The fact that five types of fluid inclusions were symbiotic in the same quartz grain implies that immiscibility happened in magma. Due to the decrease in temperature and pressure during the ascent of magma, the fluids became intensively immiscible. This process accelerates the degassing of CO2 from magma, but the remnant fluids with high salinity are preserved in fluid inclusions. Thus, the primary fluid inclusions are mainly in NaCl-H2O fluids and poor in CO2. The results of our study indicate that the degassing of magma and accumulation of CO2 gas at the Pingnan area are relative to the immiscibility of high salinity fluids. This discovery is important because it can help us have a further understanding of the mechanism of magma degassing and accumulation of the inorganic CO2 in eastern China.

Specularitic iron ores and shear zones in the Quadrilátero Ferrífero District

In the eastern high-strain domain of the Quadrilátero Ferrífero, Brazil, hard and soft high-grade hematite ore may occur as schistose bodies in shear zones mainly related to the Cambotas-Fundão thrust system. These orebodies are almost entirely constituted of oriented specularite platelets that develop both as a product of crystal–plastic deformation of hematite and solution-precipitation processes. Both mechanisms interact in the partitioning of the strain, while solution-precipitation is responsible for the precipitation of hematite and localised leaching of silica resulting in the formation of syntectonic ores. The analyses of fluid inclusions from specularite crystals of the Conceição and Timbopeba deposits, located in the northern and southernmost areas of the eastern high-strain domain of the Quadrilátero Ferrífero, were studied using infrared microthermometry and synchrotron X-ray fluorescence. The results indicate the participation of highly saline aqueous H2O–NaCl fluids containing other additional cations (Ca, Fe, K and probably Ti) in solution and homogenisation temperature Th averaging between 130 and 190°C. However, the partial fusion of metastable saturation phases indicates crystallisation temperatures of ∼400°C. The mineralisation process produces high-grade orebodies as well as Fe-rich specularitic itabirites that are explored in that area. The shear zones are related to thrust faults mapped and interpreted as related to the Pan-African/Brasiliano Orogeny that affected the Quadrilátero Ferrífero, thrusting the Paleoproterozoic platform sequence of the Minas Supergroup over Mesoproterozoic quartzites of the Espinhaço Supergroup. They intersect and even overprint an early metamorphic and tectonic fabric of Paleoproterozoic age (Transamazonian Orogeny). The geological and fabric relationships lead to the conclusion that the luids involved in the mineralisation were most probably of external origin, of still unknown source (possibly igneous), during the closure of the São Francisco Craton.

Gold-Bearing Mesothermal Veins from the Gubong Mine, Cheongyang Gold District, Republic of Korea: Fluid Inclusion and Stable Isotope Studies

The Gubong deposit consists of five massive, gold-bearing mesothermal quartz veins that fill fractures oriented northeast and northwest along fault shear zones over an area of 14 km2 in Precambrian metasedimentary rocks of the Gyeonggi massif. The veins are divided into three groups, based on their orientation and location. They have a ribbon texture that is interpreted to result from repeated hydraulic fracturing events. Mineral deposition was associated with hydrothermal fluid overpressuring within and below the active fault shear zones. The vein mineralogy and paragenesis of the veins allow two separate discrete mineralization episodes to be recognized, separated by a major faulting event. The ore minerals are contained within quartz and calcite associated with fracturing and healing of veins that occurred during both mineralization episodes. Wall-rock alteration minerals during stage I, the main ore stage, include sericite, chlorite, and minor pyrite and carbonates. Sulfide minerals deposited along with electrum during this stage include arsenopyrite, pyrite, pyrrhotite, sphalerite, marcasite, chalcopyrite, galena, and argentite. Electrum also was deposited during stage II mineralization in the one group of veins, along with pyrite, sphalerite, chalcopyrite, and galena, but the second stage of deposition in other veins was barren. Petrographic examination of textural relationships among sulfides, fluid inclusions, microfracturing, and quartz shows chronological and genetic relationships between gold deposition and fluid entrapment. Systematic studies of fluid inclusions in stage I vein indicate two contrasting events: a relatively high temperature (203°–432°C) and pressure (943–2,098 bars) event related to early sulfide deposition and associated with H2O-CO2-CH4-NaCl ± N2 fluids (less than about 13.4 wt % NaCl), and a lower temperature (202°–399°C) and pressure (670–850 bars) late sulfide depositional event involving H2O-NaCl fluids (3.9–17.3 wt % NaCl). The H2O-NaCl fluid involved in ore-related stage II mineralization had a salinity of 0.4 to 4.2 wt percent NaCl and a homogenization temperature of 201° to 378°C. The calculated sulfur isotope compositions of hydrothermal fluids from the stage I veins (δ34SH2S = 3.5–10.5‰) indicate that ore sulfur was derived mainly from a magmatic source but also in part from sulfur contained in the host rocks. The calculated and measured oxygen and hydrogen isotope compositions of the ore-forming fluids (stage I: δ18OH2O = 1.1–9.0‰, δD = −92 to −21‰; stage II: δ18OH2O = −0.1 to +0.3‰, δD = −95 to −93‰) indicate that the fluids were derived from magmatic and/or deep-seated metasedimentary rocks (stage I) and evolved by mixing with local meteoric water (stage II), by limited water-rock exchange and by degassing during mineralization in uplift zones. The H2O-NaCl fluids involved in the stage I development of these veins represent fluids that evolved either through unmixing of H2O-CO2-CH4-NaCl ± N2 fluids following a decrease in fluid pressure or through mixing with deeply circulating meteoric waters, possibly as a result of uplift and/or unloading during mineralization. The H2O-NaCl fluid involved in stage II was derived from meteoric water. Early deposition of gold in stage I was caused by a decrease in sulfur fugacity (H2S loss) that accompanied the immiscible separation of carbonic vapor from H2O-CO2-CH4-NaCl ± N2 fluids. Gold in late stage I and stage II veins was precipitated from H2O-NaCl fluids by cooling and by dilution caused by mixing with meteoric water.

Nahcolite in fluid inclusions from the Ryoke metamorphic rocks and its implication for fluid genesis

Nahcolite (NaHCO3) has been found in fluid inclusions in quartz veins hosted by the Ryoke metamorphic rocks in Kasado-Jima (Island), Yamaguchi Prefecture, Japan. The inclusions are classified into three types: type 1 containing vapor +/− liquid of the H2O-NaCl-CO2-CH4 system, type 2 of H2O-NaCl fluids and type 3 with nahcolite solid. Salinities of the nahcolite-bearing fluids are lower than 4 wt% NaCl eq. Extremely large volume fractions of nahcolite solids, occupying more than 50% of total inclusion volume, and various fluid compositions are indicative of their origin as accidentally trapped ones while the fluids were immiscible below the nahcolite melting temperature (270 °C). A thermodynamic calculation of the nahcolite stability and a phase analysis of the fluids show logaNa+ = 7.4 − pH as the minimum activity at P = 100 MPa and T = 270 °C where the neutral pH = 5.6. Hence, it can be concluded that the original (prior to immiscible state) liquids might have contained high Na+ and low Cl− yielded by an interaction of a low-salinity fluid and Na-bearing minerals such as plagioclase in the host metamorphic rocks below the fractures now occupied by quartz if nahcolite precipitated from boiling fluids.

Paragonite stability at 700°C in the presence of H2O–NaCl fluids: constraints on H2O activity and implications for high pressure metamorphism

We carried out reversed piston-cylinder experiments on the equilibrium paragonite = jadeite + kyanite + H2O at 700°C, 1.5–2.5 GPa, in the presence of H2O-NaCl fluids. Synthetic paragonite and jadeite and natural kyanite were used as starting materials. The experiments were performed on four different nominal starting compositions: X(H2O)=1.0, 0.90, 0.75 and 0.62. Reaction direction and extent were determined from the weight change in H2O in the capsule, as well as by optical and scanning electron microscopy (SEM). At X(H2O)=1.0, the equilibrium lies between 2.25 and 2.30 GPa, in good agreement with the 2.30–2.45 GPa reversal of Holland (Contrib Miner Petrol 68:293–301, 1979). Lowering X(H2O) decreases the pressure of paragonite breakdown to 2.10–2.20 GPa at X(H2O)=0.90 and 1.85–1.90 GPa at X(H2O)=0.75. The experiments at X(H2O) = 0.62 yielded the assemblage albite + corundum at ≤1.60 GPa, and jadeite + kyanite at ≥1.70 GPa. This constrains the position of the isothermal paragonite–jadeite–kyanite–albite–corundum–H2O invariant point in the system Na2O–Al2O3–SiO2–H2O to be at 1.6–1.7 GPa and X(H2O)~0.65±0.05. The data indicate that H2O activity, a(H2O), is 0.75–0.86, 0.55–0.58, and <0.42 at X(H2O)=0.90, 0.75, and 0.62, respectively. These values approach X(H2O)2, and agree well with the a(H2O) model of Aranovich and Newton (Contrib Miner Petrol 125:200–212, 1996). Our results demonstrate that the presence or absence of paragonite can be used to place limits on a(H2O) in high-pressure metamorphic environments. For example, nearly pure jadeite and kyanite from a metapelite from the Sesia Lanzo Zone formed during the Eo-Alpine metamorphic event at 1.7–2.0 GPa, 550–650°C. The absence of paragonite requires a fluid with low a(H2O) of 0.3–0.6, which could be due to the presence of saline brines.

Fluids and hydrothermal alteration assemblages in a Devonian gold-bearing hot-spring system, Rhynie, Scotland

ABSTRACTHydrothermal alteration at Rhynie, Aberdeenshire, Scotland, is concentrated along a fault zone, which juxtaposes surface deposits and the mineralised feeder zone to the Rhynie hotspring system. Mineralisation consists of breccias and veins filled with quartz, chert, calcite, K-feldspar and pyrite. Associated pervasive alteration comprises a high-temperature K-feldsparquartz-illite facies (formed at 250–350°C), a medium-temperature mixed layered illite/smectitequartz-K-feldspar-chlorite-calcite facies (formed at 150–200°C) and a low-temperature mixed layered illite/smectite-chlorite-calcite facies (formed at 100 to +150°C). The fluids responsible for mineralisation were mainly moderate- to high-temperature (Th =91–360°C), low-salinity (&lt;0·2 to 2·9 wt.% NaCl eq.) H2O-NaCl-heated meteoric fluids comparable to modern and ancient hot-spring systems. The migration of these fluids was mainly restricted to a major fault zone bounding the Devonian basin. Fluids responsible for mineralisation, alteration and cementation elsewhere in the basin were low-temperature (Th 57 to 161°C), low- to high-salinity (&lt;0·2 to 18 wt.% NaCl eq.) H2O-NaCl fluids, which resemble basinal brines.

Dissolution channels in quartz and the role of pressure changes in gold and sulfide deposition in the Archean, greenstone-hosted, Hutti gold deposit, Karnataka, India

The pressure, temperature and composition of ore fluids that resulted in gold deposition in the Archean, greenstone-hosted Hutti deposit have been studied using fluid inclusions and the compositions of arsenopyrite and chlorite. Five types of fluids have been identified in fluid inclusions in quartz veins associated with mineralization. They are (1) monophase CO2-rich fluid; (2) low-salinity (0 to 14 wt% NaCl equivalent) and high-salinity (16 to 23 wt% NaCl equiv.) aqueous fluids; (3) high-salinity (28 to 40 wt% NaCl equiv.), polyphase aqueous fluids; (4) CO2–H2O–NaCl fluids of low salinity (0–8 wt% NaCl equiv.); and (5) a few carbonic inclusions with halite±nahcolite. The diversity of entrapped fluid composition is explained in terms of changes in fluid pressure and temperature which affect a more or less uniform supply of primary low-salinity CO2–H2O–NaCl fluid to the shear zone. Geothermobarometric studies indicate that during mineralization temperature ranged between 360 and 240 °C, and fluid pressure between 3,600 and 1,600 bar. The data are interpreted in terms of the cyclic fault-valve mechanism for active shear zones. Deposition of gold and sulfides has been studied on the basis of constraints from the composition of wall-rock chlorite, ore-mineral assemblages, and textural features. Tubular channels, 20 to 100 μm wide and up to 500 μm long that arise from fractures and C-planes in sheared quartz veins are reported for the first time. The channels have pyrrhotite, arsenopyrite, pyrite and gold at their distal ends, with calcite filling up the remaining part. These channels form in response to increases in T and P, by dissolution of quartz grains, guided by dislocations in them. At the P–T conditions of interest, gold and sulfide deposition takes place in the shears and fractures of quartz veins from CO2–H2O–NaCl ore fluid of low salinity and pH due to changes in phase compositions that occur during the process of shear failure of the enclosing rocks. In the wall rock where pH is buffered, gold deposition takes place from the predominant Au(HS)2 − species with progressive sulfide deposition and decrease in ΣS, from 0.01 to 0.001 mol/kg as T falls from 360 to 240 °C.

The latest Post-Variscan fluids in the Spanish Central System: evidence from fluid inclusion and stable isotope data

The Spanish Central System has been subjected to repeated fluid incursions, which were responsible for a variety of mineralizing episodes including W–Sn, Cu–Zn–Pb–As–(Ag), F–Ba and barren quartz veins. These hydrothermal fluids occurred over a 200Ma time period and the latest hydrothermal event is recorded in barren quartz veins. This study is a multidisciplinary approach leading to the characterization of the hydrothermal fluids preserved in barren quartz veins, which are spatially but not temporally related to Hercynian upper crustal granites. The veins were dated by the 39Ar/40Ar method, and the fluids were examined using petrographic, microthermometric, chemical and isotopic methods. Fluid inclusions in barren quartz veins indicate that two fluids were related to this hydrothermal event. The main part of the quartz veins were formed from an early low salinity (<1wt% NaCl) H2O–NaCl fluid. This fluid was trapped at around 270±25°C and 0.1–1kbar under sublithostatic to hydrostatic conditions. δ18O (−9 to 2‰) and δD (−70 to −34.5‰) values indicate a meteoric origin for water, with significant water/rock interactions. The latest H2O–NaCl–CaCl2 fluid is found in two types of fluid inclusions: a primary liquid–vapour type (16–24wt% NaCl and 1–12wt% CaCl2) and secondary hypersaline type (7–15wt% NaCl and 21–27wt% CaCl2). Significant Li concentrations in this fluid were confirmed. This late Ca-bearing fluid formed quartz crystals in the central part of the veins, and was trapped at 70–140°C, at a maximum pressure of 0.5kbar. The low δ18O (−20 to −6‰) and δD (−137 to −116‰) values suggest a meteoric origin for this fluid, however its high salinity probably requires a source from Triassic evaporite basins located in the NE tip of the Spanish Central System. Anomalously low isotopic values have been previously reported from kaolinites of Lower Cretaceous age. Anomalous climatic conditions during the Cretaceous appear to be the main reason to explain this very negative meteoric water. Strong isotopic depletion in meteoric water has been observed in modern areas with monsoonal climates. The hydrothermal evolution of barren quartz veins in the Spanish Central System is comparable to other hydrothermal Post-Variscan events in central and south-western Europe related to the opening of the North-Atlantic during Cretaceous time.

Fluid Characteristics of Granitoid-Hosted Gold Deposits in the Birimian Terrane of Ghana: A Fluid Inclusion Microthermometric and Raman Spectroscopic Study

Fluid inclusions in vein quartz from 10 granitoid-hosted gold deposits and prospects in the Birimian terrane of Ghana, as well as from the Sansu mine (Ashanti shear zone type) and quartz veins in the nonmineralized Princess Town granodiorite, were studied by microthermometry and Raman microspectrometry. Fluid inclusions from the granitoid-hosted gold deposits are dominated by aqueous H2O-CO2-NaCl type 1 and liquid CO2-N2 ± CH4 type 2, with minor (<10%) aqueous H2O-NaCl type 3. Type 1 inclusions show large variations in CO2 phase volume proportions (10–90%) at 25°C and have salinities commonly between 0 and 6 wt percent NaCl equiv. Their bulk densities fall in a major range from 0.62 to 1.11 g/cm3. Type 2 inclusions show no visible H2O phase at room temperature and have bulk densities between 0.30 and 0.92 g/cm3. Type 3 inclusions, containing 10 to 20 vol percent H2O vapor, have salinities of 1 to 8 wt percent NaCl equiv and bulk densities of 0.77 to 1.03 g/cm3. In most cases, the three types of fluid inclusions coexist as groups in individual quartz grains of the samples studied. These fluid inclusions are interpreted to be trapped during phase separation of an originally homogeneous H2O-CO2 fluid, with low salinity (<6 wt % NaCl equiv) and moderate to high density (0.65–0.95 g/cm3). The type 1 fluid inclusions are suggested to be heterogeneous mixtures of the two end members of type 2 and 3 inclusions. Fluid immiscibility is documented by petrographic characteristics and microthermometric results of the three types of inclusions. Trapping temperatures and pressures, estimated from microthermometry of type 3 inclusions, equation of state, and the P-T-X nature of the H2O-CO2-NaCl system, are mainly between 200° and 350°Cand 1 and 3 kbars for the gold deposits. By contrast, fluid inclusions in the Sansu mine at Ashanti mostly comprise the liquid CO2-N2 ± CH4 type 2. The inclusions are considered to represent postentrapment modifications of trapped fluids. In addition, fluid inclusions in barren vein quartz from the Princess Town granodiorite comprise the low-salinity (commonly <6 wt % NaCl equiv) H2O-NaCl type 3. Raman microspectrometry shows that gaseous compositions of fluid inclusions from both granitoid- and shear zone-hosted gold deposits are mainly composed of CO2 (80–95 mol %), with significant amounts of N2 (2–20 mol %) and CH4 (0–10 mol %). The distinct low-salinity H2O-CO2-rich fluids from the granitoid-hosted gold deposits are comparable in composition to those from the major Ashanti and Tarkwaian types of gold deposits in the Birimian terrane of Ghana. These fluids are most likely to be metamorphic in origin and associated with the waning stages of the regional Birimian orogeny. Gold deposition within the Birimian granitoids was related to fluid phase separation and sulfidization of host rocks during hydrothermal alteration and mineralization. The present study, together with previous publications, suggests that fluid inclusions are characterized by H2O-CO2-NaCl and/or CO2-N2 ± CH4 types in mineralized areas, whereas H2O-NaCl fluid compositions dominate in barren areas. Fluid inclusion characteristics may, therefore, be a useful tool for regional gold exploration in the Birimian terrane of Ghana.

Quartz, albite and diopside solubilities in H2O–NaCl and H2O–CO2 fluids at 0.5–0.9 GPa

The solubility of quartz and incongruent dissolution ('apparent solubility') of albite and diopside in H2O–NaCl and H2O–CO2 fluids have been determined at pressures up to 0.9 GPa (9 kbar) and temperatures of 500–900 °C. Solubilities of quartz and albite decrease with increasing salt concentration [X(NaCl)](salt-out effect), whereas the solubility of diopside increases with increasing X(NaCl)(salt-in effect). Quartz solubilities in the systems H2O–NaCl and H2O–CO2 are very similar and are proportional to X(H2O)2. Quartz solubility in NaCl-rich brines does not change with pressure under the P–T conditions of our experiments. At 0.9 GPa and 800 °C, albite solubility in pure water is higher (~100 g/kg H2O) than that of quartz (~74 g/kg H2O), but at NaCl concentrations >6 mol% these solubilities are very similar. Albite dissolution is slightly incongruent; formation and composition of secondary and quench phases (paragonite, Na-margarite, amorphous quench spheres) indicate that the solution is enriched in SiO2 and Na2SiO3. As fluid composition changes from H2O towards more CO2-rich fluids or NaCl-rich brines, the solubilities of albite and quartz decrease by about one order of magnitude, but are still measurable at X(H2O)<0.5. A thermodynamic analysis of new quartz solubility data for H2O–CO2 fluids at 0.9 GPa indicates that complexing is dominated by SiO2.4H2O for water-rich fluids, but for X(H2O)<0.7 the mean solvation number decreases to ≤3. This speciation is similar to that reported previously for lower pressures, and is in agreement with recent high P–T spectroscopic data for the system H2O–SiO2. For dissolution of quartz in both H2O–CO2 and H2O–NaCl fluids, the molecular proportions of silica to water are almost the same at any X(H2O). Assuming similar non-ideal water-salt interactions irrespective of whether the water is in the fluid or is complexed with silica, then the speciation of silica appears to be similar in both H2O–CO2 and H2O–NaCl fluids under the experimental conditions. We conclude that the speciation of silica in both H2O–CO2 and H2O–NaCl fluids at 0.9 GPa and 800 °C is comparable, is dominated by Si(OH)4·2H2O and/or hydrated species with lower hydration numbers, and is also comparable to that proposed for lower P–T conditions.