Physicochemical parameters of the formation of hydrothermal deposits: A fluid inclusion study. I. Tin and tungsten deposits

The author’s database, which presently includes data from more than 18500 publications on fluid and melt inclusions in minerals and is continuing to be appended, was used to generalize results on physicochemical parameters of the formation of hydrothermal deposits and occurrences of tin and tungsten. The database includes data on 320 tin and tin-tungsten deposits and occurrences and 253 tungsten and tungstentin deposits around the world. For most typical minerals of these deposits (quartz, cassiterite, tungsten, scheelite, topaz, beryl, tourmaline, fluorite, and calcite), histograms of homogenization temperatures of fluid inclusions were plotted. Most of 463 determinations made for cassiterite are in the range of 300–500°C with maximum at 300–400°C, while those for wolframite and scheelite (453 determinations) fall in the range of 200–400°C with maximum at 200–300°C. Representative material on pressures of hydrothermal fluids included 330 determinations for tin and 430 determinations for tungsten objects. It was found that premineral, ore, and postmineral stages spanned a wide pressure range from 70–110 bar to 6000–6400 bar. High pressures of the premineral stages at these deposits are caused by their genetic relation with felsic magmatism. Around 50% of pressure determinations lie in the range of 500–1500 bar. The wide variations in total salinity and temperatures (from 0.1 to 80 wt % NaCl equiv and 20–800°C) were obtained for mineral-forming fluids at the tin (1800 determinations) and tungsten (2070 determinations) objects. Most of all determinations define a salinity less than 10 wt % NaCl equiv. (∼60%) and temperature range of 200–400°C (∼70%). The average composition of volatile components of fluids determined by different methods is reported. Data on gas composition of the fluids determined by Raman spectroscopy are examined. Based on 180 determinations, the fluids from tin objects have the following composition (in mol %): 41.2 CO₂, 39.5 CH₄, 19.15 N₂, and 0.15 H₂S. The volatile components of tungsten deposits (190 determinations) are represented by 56.1 CO₂, 30.7 CH₄, 13.2 N₂, and 0.01 H₂S. Thus, the inclusions of tungsten deposits are characterized by higher CO₂ content and lower (but sufficiently high) contents of CH₄ and N₂. The concentrations of tin and tungsten in magmatic melts and mineral-forming fluids were estimated from analysis of individual inclusions. The geometric mean Sn contents are 87 ppm (+ 610 ppm/−76 ppm) in the melts (569 determinations) and 132 ppm (+ 630 ppm/−109 ppm) in the fluids (253 determinations). The geometric mean W values are 6.8 ppm (+ 81/−6.2 ppm) in the magmatic melts (430 determinations) and 30 ppm (+ 144 ppm/−25 ppm) in the mineral-forming fluids (391 determinations).     

Physicochemical formation parameters of hydrothermal mineral deposits: Evidence from fluid inclusions. II. Gold,silver, lead,and zink deposits

Information from a database, which was compiled and continuously updated by the authors of this paper and now includes information from 19500 publication on fluid and melt inclusions in minerals, is used to summarize results on the physicochemical formation parameters of hydrothermal Au, Ag, Pb, and Zn deposits. The database provides information on fluid inclusions in minerals from 970 Pb-Zn, 220 Au-Ag-Pb-Zn, and 825 Au-Ag deposits in various settings worldwide. Histograms for the homogenization temperatures of fluid inclusion are presented for the most typical minerals of the deposits. In sphalerite, most homogenization temperatures (1327 measurements) of fluid inclusions lie within the range of 50–200°C with a maximum at 100–200°C for this mineral from Pb-Zn deposits and within the range of 100–350°C (802 measurements) with a maximum at 200–300°C for this mineral from Au deposits. Data are presented on fluid pressures at Au (1495 measurements) and Pb-Zn (180 measurements) deposits. The pressure during the preore, ore-forming, and postore stages at these deposits ranged from 4–10 to 6000 bar. The reason for the high pressures during preore stages at the deposits is the relations of the fluids to acid magmatic and metamorphic processes. More than 70% of the fluid pressures values measured at Pb-Zn deposits lie within the range of 1–1500 bar. Au-Ag deposits are characterized by higher fluid pressures of 500–2000 bar (61% of the measurements). The overall ranges of the salinity and temperature of the mineral-forming fluid at Au-Ag (6778 measurements) and Pb-Zn (3395 measurements) deposits are 0.1–80 wt % equiv. NaCl and 20–800°C. Most measurements (～64%) for Au-Ag deposits yield fluid salinity <10 wt % equiv. NaCl and temperatures of 200–400°C (63%). Fluids at Pb-Zn deposits are typically more saline (10–25 wt % equiv. NaCl, 51% measurements) and lower temperature (100–300°C, 74% measurements). Several measurements of the fluid density fall within the range of 0.8–1.2 g/cm³. The average composition of volatile components of the fluids was evaluated by various techniques. The average composition of volatile components of fluid inclusions in minerals is calculated for hydrothermal W, Au, Ag, Sn, and Pb-Zn deposits, metamorphic rocks, and all geological objects. The Au, Ag, Pb, and Zn concentrations in magmatic melts and mineral-forming fluids is evaluated based on analyses of individual inclusions.     

The nature, origin and physicochemical controls of hydrothermal Mo-Bi mineralization in the Cadillac deposit, Quebec, Canada

Mo-Bi mineralization occurs in subvertical and subhorizontal quartz-muscovite-± K-feldspar veins surrounded by early albitic and later K-feldspathic alteration halos in monzogranite of the Archean Preissac pluton, Abitibi region, Québec, Canada. Molybdenite is intergrown with muscovite in the veins or associated with K-feldspar in the alteration halos. Mineralized veins contain five main types of fluid inclusions: aqueous liquid and liquid-vapor inclusions, aqueous carbonic liquid-liquid-vapor inclusions, carbonic liquid and vapor inclusions, halite-bearing aqueous liquid and liquid-vapor inclusions, trapped mineral-bearing aqueous liquid and liquid-vapor inclusions. The carbonic solid in frozen carbonic and aqueous-carbonic inclusions melts in most cases at −56.7 ± 0.1 °C indicating that the carbonic fluid consists largely of CO₂. All aqueous inclusion types and the aqueous phase in carbonic inclusions have low initial melting temperatures (≥70 °C), requiring the presence of salts other than NaCl. Leachate analyses show that the bulk fluid contains variable proportions of Na, K, Ca, Cl, and traces of Mg and Li. The following solids were identified in the fluid inclusions by SEM-EDS analysis: halite, calcite, muscovite, millerite (NiS), barite and antarcticite (CaCl₂ · 6H₂O). All are interpreted to be trapped phases except halite which is a daughter mineral, and antarcticite which formed during sample preparation (freezing). Aqueous inclusions homogenize to liquid at temperatures between 75 °C and 400 °C; the mode is 375 °C. Aqueous-carbonic inclusions homogenize to liquid or vapor between 210 °C and 400 °C. Halite-bearing aqueous inclusions homogenize by halite dissolution at approximately 170 °C. Aqueous inclusions containing trapped solids exhibit liquid-vapor homogenization at temperatures similar to those of halite-bearing aqueous inclusions. Temperatures of vein formation, based on oxygen isotopic fractionation between quartz and muscovite, range from 342 °C to 584 °C. The corresponding oxygen isotope composition of the aqueous fluid in equilibrium with these minerals ranges from 1.2 to 5.5 per mil with a mean of 3.9 per mil, suggesting that the liquid had a significant meteoric component. Isochores for aqueous fluid inclusions intersect the modal isotopic isotherm of 425 °C at pressures between 590 and 1900 bar. A model is proposed in which molybdenite was deposited owing to decreasing temperature and/or pressure from CO₂-bearing, moderate to high salinity fluids of mixed magmatic-meteoric origin that were in equilibrium with K-feldspar and muscovite. These fluids resulted from the degassing of a monzogranitic magma and evolved through interaction with volcanic (komatiitic) and sedimentary country rocks. Received: 6 February 1997 / Accepted: 28 January 1998     

Fluid inclusion study of the Wunugetu Cu–Mo deposit,Inner Mongolia,China

Hydrothermal alteration and mineralization at the Wunugetu porphyry Cu–Mo deposit, China, include four stages, i.e., the early stage characterized by quartz, K-feldspar and minor mineralization, followed by a molybdenum mineralization stage associated with potassic alteration, copper mineralization associated with sericitization, and the last Pb–Zn mineralization stage associated with carbonation. Hydrothermal quartz contains three types of fluid inclusions, namely aqueous (W-type), daughter mineral-bearing (S-type) and CO₂-rich (C-type) inclusion, with the latter two types absent in the late stage. Fluid inclusions in the early stage display homogenization temperatures above 510°C, with salinities up to 75.8 wt.% NaCl equivalent. The presence of S-type inclusions containing anhydrite and hematite daughter minerals and C-type inclusions indicates an oxidizing, CO₂-bearing environment. Fluid inclusions in the Mo- and Cu-mineralization stages yield homogenization temperatures of 342–508°C and 241–336°C, and salinities of 8.6–49.4 and 6.3–35.7 wt.% NaCl equivalent, respectively. The presence of chalcopyrite instead of hematite and anhydrite daughter minerals in S-type inclusions indicates a decreasing of oxygen fugacity. In the late stage, fluid inclusions yield homogenization temperatures of 115–234°C and salinities lower than 12.4 wt.% NaCl equivalent. It is concluded that the early stage fluids were CO₂ bearing, magmatic in origin, and characterized by high temperature, high salinity, and high oxygen fugacity. Phase separation occurred during the Mo- and Cu-mineralization stages, resulting in CO₂ release, oxygen fugacity decrease and rapid precipitation of sulfides. The late-stage fluids were meteoric in origin and characterized by low temperature, low salinity, and CO₂ poor.     

First Data on Formation Conditions of the Zhilnoye Au–Ag Epithermal Gold Deposit (Eastern Chukotka,Russia)

The first data on study of individual fluid inclusions in the Zhilnoye deposit have been obtained. It has been found that the gold-bearing quartz veins of the deposit were formed by heterogeneous hydrothermal fluids with low salt concentrations (0.2–3.6 wt% equiv. NaCl under intermediate temperature conditions of 246–350°C). The fluid pressure was 80–160 bar corresponding to 0.3–0.6 km depths of formation under hydrostatic conditions. The parameters of the mineral-forming fluids of the Zhilnoye deposit correspond to typical parameters of the fluids of epithermal deposits.     

Geological and fluid inclusion studies of the Dongpo tungsten skarn ore deposit,China

The Dongpo tungsten ore deposit, the largest scheelite skarn deposit in China, is located at the contact of a 172-m. y. biotite granite with a Devonian marble. The mineralization associated with the granite includes W, Bi-Mo, Cu-Sn and Pb-Zn ores. Several W mineralization stages are shown by the occurrence of ore in massive skarn deposits and in later cross-cutting veins. The high garnet/pyroxene ratio, the hedenbergite and diopside-rich pyroxene and the andradite-rich garnet show the deposit belongs to the oxidized skarn type. Detailed fluid inclusion studies of granite, greisen, skarn and vein samples reveal three types of fluid inclusion: (1) liquid-rich, (2) gas-rich and (3) inclusions with several daughter minerals. Type (3) is by far the most common in both skarn and vein samples. The dominant daughter mineral in fluid inclusions is rhembic, highly birefringent, and does not dissolve on heating even at 530°C. We assume that this mineral is calcite. The liquid phase in most of the fluid inclusions has low to moderate salinities: 0–15 wt. %; in a few has higher salinities (30–40 wt. % NaCl equivalent). The homogenization temperatures of inclusions in the skarn stage range from 350°C to 530°C, later tungsten mineralization-stage inclusions homogenize between 200°C and 300°C, as do inclusions in veins. Fluid inclusions in granite and greisen resemble those of the late tungsten mineralization stage, with low salinity and homogenization temperatures of 200°–360°C. The tungsten-forming fluids are probably a mixture that came from biotite granite and the surrounding country rocks.     

Silicate and salt melts in the genesis of the industrial’noe tin deposit: Evidence from inclusions in minerals

The data obtained on melt and fluid inclusions in minerals of granites, metasomatic rocks, and veins with tin ore mineralization at the Industrial’noe deposit in the southern part of the Omsukchan trough, northeastern Russia, indicate that the melt from which the quartz of the granites crystallized contained globules of salt melts. Silicate melt inclusions were used to determine the principal parameters of the magmatic melts that formed the granites, which had temperatures at 760–1020°C, were under pressures of 0.3–3.6 kbar, and had densities of 2.11–2.60 g/cm³ and water concentrations of 1.7–7.0 wt %. The results obtained on the fluid inclusions testify that the parameters of the mineral-forming fluids broadly varied and corresponded to temperatures at 920–275°C, pressures 0.1–3.1 kbar, densities of 0.70–1.90 g/cm³, and salinities of 4.0–75.0 wt % equiv. NaCl. Electron microprobe analyses of the glasses of twelve homogenized inclusions show concentrations of major components typical of an acid magmatic melt (wt %, average): 73.2% SiO₂, 15.3% Al₂O₃, 1.3% FeO, 0.6% CaO, 3.1% Na₂O, and 4.5% K₂O at elevated concentrations of Cl (up to 0.51 wt %, average 0.31 wt %). The concentrations and distribution of some elements (Cl, K, Ca, Mn, Fe, Cu, Zn, Pb, As, Br, Rb, Sr, and Sn) in polyphase salt globules in quartz from both the granites and a mineralized miarolitic cavity in granite were assayed by micro-PIXE (proton-induced X-ray emission). Analyses of eight salt globules in quartz from the granites point to high concentrations (average, wt %) of Cl (27.5), Fe (9.7), Cu (7.2), Mn (1.1), Zn (0.66), Pb (0.37) and (average, ppm) As (2020), Rb (1850), Sr (1090), and Br (990). The salt globules in the miarolitic quartz are rich in (average of 29 globules, wt %) Cl (25.0), Fe (5.4), Mn (1.0), Zn (0.50), Pb (0.24) and (ppm) Rb (810), Sn (540), and Br (470). The synthesis of all data obtained on melt and fluid inclusions in minerals from the Industrial’noe deposit suggest that the genesis of the tin ore mineralization was related to the crystallization of acid magmatic melts. Original Russian Text@ V.B. Naumov, V.S. Kamenetsky, 2006, published in Geokhimiya, 2006, No. 12, pp. 1279–1289.     

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. Translated from Acta Geologica Sinica, 2006, 80(11): 1699–1705 [译自: 地质学报]     

Formation of the Vysoká–Zlatno Cu–Au skarn–porphyry deposit, Slovakia

The central zone of the Miocene Štiavnica stratovolcano hosts several occurrences of Cu–Au skarn–porphyry mineralisation, related to granodiorite/quartz–diorite porphyry dyke clusters and stocks. Vysoká–Zlatno is the largest deposit (13.4 Mt at 0.52% Cu), with mineralised Mg–Ca exo- and endoskarns, developed at the prevolcanic basement level. The alteration pattern includes an internal K- and Na–Ca silicate zone, surrounded by phyllic and argillic zones, laterally grading into a propylitic zone. Fluid inclusions in quartz veinlets in the internal zone contain mostly saline brines with 31–70 wt.% NaCl eq. and temperatures of liquid–vapour homogenization (Th) of 186–575°C, indicating fluid heterogenisation. Garnet contains inclusions of variable salinity with 1–31 wt.% NaCl eq. and Th of 320–360°C. Quartz–chalcopyrite veinlets host mostly low-salinity fluid inclusions with 0–3 wt.% NaCl eq. and Th of 323–364°C. Data from sphalerite from the margin of the system indicate mixing with dilute and cooler fluids. The isotopic composition of fluids in equilibrium with K-alteration and most skarn minerals (both prograde and retrograde) indicates predominantly a magmatic origin (δ¹⁸O_fluid 2.5–12.3‰) with a minor meteoric component. Corresponding low δD_fluid values are probably related to isotopic fractionation during exsolution of the fluid from crystallising magma in an open system. The data suggest the general pattern of a distant source of magmatic fluids that ascended above a zone of hydraulic fracturing below the temperature of ductile–brittle transition. The magma chamber at ∼5–6 km depth exsolved single-phase fluids, whose properties were controlled by changing PT conditions along their fluid paths. During early stages, ascending fluids display liquid–vapour immiscibility, followed by physical separation of both phases. Low-salinity liquid associated with ore veinlets probably represents a single-phase magmatic fluid/magmatic vapour which contracted into liquid upon its ascent.     

Imprints of hydrocarbon-bearing basinal fluids on a karst system: mineralogical and fluid inclusion studies from the Buda Hills,Hungary

Calcite veins and related sulphate–sulphide mineralisation are common in the Buda Hills. Also, abundant hypogenic caves are found along fractures filled with these minerals pointing to the fact that young cave-forming fluids migrated along the same fractures as the older mineralising fluids did. The studied vein-filling paragenesis consists of calcite, barite, fluorite and sulphides. The strike of fractures is consistent—NNW–SSE—concluding a latest Early Miocene maximum age for the formation of fracture-filling minerals. Calcite crystals contain coeval primary, hydrocarbon-bearing- and aqueous inclusions indicating that also hydrocarbons have migrated together with the mineralising fluids. Hydrocarbon inclusions are described here for the first time from the Buda Hills. Mixed inclusions, i.e., petroleum with ‘water-tail’, were also detected, indicating that transcrystalline water migration took place. The coexistence of aqueous and petroleum inclusions permitted to establish the entrapment temperature (80°C) and pressure (85 bar) of the fluid and thus also the thickness of sediments, having been eroded since latest Early Miocene times, was calculated (800 m). Low salinity of the fluids (<1.7 NaCl eq. wt%) implies that hydrocarbon-bearing fluids were diluted by regional karst water. FT-IR investigations revealed that CO₂ and CH₄ are associated with hydrocarbons. Groundwater also contains small amounts of HC and related gases on the basin side even today. Based on the location of the paleo- and recent hydrocarbon indications, identical migration pathways were reconstructed for both systems. Hydrocarbon-bearing fluids are supposed to have migrated north-westward from the basin east to the Buda Hills from the Miocene on.     

In situ strength measurements on natural upper-mantle minerals

Using in situ strength measurements at pressures up to 10 GPa and at room temperature, 400, 600, and 700°C, we examined rheological properties of olivine, orthopyroxene, and chromian-spinel contained in a mantle-derived xenolith. Mineral strengths were estimated using widths of X-ray diffraction peaks as a function of pressure, temperature, and time. Differential stresses of all minerals increase with increasing pressure, but they decrease with increasing temperature because of elastic strain on compression and stress relaxation during heating. During compression at room temperature, all minerals deform plastically at differential stress of 4–6 GPa. During subsequent heating, thermally induced yielding is observed in olivine at 600°C. Neither orthopyroxene nor spinel shows complete stress relaxation, but both retain some stress even at 700°C. The strength of the minerals decreases in the order of chromian-spinel ≈ orthopyroxene > olivine for these conditions. This order of strength is consistent with the residual pressure of fluid inclusions in mantle xenoliths.     

Influence of crude oil cracking on distribution of hydrocarbons in the Earth’s interior (experimental data)

The compositions and phase conditions of water-hydrocarbon fluids in synthetic quartz inclusions were studied by the methods of microthermometry, local IR spectroscopy, and gas-liquid chromatography. Synthetic quartz was grown in near-neutral fluoride, low-alkali bicarbonate, and alkali carbonate solutions with crude oil and its major fractions. The crystals with fluid inclusions were grown under thermal gradient conditions at relatively low temperatures (240–280°C) and pressures (6–45 MPa). After the study, the inclusions of grown crystals were subject to thermal processing in autoclaves at 350–380°C and 80–125 MPa. As a result, the initial water-hydrocarbon inclusions underwent significant changes. Hydrocarbon gases, largely methane and residual solid bitumens, appeared in their composition; the gasoline-kerosene fraction content increased substantially in liquid hydrocarbons (HCs). These changes are caused, first of all, by crude oil cracking, which is manifested already at 330°C and attains its maximum activity at 350–500°C (pressure of saturated vapor and higher). In natural conditions with increase in depths and, thus, the thermobaric parameters, this process is inevitable. According to the obtained experimental data, this very phenomenon and the existence of real thermal and baric gradients in the Earth’s interior provide for the formation of vertical zoning in the distribution of hydrocarbon deposits of different types.     

Multi-stage Ag–Bi–Co–Ni–U and Cu–Bi vein mineralization at Wittichen,Schwarzwald, SW Germany: geological setting,ore mineralogy,and fluid evolution

The Wittichen Co–Ag–Bi–U mining area (Schwarzwald ore district, SW Germany) hosts several unconformity-related vein-type mineralizations within Variscan leucogranite and Permian to Triassic redbeds. The multistage mineralization formed at the intersection of two fault systems in the last 250 Ma. A Permo-Triassic ore stage I with minor U–Bi–quartz–fluorite mineralization is followed by a Jurassic to Cretaceous ore stage II with the main Ag and Co mineralization consisting of several generations of gangue minerals that host the sub-stages of U–Bi, Bi–Ag, Ni–As–Bi and Co–As–Bi. Important ore minerals are native elements, Co and Ni arsenides, and pitchblende; sulphides are absent. The Miocene ore stage III comprises barite with the Cu–Bi sulfosalts emplectite, wittichenite and aikinite, and the sulphides anilite and djurleite besides native Bi, chalcopyrite, sphalerite, galena and tennantite. The mineral-forming fluid system changed from low salinity (<5 wt.% NaCl) at high temperature (around 300°C) in Permian to highly saline (around 25 wt.% NaCl + CaCl₂) at lower temperatures (50–150°C) in Triassic to Cretaceous times. Thermodynamic calculations and comparison with similar mineralizations worldwide show that the Mesozoic ore-forming fluid was alkaline with redox conditions above the hematite–magnetite buffer. We suggest that the precipitation mechanism for native elements, pitchblende and arsenides is a decrease in pH during fluid mixing processes. REE patterns in fluorite and the occurrence of Bi in all stages suggest a granitic source of some ore-forming elements, whereas, e.g. Ag, Co and Ni probably have been leached from the redbeds. The greater importance of Cu and isotope data indicates that the Miocene ore stage III is more influenced by fluids from the overlying redbeds and limestones than the earlier mineralization stages.     

Fluid evolution of rare-element and muscovite granitic pegmatites from central Galicia, NW Spain

Fluid inclusions have been studied in three pegmatite fields in Galicia, NW Iberian Peninsula. Based on microthermometry and Raman spectroscopy, eight fluid systems have been recognized. The first fluid may be considered to be a pegmatitic fluid which is represented by daughter mineral (silicates)-rich aqueous inclusions. These inclusions are primary and formed above 500 °C (dissolution of daughter minerals). During pegmatite crystallization, this fluid evolved to a low-density, volatile-rich aqueous fluid with low salinity (93% H₂O; 5% CO₂; 0.5% CH₄; 0.2% N₂; 1.3% NaCl) at minimum P–T conditions around 3 ± 0.5 kbar and 420 °C. This fluid is related to rare-metal mineralization. The volatile enrichment may be due to mixing of magmatic fluids and fluids equilibrated with the host rock. A drop in pressure from 3 ± 0.5 to 1 kbar at a temperature above 420 °C, which may be due to the transition from predominantly lithostatic to hydrostatic pressure, is recorded by two-phase, water-rich inclusions with a low-density vapour phase (CO₂, CH₄ and N₂). Another inclusion type is represented by two-phase, vapour-rich inclusions with a low-density vapour phase (CO₂, CH₄ and N₂), indicating a last stage of decreasing temperature (360 °C) and pressure (around 0.5 kbar), probably due to progressive exhumation. Finally, volatile (CO₂)-rich aqueous inclusions, aqueous inclusions (H₂O-NaCl) and mixed-salt aqueous inclusions with low Th, are secondary in charac- ter and represent independent episodes of hydrothermal fluid circulation below 310 °C and 0.5 kbar. Received: 14 October 1999 / Accepted: 5 October 1999     

Fluid evolution in a slate-belt gold deposit

Auriferous quartz veins in the Hill End goldfield, NSW, Australia, comprise bedding-parallel vein sets and minor extension and fault-controlled veins which are hosted by a multiply deformed, Late Silurian slate-metagreywacke turbidite sequence. Fluid inclusions in quartz, either from bedding-parallel veins or from narrow, steeply N-dipping veins (‘leader’ veins) indicate a similar range in homogenisation temperatures (T_h) from 350°C to 110°C. Within this range, T_h data demonstrate five groupings in the temperature intervals 350–280°C, 280–250°C, 250–190°C, 190–150°C, and 150–110°C, corresponding to a variety of primary and secondary inclusions developed during five periods of vein growth under a generally declining temperature regime. Inclusion fluids are characterised by a low salinity of around 0.1 to 3.6 wt% NaCl equivalent. Laser Raman microprobe inclusion analysis indicates that gas-phase compositions relate to the paragenetic stage of the host quartz. H₂O_(g) and N₂ dominate in the primary inclusions from barren, Stage I quartz; CH₄ and CH₄ + H₂O_(g) are important in inclusions related to the early gold forming events (equivalent to Stages II and III quartz), but inclusions developed during the last episode of gold deposition are characterised by H₂O_(g), CO₂-rich and liquid-CO₂ bearing fluids. Precipitation of gold was aided by sulphidation reactions or phase separation in response to periods of vein opening. Late in the paragenesis, gold deposition may have been promoted by oxidation of the ore fluid.     

Evidence for fluid phase separation in high-grade ore zones at the Porgera gold deposit, Papua New Guinea

Coexisting, liquid-rich and vapor-rich primary fluid inclusions in quartz provide direct evidence for fluid phase separation in high-grade quartz–roscoelite–gold veins and breccias from the Porgera alkalic-type gold deposit. Vapor-rich fluid inclusions are CO₂-rich, and sometimes contain liquid CO₂ at room temperature. The close spatial and paragenetic relationship between these “boiling assemblage” fluid inclusions and gold suggests that gold was precipitated by phase separation, at least locally. Additionally, the occurrence of carbonate and sulfate minerals in high-grade veins (reflecting pH increase and oxidation of the boiled fluid) and the appearance of hydrothermal breccias, are consistent with the process of fluid phase separation. Liquid CO₂-bearing fluid inclusions are rare in near-surface epithermal deposits, and indicate that the Porgera vein system was formed at greater depths and pressures (our estimates suggest pressures between 250 and 340 bars). It is suggested that alkalic-type gold deposits may be distinguished from other epithermal deposit types by the more gaseous nature of the ore-forming fluids, in addition to their association with alkalic magmas. Received: 24 February 2000 / Accepted: 6 April 2000     

Semial ophiolite veins of United Arab Emirates—A fluid inclusions study

Calcite and quartz veins in the gabbroic and dunite rocks of the Semial ophiolite (UAE) were selected for fluid inclusion analysis. The inclusions contain both aqueous low-salinity and hydrocarbon-dominated fluids. Mi-crothermometry data indicate that the aqueous fluids contain 0.22 to 1.45 equivalent wt% NaCl and occasionally contain traces of hydrocarbons. Homogenization to liquid occurred between 91 and 152℃. Modeling based on these fluid inclusion observations indicates that the trapping conditions of the studied rocks were subjected to temperatures of 162 and 172℃, occasional pressures of 610-710 Pa and the sequence percolation of aqueous and hydrocarbon fluids.     

Isotope geochemistry and fluid inclusion study of skarns from Vesuvius

Summary We present new mineral chemistry, fluid inclusion, stable carbon and oxygen, as well as Pb, Sr, and Nd isotope data of Ca-Mg-silicate-rich ejecta (skarns) and associated cognate and xenolithic nodules from the Mt. Somma-Vesuvius volcanic complex, Italy. The typically zoned skarn ejecta consist mainly of diopsidic and hedenbergitic, sometimes “fassaitic” clinopyroxene, Mg-rich and Ti-poor phlogopite, F-bearing vesuvianite, wollastonite, gehlenite, meionite, forsterite, clinohumite, anorthite and Mg-poor calcite with accessory apatite, spinell, magnetite, perovskite, baddeleyite, and various REE-, U-, Th-, Zr- and Ti-rich minerals. Four major types of fluid inclusions were observed in wollastonite, vesuvianite, gehlenite, clinopyroxene and calcite: a) primary silicate melt inclusions (T_HOM = 1000–1050 °C), b) CO₂ ± H₂S-rich fluid inclusions (T_HOM = 20–31.3 °C into the vapor phase), c) multiphase aqueous brine inclusions (T_HOM = 720–820 °C) with mainly sylvite and halite daughter minerals, and d) complex chloride-carbonate-sulfate-fluoride-silicate-bearing saline-melt inclusions (T_HOM = 870–890 °C). The last inclusion type shows evidence for immiscibility between several fluids (silicate melt – aqueous chloride-rich liquid – carbonate/sulfate melt?) during heating and cooling below 870 °C. There is no evidence for fluid circulation below 700 °C and participation of externally derived meteoric fluids in skarn formation. Skarns have considerably variable ²⁰⁶Pb/²⁰⁴Pb (19.047–19.202), ²⁰⁷Pb/²⁰⁴Pb (15.655–15.670), and ²⁰⁸Pb/²⁰⁴Pb (38.915–39.069) and relatively low ¹⁴³Nd/¹⁴⁴Nd (0.51211–0.51244) ratios. The carbon and oxygen isotope compositions of skarn calcites (δ¹³C_V-PDB = −5.4 to −1.1‰; δ18O_V-SMOW = 11.7 to 16.4‰) indicate formation from a ¹⁸O- and ¹³C-enriched fluid. The isotope composition of skarns and the presence of silicate melt inclusion-bearing wollastonite nodules suggests assimilation of carbonate wall rocks by the alkaline magma at moderate depths (< 5 km) and consequent exsolution of CO₂-rich vapor and complex saline melts from the contaminated magma that reacted with the carbonate rocks to form skarns. Received March 1, 2000; revised version accepted November 2, 2000     

Geochemical structure of base-metal filling veins and parameters of hydrothermal ore formation

The aim of this study was to determine at which parameters hydrothermal systems generate rich veins with bulk sphalerite contents of 30% and local concentrations in vein cross sections up to 60–70% and more. Such contents were found in the vein bodies of the Dzhimi deposit in the Sadon ore district, North Osetiya. For this purpose, we examined the thermodynamic models of the formation of base-metal filling veins. Ore-bearing fluids are formed in the root part of the hydrothermal system by the interaction of barren solutions with the host rocks (granites), which contain background contents of ore elements. The thermodynamic simulations were conducted for the system H-O-K-Na-Ca-Mg-Al-Si-Fe-C-Cl-S-Zn-Pb-Cu, which is described by 54 minerals of constant and variable composition and 78 aqueous species. The calculations for the mobilization zone were carried out for the temperature range of 360–440°C (through 10°C) and pressures of 600–1200 bar (with a 100 bar step). At each of the indicated temperature and pressure values, 100 waves (portions) of primary barren solution were subsequently passed through the granites. More than 20 complete models of the formation of filling veins (each model involving from 1000 to 1300 calculations) were constructed for individual T-P points in the mobilization zone, which was modeled by a sequence of multiwave step flowing reactors with a step of 10°C from 350–420 to 100°C at a constant pressure within the range of 600–1100 bar. We studied the effect of different background contents of Zn and Pb in granites on the efficiency of mobilization and ore formation and compared the relations in the naturally occurring distribution of ore elements along the continuous cross sections through Pb-Zb veins with the results of thermodynamic simulation. It was established that ore bodies with indicated bulk and local cross sectional contents of sphalerite could be formed in a narrow range of conditions in the mobilization zone (410–440°C and 900–1200 bar) and elevated background contents of Zn (more than 0.007 wt %) in the host granite. The maximum sphalerite contents (bulk and local in vein cross sections) are achieved updip the model veins within the temperature range of 150–200°C. Original Russian Text ? M.V. Borisov, D.A. Bychkov, Yu.V. Shvarov, 2006, published in Geokhimiya, 2006, No. 11, pp. 1218–1239.     

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 (δ³⁴S_H2S = 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 (δ¹⁸O_H2O = −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.