High CO2 content of fluid inclusions in gold mineralisations in the Ashanti Belt, Ghana: a new category of ore forming fluids?

Fluid inclusions were studied in samples from the Ashanti, Konongo-Southern Cross, Prestea, Abosso/Damang and Ayanfuri gold deposits in the Ashanti Belt, Ghana. Primary fluid inclusions in quartz from mineralised veins of the Ashanti, Prestea, Konongo-Southern Cross, and Abosso/Damang deposits contain almost exclusively volatile species. The primary setting of the gaseous (i.e. the fluid components CO₂, CH₄ and N₂) fluid inclusions in clusters and intragranular trails suggests that they represent the mineralising fluids. Microthermometric and Raman spectroscopic analyses of the inclusions revealed a CO₂ dominated fluid with variable contents of N₂ and traces of CH₄. Water content of most inclusions is below the detection limits of the respective methods used. Aqueous inclusions are rare in all samples with the exception of those from the granite-hosted Ayanfuri mineralisation. Here inclusions associated with the gold mineralisation contain a low salinity (<6 eq.wt.% NaCl) aqueous solution with variable quantities of CO₂. Microthermometric investigations revealed densities of the gaseous inclusions of 0.65 to 1.06 g/cm³ at Ashanti, 0.85 to 0.98 g/cm³ at Prestea, up to 1.02 g/cm³ at Konongo-Southern Cross, and 0.8 to 1.0 g/cm³ at Abosso/Damang. The fluid inclusion data are used to outline the PT ranges of gold mineralisation of the respective gold deposits. The high density gaseous inclusions found in the auriferous quartz at Ashanti and Prestea imply rather high pressure trapping conditions of up to 5.4 kbar. In contrast, mineralisation at Ayanfuri and Abosso/Damang is inferred to have occurred at lower pressures of only up to 2.2 kbar. Mesothermal gold mineralisation is generally regarded to have formed from fluids characterized by H₂O > CO₂ and low salinity ( ±  6 eq.wt.%NaCl). However, fluid inclusions in quartz from the gold mineralisations in the Ashanti belt point to distinctly different fluid compositions. Specifically, the predominance of CO₂ and CO₂ >> H₂O have to be emphasized. Fluid systems with this unique bulk composition were apparently active over more than 200␣km along strike of the Ashanti belt. Fluids rich in CO₂ may present a hitherto unrecognised new category of ore-forming fluids. Received: 30 May 1996 / Accepted: 8 October 1996     

The Malanjkhand copper ( + molybdenum) deposit, India: mineralization from a low-temperature ore-fluid of granitoid affiliation

  Copper and subordinate molybdenum mineralization at Malanjkhand occurs within a fracture-controlled quartz-reef enclosed in a pink granitoid body surrounded by grey-granitoids constituting the regional matrix. Sulfide-bearing stringers, pegmatites with only quartz + microcline and sulfide disseminations, all within the pink-granitoid, represent other minor modes of occurrences. Despite this diversity in mode of occurrence, the mineralogy of ores is quite consistent and conform to a common paragenetic sequence comprising an early `ferrous' stage of precipitation of magnetite (I) and pyrite (I) and, the main-stage chalcopyrite mineralization with minor sphalerite, pyrite (II), magnetite (II), molybdenite and hematite. Both stages witnessed continuous precipitation of quartz ± microcline ± (chlorite, biotite and epidote). The enclosing pink-granitoid and the regional grey-granitoids display alteration features such as saussuritization of plagioclase, breakdown of hornblende and chloritization of biotite on a regional scale, indicating interaction with a pervasive fluid. Quartz and microcline precipitation mostly restricted within the pink granitoid, postdates this alteration. Four types of primary inclusions were encountered in quartz from ore samples: (1) type-I – aqueous-biphase(L + V) inclusions, the commonest variety in all ore types; (2) type-II – aqueous-carbonic(L_aq + L_carb ± V_carb); (3) type-III – pure-carbonic(L_carb ± V_carb) – type-II and III being restricted to stringer and pegmatitic ores, and (4) rare polyphase (L_aq + V_aq + calcite/gypsum) inclusions. Quartz in granitoids contain primary type-I inclusions only. Type-I inclusions from ore samples furnish a temperature range (after a rough pressure correction to the T _H  -maxima of 140–180 °C) of 150–275 °C and a moderately low salinity of 4–12 wt.% NaCl equivalent. This is inferred to represent the signature of the major component (F2) of the ore fluid. A few type-I inclusions of higher T _M (up to 380 °C) and low salinity and density represent the other (F1) identifiable component of the ore fluid present in low proportion. The T _H  -maxima and the total range in salinity of type-I inclusions in quartz from granitoids are strikingly similar to those from the ore samples. Composition of syn-ore chlorites furnished a temperature range of 185–327 °C, which conforms to the fluid inclusion microthermometric data. Pressure estimates using standard fluid inclusion geobarometric methods, vary from 550 to 1790 bar in the stringer ores. Observed temperature-salinity/density relationships are best explained by a two-stage evolution model of the ore fluid: the first stage witnessed mixing of the two components, F1 and F2 in unequal proportion, bringing about mineralization. The second stage of evolution was marked by the separation of a carbonic component on continued sulfide precipitation and attendant increase in salinity of the fluid. The F1 component emerged as a distinct, heated and (CO₂ + S)-charged entity due to steam-heating and contamination of the early-ingressed F2 fluid at the fracture zone. The pervasive fluid phase in the surrounding granitoids contributed the F2 component. Received: (10 August 1994), 15 August 1995 / Accepted: 12 January 1996     

Fluid inclusion microthermometry and the P-T evolution of gold-bearing hydrothermal fluids in the Niuxinshan gold deposit, eastern Hebei province, NE China

Niuxinshan is a typical example of the numerous mesothermal gold deposits formed during Mesozoic tectono-magmatic reactivation of the Archean North China Craton in eastern Hebei province. Gold occurs in quartz-sulfide lodes in Archean amphibolites and also in greisen zones in the Mesozoic Niuxinshan granite stock. Four mineralization stages can be recognized from early to late: (1) quartz-K-feldspar, (2) quartz-pyrite, (3) quartz-polysulfide, and (4) quartz-carbonate. Gold mineralization mainly occurs in stages 2 and 3. Fluid inclusions in quartz and fluorite from greisen zones in the Niuxinshan granite, and inclusions in vein quartz and sphalerite from stages 1 to 3 in the amphibolites, have been studied by microthermometry. Three compositional types of inclusions are recognized: type 1 (Tp1) are H₂O-CO₂-bearing inclusions and include primary (Tp1-P) and secondary (Tp1-S) inclusions. These are found in quartz and fluorite from the greisen zones as well as in vein quartz and sphalerite from stages 1 to 3. The Tp1-P inclusions are considered to represent the gold-bearing hydrothermal fluids. Type 2 (Tp2-S) are secondary H₂O-CO₂ + solid phase inclusions in fluorite from the greisen zones. Type 3 (Tp3-S) are secondary aqueous inclusions with a solid phase which coexist with the Tp2-S in fluorite from the greisen zones. The Tp1-P inclusions show variable V_CO2 (commonly 0.3 to 0.6) and X_CO2 values (mainly 0.1 to 0.4). The salinities of inclusions cluster around 3 to 11 wt.% NaCl equivalent and their homogenization temperatures to the liquid phase (Th(L)) fall dominantly in the range of 260 to 360 °C. The compositional variations of inclusions in stage 1 probably result from exsolution of magmatic fluids at various stages; immiscibility or boiling of the fluids can be ruled out. The compositional variations of inclusions in the greisen zones and in vein stages 2 and 3 are attributed to cooling, mixing (dilution), and necking-down of the fluids. The Tp1-S and Tp2-S inclusions show salinities of 3 to 6 wt.% NaCl equivalent and X_CO2 values of 0.04 to 0.17. Th(L) clusters at 240 to 260 °C. The Tp3-S inclusions have salinities of 3 to 6 wt.% NaCl equivalent and Th(L) of 170 to 240 °C. Isochoric reconstructions, combined with oxygen and sulfur isotope geothermometry of mineral pairs, give trapping P-T conditions for the gold-bearing fluids. The greisen zones formed at 310 to 460 °C and 1.3 to 3.7 kbar; stage 1 veins at 300 to 430 °C and 1.2 to 3.7 kbar; stage 2 veins at 290 to 380 °C and 1 to 3 kbar; stage 3 veins at 250 to 350 °C and 1 to 3 kbar. H₂O-CO₂ fluids with low to moderate salinities and moderate to high densities (0.66 to 1.01 g/cm³) dominated at early mineralization stages, and evolved towards H₂O-richer and CO₂- and less saline fluids through time. The retrograde P-T evolution probably resulted from regional uplift and cooling of gold-bearing hydrothermal fluids. The gold bisulfide complex was dominant in the fluids during mineralization and gold deposition was mainly induced by decreases of temperature and pressure, as well as destabilization of the bisulfide complex during sulfidization of wall rocks. Received: 16 March 1998 / Accepted: 11 January 1999     

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 characteristics of mesothermal gold deposits in the Xiaoqinling district, Shaanxi and Henan Provinces, People's Republic of China

Fluid inclusions were studied in quartz samples from early (stage I) gold-poor quartz veins and later (stage II) gold- and sulphide-rich quartz veins from the Wenyu, Dongchuang, Qiangma, and Guijiayu mesothermal gold deposits in the Xiaoqinling district, China. Fluid inclusion petrography, microthermometry, and bulk gas analyses show remarkably consistent fluid composition in all studied deposits. Primary inclusions in quartz samples are dominated by mixed CO₂-H₂O inclusions, which have a wide range in CO₂ content and coexist with lesser primary CO₂-rich and aqueous inclusions. In addition, a few secondary aqueous inclusions are found along late-healed fractures. Microthermometry and bulk gas analyses suggest hydrothermal fluids with typically 15–30 mol% CO₂ in stage I inclusions and 10–20 mol% CO₂ in stage II inclusions. Estimates of fluid salinity decrease from 7.4–9.2 equivalent wt.% NaCl to 5.7–7.4 equivalent wt.% NaCl between stage I and II. Primary aqueous inclusions in both stages show consistent salinity with, but slightly lower Th _total than, their coexistent CO₂-H₂O inclusions. The coexisting CO₂-rich, CO₂-H₂O, and primary aqueous inclusions in both stage I and II quartz are interpreted to have been trapped during unmixing of a homogeneous CO₂-H₂O parent fluid. The homogenisation temperatures of the primary aqueous inclusions give an estimate of trapping temperature of the fluids. Trapping conditions are typically 300–370 °C and 2.2 kbar for stage I fluids and 250–320 °C and 1.6 kbar for stage II fluids. The CO₂-H₂O stage I and II fluids are probably from a magmatic source, most likely devolatilizing Cretaceous Yanshanian granitoids. The study demonstrates that gold is largely deposited as pressures and temperatures fall accompanying fluid immiscibility in stage II veins. Received: 15 May 1997 / Accepted: 10 June 1998     

Genesis of itabirite-hosted Au–Pd–Pt-bearing hematite-(quartz) veins, Quadrilátero Ferrífero, Minas Gerais, Brazil: constraints from fluid inclusion infrared microthermometry, bulk crush-leach analysis and U–Pb systematics

Fluid inclusions hosted in quartz and specular hematite from auriferous (jacutinga) and barren veins in the Quadrilátero Ferrífero (QF) have been studied using conventional and near infrared microscopy, respectively. The mineralization consists of veins that cross-cut metamorphosed iron formation (itabirite) of the Paleoproterozoic Itabira Group. The sample suite comprises hematite from veins from the low-strain domain in the W and SW of the study area, as well as hematite samples from the eastern high-strain domain in the central and NE parts of the QF. Halogen ratios of fluid inclusions in quartz and hematite from all studied deposits are consistent with a fluid evolved from dissolving and reprecipitating halite that was subsequently diluted. Fluid inclusions hosted in quartz and hematite are characterized by consistent Na/K ratios and considerable SO₄ contents, and suggest similar formation conditions and, perhaps, fluid origin from a common source. Na/K and Na/Li fluid mineral geothermometers indicate water–rock interaction at approximately 340±40°C. Hematites from the high-strain domain contain fluid inclusion assemblages of high-temperature aqueous-carbonic and multiphase high-salinity, high-temperature aqueous inclusions probably due to fluid immiscibility in the system H₂O–NaCl–CO₂. Fluid inclusions hosted in hematite from barren veins in the low-strain domain, as well as in hematite from jacutinga-type mineralization from the central part of the QF, only host multiphase aqueous fluid inclusions all showing narrow ranges of salinity (7.2–11.7 wt.% NaCl equiv.) and homogenization temperatures (148 to 229°C). Lower homogenization temperatures and the absence of CO₂-rich inclusions in specular hematite from these occurrences are attributed to carbonate precipitation and/or CO₂ escape due to cooling during fluid migration from the high- to the low-strain domain. Pb–Pb and U–Pb systematics of gold, hematite and hematite-hosted fluid inclusions in combination with geochemical evidence indicate distinct sources for Pd, Au, and Pb. The formation of specular hematite veins may be related to retrograde metamorphic fluids being released during the Brazilian orogenic cycle (600–700 Ma). The Pb isotopic characteristics of all samples are readily reconciled in a simple model that involves two different Paleoproterozoic or Archean source lithologies for lead and reflects contrasting depths of fluid percolation during the Brasiliano orogeny.     

“Extreme boiling” model for variable salinity of the Hokko low-sulfidation epithermal Au prospect, southwestern Hokkaido, Japan

The Hokko prospect is located in the Minamikayabe area southwestern Hokkaido, Japan, where gold-bearing quartz veins of Pliocene age are exposed at the surface. The alteration mineral assemblage is typical of low-sulfidation epithermal systems, with the quartz veins associated with adularia alteration overprinted on Late Miocene propylitic alteration. Fluid inclusion studies of the vein quartz reveal mean homogenization temperatures of approximately 220 °C, and the co-existence of low-salinity (<2 wt.% NaCl equivalent) and moderate salinity (2 to 12 wt.% NaCl equivalent) fluid inclusions within the same veins. The moderate salinity fluid inclusions (2–12 wt.% NaCl equivalent) typically have relatively low homogenization temperatures between 150° to 200 °C. The results obtained from stable isotope analysis of  δ¹⁸O in quartz vein material showed a gradual decrease in  δ¹⁸O signatures with increasing depth. The majority of the samples have calculated fluid source signatures (δ¹⁸O_H2O) between −8.0 and −10.0‰, but there is a significant change in the composition above 185 m drill depth. The shallower samples in particular show a wide range of oxygen isotope signatures that are associated with the moderate salinity fluid inclusions. We interpret that low-salinity inclusions within the Hokko system represent the composition of the liquid phase of the fluid, before boiling, and that the moderate-salinity inclusions are representative of the residual liquid phase, after extensive non-adiabatic boiling and vapor loss in an open system. This mechanism resulted in the entrapment of fluids with variable salinities at the same time, and in close proximity to each other. This is also reflected in the  δ¹⁸O_H2O values which become more variable and heavier where the moderate-salinity inclusions occur. Deposition of ore minerals within the Hokko vein system also occurred at this time as a result of boiling and gas loss. Received: 30 May 1997 / Accepted: 6 January 1998     

Structural controls,temperature–pressure conditions and fluid evolution of orogenic gold mineralisation at the Betam mine,south Eastern Desert,Egypt

The Betam gold deposit, located in the southern Eastern Desert of Egypt, is related to a series of milky quartz veins along a NNW-trending shear zone, cutting through pelitic metasedimentary rocks and small masses of pink granite. This shear zone, along with a system of discrete shear and fault zones, was developed late in the deformation history of the area. Although slightly sheared and boudinaged within the shear zone, the auriferous quartz veins are characterised by irregular walls with a steeply plunging ridge-in-groove lineation. Shear geometry of rootless intra-folial folds and asymmetrical strain shadows around the quartz lenses suggests that vein emplacement took place under a brittle–ductile shear regime, clearly post-dating the amphibolite-facies regional metamorphism. Hydrothermal alteration is pervasive in the wallrock metapelites and granite including sericitisation, silicification, sulphidisation and minor carbonatisation. Ore mineralogy includes pyrite, arsenopyrite and subordinate galena, chalcopyrite, pyrrhotite and gold. Gold occurs in the quartz veins and adjacent wallrocks as inclusions in pyrite and arsenopyrite, blebs and globules associated with galena, fracture fillings in deformed arsenopyrite or as thin, wire-like rims within or around rhythmic goethite. Presence of refractory gold in arsenopyrite and pyrite is inferred from microprobe analyses. Clustered and intra-granular trail-bound aqueous–carbonic (L_CO2 + L_aq ± V_CO2) inclusions are common in cores of the less deformed quartz crystals, whereas carbonic (L_CO2 ± V_CO2) and aqueous H₂O–NaCl (L + V) inclusions occur along inter-granular and trans-granular trails. Clathrate melting temperatures indicate low salinities of the fluid (3–8 wt.% NaCl eq.). Homogenisation temperatures of the aqueous–carbonic inclusions range between 297 and 323°C, slightly higher than those of the intra-granular and inter-granular aqueous inclusions (263–304°C), which are likely formed during grain boundary migration. Homogenisation temperatures of the trans-granular H₂O–NaCl inclusions are much lower (130–221°C), implying different fluids late in the shear zone formation. Fluid densities calculated from aqueous–carbonic inclusions along a single trail are between 0.88 and 0.98 g/cm³, and the resulting isochores suggest trapping pressures of 2–2.6 kbar. Based on the arsenopyrite–pyrite–pyrrhotite cotectic, arsenopyrite (30.4–30.7 wt.% As) associated with gold inclusions indicates a temperature range of 325–344°C. This ore paragenesis constrains f _S2 to the range of 10⁻¹⁰ to 10^−8.5 bar. Under such conditions, gold was likely transported mainly as bisulphide complexes by low salinity aqueous–carbonic fluids and precipitated because of variations in pH and f _O2 through pressure fluctuation and CO₂ effervescence as the ore fluids infiltrated the shear zone, along with precipitation of carbonate and sericite. Wallrock sulphidation also likely contributed to destabilising the gold–bisulphide complexes and precipitating gold in the hydrothermal alteration zone adjacent to the mineralised quartz veins.     

Hydrothermal fluid evolution and structural control of the Guarim gold mineralisation, Tapajós Province, Amazonian Craton, Brazil

Fluid inclusion and structural studies were carried out at the Guarim gold deposit in the Palaeoproterozoic Tapajós province of the Amazonian craton. Guarim is a fault-hosted gold deposit cutting basement granitoids. It consists of a quartz vein, which is massive in its inner portions, grading laterally either to a massive or to cavity-bearing quartz vein associated with hydrothermal breccias. The wallrock alteration comprises chlorite, carbonate, white mica and sulphide minerals, with free gold occurring within quartz grains and spatially associated with sulphide mineral grains. Petrographic, microthermometric and Laser Raman investigations recognised CO₂-rich, mixed H₂O–CO₂, and H₂O fluid inclusions. The coexisting CO₂ and H₂O–CO₂ inclusions were interpreted as primary immiscible fluids that formed the gold-bearing vein. The H₂O inclusions were considered a product of later infiltration of fluids unrelated to the mineralising episode. The mineralising fluid has CO₂ ranging typically from 5–10 mol%, contains traces of N₂, has salinities of ∼5 wt% NaCl equiv., and densities varying between 0.85 and 0.95 g/cm³. The P–T estimations bracket gold deposition between 270–320 °C and 0.86–2.9 kb; ƒ_O2–ƒ_S2–pH estimates suggest a reduced, near-neutral character for the fluid. Variations in the physico-chemical properties, as demonstrated by the fluid inclusion study, resulted from a combination of fluid immiscibility and pressure fluctuation. This interpretation, combined with textural and structural evidence, suggests the emplacement of the mineralised vein in an active fault and at a rather shallow level (4–7 km). The geological and structural setting, deposit-scale textures and structures, wallrock alteration and physico-chemical fluid properties are compatible with those of epizonal to mesozonal orogenic lode gold deposits. Received: 3 March 2000 / Accepted: 21 October 2000     

Origin of CO2-rich fluid inclusions in synorogenic veins from the Eastern Mount Isa Fold Belt, NW Queensland, and their implications for mineralization

Synorogenic veins from the Proterozoic Eastern Mount Isa Fold Belt contain three different types of fluid inclusions: CO₂-rich, aqueous two-phase and rare multiphase. Inclusions of CO₂ without a visible H₂O phase are particularly common. The close association of CO₂-rich inclusions with aqueous two-phase, and possibly multiphase inclusions suggests that phase separation of low- to -moderate salinity CO₂-rich hydrothermal fluids led to the selective entrapment of the CO₂. Microthermometric results indicate that CO₂-rich inclusions homogenize between –15.5 and +29.9 °C which corresponds to densities of 0.99 to 0.60 g.cm⁻³. The homogenization temperatures of the associated aqueous two-phase inclusions are 127–397 °C, with salinities of 0.5 to 18.1 wt.% NaCl equivalent. The rarely observed multiphase inclusions homogenize between 250 and 350 °C, and have salinities ranging from 34.6 to 41.5 wt.% NaCl equivalent. Evidence used to support the presence of fluid immiscibility in this study is mainly derived from observations of coexisting H₂O-rich and CO₂-rich inclusions in groups and along the same trail. In addition, these two presumably unmixed fluids are also found on adjacent fractures where monophase CO₂-rich inclusions are closely related to H₂O-rich inclusions. Similar CO₂-rich inclusions are widespread in mineral deposits in this region, which are simply metal-enriched synorogenic veins. Therefore, we argue that fluid immiscibility caused volatile species such as CO₂ and H₂S to be lost from liquid, thus triggering ore deposition by increasing the fluid pH and decreasing the availability of complexing ligands. Received: 28 April 1997 / Accepted: 4 January 1999     

Epithermal mineralization and ore controls of the Shasta Au-Ag deposit, Toodoggone District, British Columbia, Canada

The Shasta gold-silver deposit, British Columbia, Canada, is an adularia-sericite-type epithermal deposit in which deposition of precious metals coincided with the transition of quartz- to calcite-dominant gangue. Mineralization is associated with stockwork-breccia zones in potassically altered dacitic lapilli tuffs and flows, and consists of pyrite, sphalerite, chalcopyrite, galena, acanthite, electrum and native silver. Pre- and post-ore veins consist solely of quartz and calcite, respectively. Fluid inclusion microthermometry indicates that ore minerals were deposited between 280 ° and 225 °C, from a relatively dilute hydrothermal fluid (˜1.5 wt.% NaCl equivalent). Abundant vapor-rich inclusions in ore-stage calcite are consistent with boiling. Oxygen and hydrogen isotopic data (δ¹⁸O_fluid = −1.5 to −4.1‰; δD_fluid = −148 to −171‰) suggest that the fluid had a meteoric origin, but was ¹⁸O-enriched by interaction with volcanic wallrocks. Initial (˜280 °C) fluid pH and log f O₂ conditions are estimated at 5.3 to 6.0, and −32.5 to −33 bar, respectively; during ore deposition, the fluid became more alkaline and oxidizing. Ore deposition at Shasta is attributed to localization of meteoric hydrothermal fluids by extensional faults; mineralization was controlled by boiling in response to hydraulic brecciation. Calcite and base metal sulfides precipitated due to the increase in pH that accompanied boiling, and the associated decrease in H₂S concentration led to precipitation of gold and silver. Received: 23 February 1995 / Accepted: 16 April 1996     

Fluid inclusion study of the Ballinglen W-Sn-sulphide mineralization, SE Ireland

Scheelite-mineralized microtonalite sheets occur on the SE margin of the end-Caledonian Leinster Granite in SE Ireland. Scheelite, polymetallic sulphides and minor cassiterite occur in veins in the microtonalites, disseminated throughout the greisened microtonalite sheets and in the adjacent wallrocks. Two major mineralized vein types occur in the microtonalite sheets: (1) Scheelite ± arsenopyrite ± pyrrhotite occur in quartz-fluorite veins, generally without a muscovite selvage; (2) Sphalerite ± chalcopyrite ± pyrite ± galena ± cassiterite ± stannite occur in quartz + fluorite veins with a coarse muscovite selvage and are often intergrown with the muscovite. Quartz-hosted fluid inclusions were examined from representative samples of both vein types using petrographic, microthermometric and laser Raman spectroscopic techniques. Three distinct types of fluid inclusions have been recognized. Primary, vapour rich Type 1 inclusions in quartz from the scheelite-mineralized veins are of H₂O-CO₂-CH₄-N₂ ± H₂S ± NaCl composition and formed between 360–530 °C. Primary and secondary, liquid-rich Type 2 fluid inclusions in the base metal sulphide-mineralized veins are of H₂O-CH₄-N₂ ± H₂S-NaCl composition and formed between 340–480 °C. They also occur as pseudosecondary and secondary inclusions in scheelite-mineralized veins. Late dilute, low temperature H₂O-NaCl + KCl fluid inclusions may be related to late-Caledonian convection of meteoric waters around the cooling Leinster Granite batholith. Received: 4 September 1996 / Accepted: 23 May 1997     

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     

Retrograde mineral and fluid evolution in high-pressure metapelites (Schistes lustrés unit, Western Alps)

Fluid inclusions have been analysed in successive generations of syn-metamorphic segregations within low-grade, high-pressure, low-temperature (HP–LT) metapelites from the Western Alps. Fluid composition was then compared to mass transfer deduced from outcrop-scale retrograde mineral reactions. Two types of quartz segregations (veins) occur in the `Schistes lustrés' unit: early blueschist-facies carpholite-bearing veins (BS) and retrograde greenschist-facies chlorite-bearing veins (GS). Fluid inclusions in both types of segregations are aqueous (no trace of dissolved gases such as CO₂, CH₄, N₂), with significant differences in density and composition (salinity). BS fluids are moderately saline fluids (average 9.1 wt% eq. NaCl) characterized by a chronological trend towards more dilute composition (from 15 down to 0 wt% eq. NaCl), whereas GS fluids have a very constant salinity of ∼3.7 wt% eq. NaCl. Both types of inclusions were continuously reset to lower densities along the retrograde path, until a temperature of ∼300 °C. Mass-balance calculations, together with fluid inclusion data, suggest that GS fluids result from the mixing between two fluid sources: one initial, early metamorphic, moderately saline HP fluid and a second nearly pure water fluid provided by the breakdown of carpholite. Estimates of the amount of water released by carpholite breakdown result in a dilution of the interstitial fluid phase (from 10 to 2.5–4 wt% eq. NaCl) consistent with the actual shift of the fluid composition. Alkali elements required for the formation of the GS chlorite + phengite assemblage after carpholite could be locally provided by HP phengite. This is taken as an indirect evidence that, during the generation of both BS and GS fluids, mixing with externally derived fluids may have been very limited. The location, amount and constant composition of the less saline GS fluids appear to be related to an interconnected porosity at the time of inclusion formation. Received: 19 October 1998 / Accepted: 19 July 2000     

Hydrocarbon- and ore-bearing basinal fluids: a possible link between gold mineralization and hydrocarbon accumulation in the Youjiang basin,South China

The Youjiang basin, which flanks the southwest edge of the Yangtze craton in South China, contains many Carlin-type gold deposits and abundant paleo-oil reservoirs. The gold deposits and paleo-oil reservoirs are restricted to the same tectonic units, commonly at the basinal margins and within the intrabasinal isolated platforms and/or bioherms. The gold deposits are hosted by Permian to Triassic carbonate and siliciclastic rocks that typically contain high contents of organic carbon. Paragenetic relationships indicate that most of the deposits exhibit an early stage of barren quartz ± pyrite (stage I), a main stage of auriferous quartz + arsenian pyrite + arsenopyrite + marcasite (stage II), and a late stage of quartz + calcite + realgar ± orpiment ± native arsenic ± stibnite ± cinnabar ± dolomite (stage III). Bitumen in the gold deposits is commonly present as a migrated hydrocarbon product in mineralized host rocks, particularly close to high grade ores, but is absent in barren sedimentary rocks. Bitumen dispersed in the mineralized rocks is closely associated and/or intergrown with the main stage jasperoidal quartz, arsenian pyrite, and arsenopyrite. Bitumen occurring in hydrothermal veins and veinlets is paragenetically associated with stages II and III mineral assemblages. These observations suggest an intimate relationship between bitumen precipitation and gold mineralization. In the paleo-petroleum reservoirs that typically occur in Permian reef limestones, bitumen is most commonly observed in open spaces, either alone or associated with calcite. Where bitumen occurs with calcite, it is typically concentrated along pore/vein centers as well as along the wall of pores and fractures, indicating approximately coeval precipitation. In the gold deposits, aqueous fluid inclusions are dominant in the early stage barren quartz veins (stage I), with a homogenization temperature range typically of 230°C to 270°C and a salinity range of 2.6 to 7.2 wt% NaCl eq. Fluid inclusions in the main and late-stage quartz and calcite are dominated by aqueous inclusions as well as hydrocarbon- and CO₂-rich inclusions. The presence of abundant hydrocarbon fluid inclusions in the gold deposits provides evidence that at least during main periods of the hydrothermal activity responsible for gold mineralization, the ore fluids consisted of an aqueous solution and an immiscible hydrocarbon phase. Aqueous inclusions in the main stage quartz associated with gold mineralization (stage II) typically have a homogenization temperature range of 200–230°C and a modal salinity around 5.3 wt% NaCl eq. Homogenization temperatures and salinities of aqueous inclusions in the late-stage drusy quartz and calcite (stage III) typically range from 120°C to 160°C and from 2.0 to 5.6 wt% NaCl eq., respectively. In the paleo-oil reservoirs, aqueous fluid inclusions with an average homogenization temperature of 80°C are dominant in early diagenetic calcite. Fluid inclusions in late diagenetic pore- and fissure-filling calcite associated with bitumen are dominated by liquid C₂H₆, vapor CH₄, CH₄–H₂O, and aqueous inclusions, with a typical homogenization temperature range of 90°C to 180°C and a salinity range of 2–8 wt% NaCl eq. It is suggested that the hydrocarbons may have been trapped at relatively low temperatures, while the formation of gold deposits could have occurred under a wider and higher range of temperatures. The timing of gold mineralization in the Youjiang basin is still in dispute and a wide range of ages has been reported for individual deposits. Among the limited isotopic data, the Rb–Sr date of 206 ± 12 Ma for Au-bearing hydrothermal sericite at Jinya as well as the Re–Os date of 193 ± 13 Ma on auriferous arsenian pyrite and ⁴⁰Ar/³⁹Ar date of 194.6 ± 2 Ma on vein-filling sericite at Lannigou may provide the most reliable age constraints on gold mineralization. This age range is comparable with the estimated petroleum charging age range of 238–185 Ma and the Sm–Nd date of 182 ± 21 Ma for the pore- and fissure-filling calcite associated with bitumen at the Shitouzhai paleo-oil reservoir, corresponding to the late Indosinian to early Yanshanian orogenies in South China. The close association of Carlin-type gold deposits and paleo-oil reservoirs, the paragenetic coexistence of bitumens with ore-stage minerals, the presence of abundant hydrocarbons in the ore fluids, and the temporal coincidence of gold mineralization and hydrocarbon accumulation all support a coeval model in which the gold originated, migrated, and precipitated along with the hydrocarbons in an immiscible, gold- and hydrocarbon-bearing, basinal fluid system.     

Implications from inclusions in topaz for greisenisation and mineralisation in the Hensbarrow topaz granite, Cornwall, England

Textural and geochemical studies of inclusions in topaz from greisens in the Hensbarrow topaz granite stock (St. Austell, Cornwall) are used to constrain the composition of fluids responsible for late stage greisening and mineralisation. The topaz contains an abundant and varied suite of inclusions including aqueous liquid + vapour (L + V), quartz, zinnwaldite, albite, K-feldspar, muscovite, ilmenorutile, apatite, columbite, zircon, varlamoffite [(Sn, Fe)(O, OH)₂] and qitianlingite [(Fe⁺²,Mn⁺²)₂(Nb,Ta)₂W⁺⁶O₁₀]. Primary L + V inclusions in topaz show relatively high T _h (mainly 300 to >500 °C) and a narrow range of salinities (23–30 wt % NaCl equivalent) compared with those in greisen quartz (150–450 °C, 0–50 wt % NaCl equivalent). Textures indicate that topaz formed earlier than quartz and the fluid inclusion data are interpreted as indicating a cooling of the hydrothermal fluids during greisenisation, mixing with meteoric waters and a decrease in pressure causing intermittent boiling. The presence of early-formed albite and K-feldspar as inclusions in the topaz is likely to indicate that the greisen-forming fluid became progressively more acid during greisenisation. The most distinctive inclusions in the topaz are wisp- and bleb-shaped quartz, < 50 μm in size, which show textural characteristics indicating former high degrees of plasticity. They often have multiple shrinkage bubbles at their margins rich in Sn, Fe, Mn, S and Cl and, more rarely, contain euhedral albite, K-feldspar, stannite or pyrrhotite crystals up to 40 μm in size. The quartz inclusions show similar morphologies to inclusions in topaz from quartz-topaz rocks elsewhere which have been interpreted as trapped “silicate melt”. Their compositions are, however, very different to those expected for late stage topaz-normative granitic melts. From their textural and chemical characteristics they are interpreted as representing crystallised silica colloid, probably trapped as a hydro gel during greisenisation. There is also evidence for the colloidal origin of inclusions of varlamoffite in the topaz. These occurrences offer the first reported evidence in natural systems for the formation of colloids in high temperature hydrothermal fluids. Their high ore carrying potential is suggested by the presence of varlamoffite and the occurrence of stannite, pyrrhotite and SnCl within the quartz inclusions. Received: 9 April 1996 / Accepted: 12 November 1996     

Fluid inclusions in the Niquelândia and Barro Alto Complexes, Goias State, Brazil

Summary ?Fluid inclusions from two Mesoproterozoic, metamorphosed layered intrusive complexes, Niquelandia and Barro Alto, Goiás State, Brazil record multiple fluid influx events from the magmatic to granulitic and retrograde metamorphic stages. 1. The oldest inclusions contain high density CO₂ ± N₂ ± CH₄ and are found as primaries in plagioclase and orthopyroxene in mafic granulite with homogenization temperatures between − 48 and − 28 °C. These inclusions may correspond to the early, magmatic stage. This type was found in samples from both the Niquelandia and the Barro Alto complexes. 2. Intragranular, relatively high density CO₂ + N₂ inclusions (T_h between − 33 and − 26 °C) together with decrepitated and reequilibrated N₂ inclusions (T_h between − 160 and − 151 °C) in the rock-forming minerals can be associated with the granulite facies metamorphism. Such inclusions were found only in the Barro Alto complex. 3. Transgranular, high density, CO₂–N₂ inclusions (93% CO₂ and 7% N₂, according to Raman analysis, with T_h between − 66.6 and − 50.4 °C) as well as the low density, secondary CO₂ ± N₂ ± CH₄ inclusions (T_h between − 13.0 and + 18.7 °C) and the H₂O–NaCl–CaCl₂ hypersaline inclusions (with halite dissolution temperature between 132 and 354 °C, and T_h between 212 and 490 °C) are attributed to different fluid influx events during the retrograde metamorphism. This inclusion type can be found both in the Niquelandia and in the Barro Alto complexes. The fluid inclusion textures and compositions show several stages of fluid evolution. The fluid inclusion measurements and the geothermobarometric data indicate an anticlockwise P-T path for both the Barro Alto and the Niquelandia complexes. Received October 16, 2000; revised version accepted November 20, 2001     

Evolution of metamorphic volatiles during exhumation of microdiamond-bearing granulites in the Western Gneiss Region, Norway

Fluid inclusions in garnet, kyanite and quartz from microdiamond-bearing granulites in the Western Gneiss Region, Norway, document a conspicuous fluid evolution as the rocks were exhumed following Caledonian high- and ultrahigh-pressure (HP–UHP) metamorphism. The most important of the various fluid mixtures and daughter minerals in these rocks are: (N₂ + CO₂ + magnesian calcite), (N₂ + CO₂ + CH₄ + graphite + magnesian calcite), (N₂ + CH₄), (N₂ + CH₄ + H₂O), (CO₂) and (H₂O + NaCl + CaCl₂ + nahcolite). Rutile also occurs in the N₂ + CO₂ inclusions as a product of titanium diffusion from the garnet host into the fluid inclusions. Volatiles composed of N₂ + CO₂ + magnesian calcite characterise the ambient metamorphic environment between HP–UHP (peak) and early retrograde metamorphism. During progressive decompression, the mole fraction of N₂ increased in the fluid mixtures; as amphibolite-facies conditions were reached, CH₄ and later, H₂O, appeared in the fluids, concomitant with the disappearance of CO₂ and magnesian calcite. Graphite is ubiquitous in the host lithologies and fluid inclusions. Thermodynamic modelling of the metamorphic volatiles in a graphite-buffered C-O-H system demonstrates that the observed metamorphic volatile evolution was attainable only if the f _O2 increased from c. −3.5 (±0.3) to −0.8 (±0.3) log units relative to the FMQ oxygen buffer. External introduction of oxidising aqueous solutions along a system of interconnected ductile shear zones adequately explains the dramatic increase in the f _O2. The oxidising fluids introduced during exhumation were likely derived from dehydration of oceanic crust and continental sediments previously subducted during an extended period of continental collision in conjunction with the Caledonian orogeny. Received: 15 December 1997 / Accepted: 25 May 1998     

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.     

Depth of emplacement, fluid provenance and metallogeny in granitic terranes: a comparison of western Thailand with other tin belts

The most important tin mineralization in Thailand is associated with the Late Cretaceous to Middle Tertiary western Thai granite belt. A variety of deposit types are present, in particular pegmatite, vein and greisen styles of mineralization. A feature common to most of the deposits is that they are associated with granites that were emplaced into the Khang Krachan Group, which consists of poorly sorted, carbonaceous, pelitic metasediments. Most of the deposits contain low to moderately saline aqueous fluid inclusions and aqueous-carbonic inclusions with variable CH₄/CO₂ ratios. Low salinity aqueous inclusions represent trapped magmatic fluid in at least one case, the Nong Sua pegmatite, based on their occurrence as primary inclusions in magmatic garnet. Aqueous-carbonic inclusions are commonly secondary and neither the CO₂ nor NaCl contents of these inclusions decrease in progressively younger inclusions, implying that they are not magmatic in origin. Reduced carbon is depleted in the metasediments adjacent to granites and the δD values greisen muscovites are variable, but are as low as −134 per mil, indicative of fluid interaction with organic (graphitic) material. This suggests that the aqueous-carbonic fluid inclusions represent fluids that were produced, at least in part, during contact metamorphism-metasomatism. By comparing the western Thai belt with other Sn-W provinces it is evident that there is a strong correlation between fluid composition and pressure in general. Low to moderately saline aqueous inclusions and aqueous-carbonic inclusions are characteristic of mineralization associated with relatively deep plutonic belts. Mineralized pegmatites are also typically of deeper plutonic belts, and pegmatite-hosted deposits may contain cassiterite that is magmatic (crystallized from granitic melt) or is orthomagmatic-hydrothermal (crystallized from aqueous or aqueous-carbonic fluids) in origin. The magmatic aqueous fluids (those that were exsolved from granitic melts) are interpreted to have had low salinities. As a consequence of the low salinities, tin is partitioned in favour of the melt on vapour saturation. Thus with a high enough degree of fractionation, the crystallization of a magmatic cassiterite (or different Sn phase such as wodginite) is inevitable. Because tin is not partitioned in favour of the vapour phase upon water saturation of the granitic melts, it is proposed that relatively deep vein and greisen systems tend to form by remobilization processes. In addition, many deeper greisen systems are hosted, in part, by carbonaceous pelitic metasediments and the reduced nature of the metasediments may play a key role in remobilizing tin. Sub-volcanic systems by contrast are characterized by high temperature-high salinity fluids. Owing to the high chlorinity, tin is strongly partitioned in favour of the vapour and cassiterite mineralization can form by of orthomagmatic-hydrothermal processes. Similar relationships between the depth of emplacement and fluid composition also appear to apply to other types of granite-hosted deposits, such as different types of molybdenum deposits. Received: 8 September 1997 / Accepted: 28 October 1997