Hydrocarbon migration in the Zagros Basin,offshore Iran,for understanding the fluid flow in the Oligocene–Miocene carbonate reservoirs

Kuh-e Mond Field is a conventional heavy oil resource in the Zagros foreland Basin, Iran, produced from the fractured carbonates partially filled by dolomite, calcite, and anhydrite cement. Vitrinite reflectance data from carbonate reservoir suggest low-maturation levels corresponding to paleotemperatures as low as 50 °C. The observed maturation level (< 0.5% Rmax) does not exceed values for simple burial maturation based on the estimated burial history. Oil inclusions within fracture-filled calcite and dolomite cement indicate the key role of these fractures in oil migration.The fluid inclusion temperature profiles constructed from the available data revealed the occurrence of petroleum in dolomite, calcite, and anhydrite and characterize the distinct variations in the homogenization temperatures (T_h). Fluid inclusions in syntectonic calcite veins homogenize between 22 °C and 90 °C, showing a salinity decrease from 22 to 18 eq. wt.% NaCl. Fluid inclusions in anhydrite homogenize at < 50 °C, showing that the pore fluids became warmer and more saline during burial. The T_h range in the calcite-dolomite cement depicts a change in water composition; therefore, we infer these cements precipitated from petroleum-derived fluids. The microthermometry data on the petroleum fluid inclusions suggest that the reservoir was filled with heavy black oils and high-salinity waters and indicate that undersaturated oil was present in a hydrostatically pressured reservoir.The T_h data do not support vertical migration of hot fluids througout the section, but extensive lateral fluid migration, most likely, drove tectonically dewatering in the south or west of the pool.     

Mineralisation of amethyst-bearing geodes in Ametista do Sul (Brazil) from low-temperature sedimentary brines: evidence from monophase liquid inclusions and stable isotopes

Fluid inclusion studies in combination with hydrogen, oxygen and sulphur isotope data provide novel insights into the genesis of giant amethyst-bearing geodes in Early Cretaceous Paraná continental flood basalts at Amestita do Sul, Brazil. Monophase liquid inclusions in colourless quartz, amethyst, calcite, barite and gypsum were analysed by microthermometry after stimulating bubble nucleation using single femtosecond laser pulses. The salinity of the fluid inclusions was determined from ice-melting temperatures and a combination of prograde and retrograde homogenisation temperatures via the density maximum of the aqueous solutions. Four mineralisation stages are distinguished. In stage I, celadonite, chalcedony and pyrite formed under reducing conditions in a thermally stable environment. Low δ³⁴S_V-CDT values of pyrite (?25 to ?32?‰) suggest biogenic sulphate reduction by organotrophic bacteria. During the subsequent stages II (amethyst, goethite and anhydrite), III (early subhedral calcite) and IV (barite, late subhedral calcite and gypsum), the oxidation state of the fluid changed towards more oxidising conditions and microbial sulphate reduction ceased. Three distinct modes of fluid salinities around 5.3, 3.4 and 0.3 wt% NaCl-equivalent characterise the mineralisation stages II, III and IV, respectively. The salinity of the stage I fluid is unknown due to lack of fluid inclusions. Variation in homogenisation temperatures and in δ¹⁸O values of amethyst show evidence of repeated pulses of ascending hydrothermal fluids of up to 80–90 °C infiltrating a basaltic host rock of less than 45 °C. Colourless quartz and amethyst formed at temperatures between 40 and 80 °C, while the different calcite generations and late gypsum precipitated at temperatures below 45 °C. Calculated oxygen isotope composition of the amethyst-precipitating fluid in combination with δD values of amethyst-hosted fluid inclusions (?59 to ?51?‰) show a significant ¹⁸O-shift from the meteoric water line. This ¹⁸O-shift, high salinities of the fluid inclusions with chloride-sulphate composition, and high δ³⁴S values of anhydrite and barite (7.5 to 9.9?‰) suggest that sedimentary brines from deeper parts of the Guaraní aquifer system must have been responsible for the amethyst mineralisation.     

Fluid and gas migration in the North German Basin: fluid inclusion and stable isotope constraints

Fluid inclusions have been studied in minerals infilling fissures (quartz, calcite, fluorite, anhydrite) hosted by Carboniferous and Permian strata from wells in the central and eastern part of the North German Basin in order to decipher the fluid and gas migration related to basin tectonics. The microthermometric data and the results of laser Raman spectroscopy reveal compelling evidence for multiple events of fluid migration. The fluid systems evolved from a H₂O–NaCl±KCl type during early stage of basin subsidence to a H₂O–NaCl–CaCl₂ type during further burial. Locally, fluid inclusions are enriched in K, Cs, Li, B, Rb and other cations indicating intensive fluid–rock interaction of the saline brines with Lower Permian volcanic rocks or sediments. Fluid migration through Carboniferous sediments was often accompanied by the migration of gases. Aqueous fluid inclusions in quartz from fissures in Carboniferous sedimentary rocks are commonly associated with co-genetically trapped CH₄–CO₂ inclusions. P–T conditions estimated, via isochore construction, yield pressure conditions between 620 and 1,650 bar and temperatures between 170 and 300°C during fluid entrapment. The migration of CH₄-rich gases within the Carboniferous rocks can be related to the main stage of basin subsidence and stages of basin uplift. A different situation is recorded in fluid inclusions in fissure minerals hosted by Permian sandstones and carbonates: aqueous fluid inclusions in calcite, quartz, fluorite and anhydrite are always H₂O–NaCl–CaCl₂-rich and show homogenization temperatures between 120 and 180°C. Co-genetically trapped gas inclusions are generally less frequent. When present, they show variable N₂–CH₄ compositions but contain no CO₂. P–T reconstructions indicate low-pressure conditions during fluid entrapment, always below 500 bar. The entrapment of N₂–CH₄ inclusions seems to be related to phases of tectonic uplift during the Upper Cretaceous. A potential source for nitrogen in the inclusions and reservoirs is C_org-rich Carboniferous shales with high nitrogen content. Intensive interaction of brines with Carboniferous or even older shales is proposed from fluid inclusion data (enrichment in Li, Ba, Pb, Zn, Mg) and sulfur isotopic compositions of abundant anhydrite from fissures. The mainly light δ³⁴S values of the fissure anhydrites suggest that sulfate is either derived through oxidation and re-deposition of biogenic sulfur or through mixing of SO₄²⁻-rich formation waters with variable amounts of dissolved biogenic sulfide. An igneous source for nitrogen seems to be unlikely since these rocks have low total nitrogen content and, furthermore, even extremely altered volcanic rocks from the study area do not show a decrease in total nitrogen content.     

Chemical and isotopic effects of retrogression in metamorphic fluid inclusions

Fluid inclusions may provide compositional and isotopic information about fluids from which the host mineral precipitated as long as the host mineral does not react with the fluid. Our transmission electron microscope (TEM) investigation of grain boundaries and of fluid inclusions in zoisite and quartz of high-pressure metamorphic rocks from Dabie Shan (eastern China) demonstrates daughter minerals, such as margarite, muscovite, calcite, and anhydrite. Their precipitation changes (1) the composition of the fluid by selective and mineral-specific removal of CO₂ (carbonates), H₂O (sheet silicates, hydration of the walls), or S (gypsum, anhydrite, sulfides), (2) the concentrations and proportions of ions dissolved in the fluid, and (3) the isotopic composition of the fluid because of isotopic fractionation between mineral precipitate and fluid and between unmixed fluids. Fluid leakage from overpressurized fluid inclusions with daughter minerals changes the overall chemical and isotopic composition of the inclusion irreversibly, even when the daughter crystals later redissolve. Such fluid loss yields a wide range of compositionally and isotopically different fluids from a single starting fluid. Depending on the relation between mineral reactions in and fluid loss from the inclusion, the fluid remaining in the inclusion and the fluid lost from the inclusion may appear entirely unrelated.     

Origin, timing, and temperature of secondary calcite-silica mineral formation at Yucca Mountain, Nevada

The origin of secondary calcite-silica minerals in primary and secondary porosity of the host Miocene tuffs at Yucca Mountain has been hotly debated during the last decade. Proponents of a high-level nuclear waste repository beneath Yucca Mountain have interpreted the secondary minerals to have formed from cool, descending meteoric fluids in the vadose zone; critics, citing the presence of two-phase fluid inclusions, argued that the minerals could only have formed in the phreatic zone from ascending hydrothermal fluids. Understanding the origin, temperature, and timing of these minerals is critical in characterizing geologically recent fluid flux at the site, and has significant implications to whether waste should be stored at Yucca Mountain.Petrographic and paragenetic studies of 155 samples collected from the Exploratory Studies Facility (ESF) and repository block cross drift (ECRB) tunnels indicate that heterogeneously distributed calcite with lesser chalcedony, quartz, opal, and fluorite comprise the oldest secondary minerals. These are typically overgrown by intermediate-aged calcite, often exhibiting distinctive bladed habits. The youngest event recorded across the site is the deposition of Mg-enriched (up to ∼1 wt%) and depleted, growth-zoned calcite intergrown with U-enriched opal. The cyclical variation in Mg enrichment and depletion is probably related to climate changes that have occurred during the last few million years. The distribution of secondary minerals is consistent with precipitation in the vadose zone.Fluid inclusion petrography of sections from the 155 samples determined that 96% of the fluid inclusion assemblages (FIAs) contained liquid-only inclusions that formed at ambient temperatures (<35°C). However, 50% of the samples (n = 78) contained relatively rare FIA that contain both liquid-only and liquid plus vapor inclusions (herein termed two-phase FIAs) that formed at temperatures above 35°C. Virtually all of these two-phase FIAs occur in paragenetically old calcite; rare two-phase inclusion assemblages were also observed in early fluorite and quartz, and early-intermediate calcite. Homogenization temperatures (≡ trapping temperatures) across Yucca Mountain are generally 45 to 60°C, but higher temperatures reaching 83°C were recorded in calcite from the north portal and ramp of the ESF. Cooler temperatures of ∼35 to 45°C were recorded in the intensely fractured zone. Multiple populations of two-phase FIAs from lithophysal cavities in the ESF and ECRB cross drift indicate early fluid cooling with time from temperatures >45°C in early calcite, to <35 to 45°C in paragenetically younger calcite. Freezing point depressions range from −0.2 to −1.6°C, indicating trapping of a low salinity fluid. The majority of intermediate calcite and all outermost Mg-enriched calcite contains rare all-liquid inclusions and formed from ambient temperature (<35°C) fluids.Carbon and oxygen isotope data reveal a consistent trend of decreasing δ¹³C (from 9.5 to −8.5‰) and increasing δ¹⁸O (from 5.2 to 22.1‰) values from paragenetically early calcite to Mg-enriched growth-zoned calcite. Depleted δD values (−131 to −90‰) of inclusion fluids from intermediate and the youngest Mg-enriched calcite indicate derivation from surface meteoric fluids. Recalculation of δ¹⁸O_H2O values of −12 to −10‰ is consistent with derivation from paleometeoric fluids.Results of integrated U-Pb dating (opal and chalcedony) and fluid inclusion microthermometry indicate that two-phase FIAs that trapped fluids of >50°C are older than 6.29 ± 0.30 Ma. Two-phase FIAs in paragenetically later calcite, which formed from fluids of 35 to 45°C, are older than 5.32 ± 0.02 Ma. There is no evidence for trapping of fluids with elevated temperatures during the past 5.32 my. The youngest Mg-enriched calcite intergrown with opal began to precipitate between about 1.9 to 2.9 Ma and has continued to precipitate within the past half million years. The presence of liquid-only inclusions and the consistent occurrence of Mg-enriched calcite and opal as the youngest event indicate a minor, but chemically distinct, ambient temperature (<35°C) fluid flux during the past 2 to 3 my.     

Fluid Inclusion and Carbon-Oxygen Isotope Studies of the Hujiayu Cu Deposit, Zhongtiao Mountains, China: Implications for Syn-metamorphic Copper Remobilization

The Hujiayu Cu deposit,representative of the "HuBi-type" Cu deposits in the Zhongtiao Mountains district in the southern edge of the North China Craton,is primarily hosted in graphitebearing schists and carbonate rocks.The ore minerals comprise mainly chalcopyrite,with minor sphalerite,siegenite[(Co,Ni)_3S_4],and clausthalite[Pb(S,Se)].The gangue minerals are mainly quartz and dolomite,with minor albite.Four fluid inclusion types were recognized in the chalcopyrite-pyrite-dolomite-quartz veins,including CO_2-rich inclusions(type Ⅰ),low-salinity,liquid-dominated,biphase aqueous inclusions(type Ⅱ),solid-bearing aqueous inclusions(type Ⅲ),and solid-bearing aqueous-carbonic inclusions(type Ⅳ).Type I inclusion can be further divided into two sub-types,i.e.,monophase CO_2 inclusions(type Ⅰa) and biphase CO_2-rich inclusions(with a visible aqueous phase),and type Ⅲ inclusion is divided into a subtype with a halite daughter mineral(type Ⅲa) and a subtype with multiple solids(type Ⅲb).Various fluid inclusion assemblages(FIAs) were identified through petrographic observations,and were classified into four groups.The group-1 FIA,consisting of monophase CO_2 inclusions(type Ⅰa),homogenized into the liquid phase in a large range of temperatures from-1 to 28℃,suggesting post-entrapment modification.The group-2 FIA consists of type Ⅰb,Ⅲb and Ⅳ inclusions,and is interpreted to reflect fluid immiscibility.The group-3 FIA comprises type Ⅱ and Ⅲa inclusions,and the group-4FIA consists of type Ⅱ inclusions with consistent phase ratios.The group-1 and group-2 FIAs are interpreted to be entrapped during mineralization,whereas group-3 and group-4 FIAs probably represent the post-mineralization fluids.The solid CO_2 melting temperatures range from-60.6 to56.6℃ and from-66.0 to-63.4℃ for type Ⅰa and type Ⅳ inclusions,respectively.The homogenization temperatures for type Ⅱ inclusions range from 132 to 170℃ for group-3 FIAs and115 to 219℃ for group-4 FIAs.The halite melting temperatures range from 530 to 562℃ for typeⅢ b and Ⅳ inclusions,whereas those for type Ⅲa inclusions range from 198 to 398℃.Laser Raman and SEM-EDS results show that the gas species in fluid inclusions are mainly CO_2 with minor CH_4,and the solids are dominated by calcite and halite.The calcite in the hosting marble and dolomite in the hydrothermal veins have δ~(13)C_(V-pdb) values of-0.2 to 1.2‰ and-1.2 to-6.3‰,and δ~(18)O_(v-smow) values of 14.0 to 20.8 ‰ and 13.2 to 14.3‰,respectively.The fluid inclusion and carbon-oxygen isotope data suggest that the ore-forming fluids were probably derived from metamorphic fluids,which had reacted with organic matter in sedimentary rocks or graphite and undergone phase separation at 1.4-1.8 kbar and 230-240℃,after peak metamorphism.It is proposed that the Hujiayu Cu deposit consists of two mineralization stages.The early stage mineralization,characterized by disseminated and veinlet copper sulfides,probably took place in an environment similar to sediment-hosted stratiform copper mineralization.Ore minerals formed in this precursor mineralization stage were remobilized and enriched in the late metamorphic hydrothermal stage,leading to the formation of thick quartz-dolomite-sulfides veins.     

Production of carbonic fluids during metamorphism of graphitic pelites in a collisional orogen—An assessment from fluid inclusions

Fluid inclusions in quartz veins within Proterozoic metamorphic rocks in the Black Hills, South Dakota, were examined by microthermometry and Raman spectroscopy to assess the evolution of fluid compositions during regional metamorphism of organic-rich shales and late-orogenic magmatism, both of which were related to the collision of the Wyoming and Superior crustal blocks. Fluid inclusions occur in veins that began to be generated before or during regional compression and metamorphism that reached at least garnet-grade conditions, and in veins within the aureole of the Harney Peak Granite (HPG), where temperatures reached second-sillimanite grade conditions. Early veins in the schists have undergone recrystallization during heating and deformation that modified the composition of early CH₄ or CO₂ and N₂-dominated inclusions. These fluids were apparently trapped under conditions of immiscibility with a saline aqueous fluid phase. They are interpreted to represent components generated during maturation of organic matter and dehydration of phyllosilicates during incipient metamorphism at reducing fO₂ conditions. Most inclusions in the quartz veins are, however, secondary CO₂-bearing. They imply a transition to higher fO₂ conditions with increasing temperature of regional metamorphism. The fO₂ conditions may have been controlled by the mineral assemblage in the host metapelites. The prevalence of bimodal distributions of trapped CO₂-N₂ and aqueous endmembers in the biotite and garnet zones also suggests that two immiscible fluid phases existed during the regional metamorphism.In the aureole of the HPG, graphite was evidently consumed by influx of magmatic fluids. CO₂-H₂O fluid inclusions dominate, but they have significantly less N₂ than inclusions at lower metamorphic grades. All inclusions define secondary trails in mostly unstrained quartz. The bimodality of inclusion compositions is not as well defined as at lower grades, with many inclusions containing intermediate CO₂-H₂O compositions. This suggests that a single fluid phase existed at the high temperatures in the granite aureole, but then unmixed during cooling. A set of late quartz veins with graphitized and tourmalinized selvages in the granite aureole contains CH₄-bearing inclusions with little N₂. The existence of CH₄ in these inclusions is attributed to complexing of magmatic B with hydroxyl anions taken from the CO₂-H₂O fluid phase, effectively causing reduction in fO₂ and promoting precipitation of graphite.     

Diagenesis of Ordovician carbonates from the north-east Michigan Basin, Manitoulin Island area, Ontario: evidence from petrography, stable isotopes and fluid inclusions

Middle to Late Ordovician subtidal carbonates in the Manitoulin Island area of Ontario are predominantly limestone in composition, but non-ferroan and ferroan dolomite is a common cement as well as a selective or locally pervasive replacement phase. Integration of field, petrographic, geochemical (δ¹³C, δ¹⁸O) and fluid inclusion data indicates that lithification of these carbonates occurred during burial diagenesis, with much of the alteration controlled by regional fracturing and hydrothermal influences. Aqueous (type 1) fluid inclusions in early calcite (pre-dolomite) and dolomite are saline (> 29 wt% NaCl eq.) solutions with Ca and/or Mg in excess of Na and display homogenization temperatures with modes of 95 and 101°C, respectively. These temperatures can be explained by significantly more burial than can be accounted for either by the available stratigraphic information or by an unusually high palaeogeothermal gradient, which also is not well supported. The fluid inclusion temperatures are interpreted to have resulted from hydrothermal fluids which circulated during the burial diagenesis of these strata. Type 1 inclusions in late (post-dolomite) calcite are less saline (<19 wt% NaCl eq.) and have a bimodal distribution of homogenization temperatures with a relatively well defined low temperature peak similar to those in early calcite and dolomite and a broad higher temperature grouping with a mode at 183°C. A small proportion of methane and light hydrocarbon-bearing fluid inclusions (type 2) are present in all stages of carbonate. Dolomitizing fluids were derived from burial compaction of argillaceous sediments in the more central parts of the Michigan Basin and the updip migration of these brines along fractures to the basin margin where the carbonates of the Manitoulin Island area were dolomitized. Alternatively, migration of dolomitizing brines downward from the overlying pervasively dolomitized Silurian sequence into fractures in the Ordovician carbonates may have occurred. Integration of the aqueous fluid inclusion data into the diagenetic history of these carbonates remains equivocal because most of the inclusions are secondary or indeterminate in origin. Nevertheless, high salinities resulting from interaction with evaporitic strata and hydrothermal effects are clearly implicated although the origin of the latter remains unclear. The alteration styles of the Ordovician carbonates in the Manitoulin area are similar to those of Ordovician hydrocarbon reservoirs described from other parts of the Michigan Basin. They indicate that fracture-related diagenesis occurred on a basin-wide scale and that hydrothermal effects were important.     

Sealing of fluid pathways in overpressure cells: a case study from the Buntsandstein in the Lower Saxony Basin (NW Germany)

We studied veins in the Triassic Buntsandstein of the Lower Saxony Basin (NW Germany) with the aim of quantifying the evolution of in-situ stress, fluids and material transport. Different generations of veins are observed. The first generation formed in weakly consolidated rocks without a significant increase in fracture permeability and was filled syntectonically with fibrous calcite and blocky to elongate-blocky quartz. The stable isotopic signature (δ¹⁸O and δ¹³C) indicates that the calcite veins precipitated from connate water at temperatures of 55–122°C. The second vein generation was syntectonically filled with blocky anhydrite, which grew in open fractures. Fluid inclusions indicate that the anhydrite veins precipitated at a minimum temperature of 150°C from hypersaline brines. Based on δ³⁴S measurements, the source of the sulphate was found in the underlying Zechstein evaporites. The macro- and microstructures indicate that all veins were formed during subsidence and that the anhydrite veins were formed under conditions of overpressure, generated by inflation rather than non-equilibrium compaction. The large amount of fluids which are formed by the dehydrating gypsum in the underlying Zechstein and are released into the Buntsandstein during progressive burial form a likely source of overpressures and the anhydrite forming fluids.     

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     

Description and interpretation of the composition of fluid and alteration mineralogy in the geothermal system,at Svartsengi,Iceland

The bulk composition and mineralogy of hydrothermally altered tholeiite, along with the composition and speciation of fluid, have been determined for a well-defined alteration zone at 240°C and 110 bars at Svartsengi, Iceland. Mass balances between the geothermal fluid and altered tholeiite, relative to a seawater/fresh water mixture and unaltered tholeiite, indicate the overall reaction per 1000 cm³ is: 1325 gm plagioclase + 1228 gm pyroxene + 215 gm oxide-minerals break down to form 685 gm chlorite + 636 gm albite + 441 gm quartz + 249 gm epidote + 266 gm calcite + 201 gm oxide-minerals + 15 gm pyrite, requiring an influx of 123 gm CO₂, 10 gm H₂S and 4 gm Na₂O and a release of 57 gm SiO₂, 35 gm FeO, 21 gm CaO, 8 gm MgO and 4 gm K₂O.Principal reactions, deduced from textural evidence, include Na-Ca exchange in plagioclase, precipitation of quartz, calcite and anhydrite, and formation of chlorite and epidote by reactions between groundmass minerals and fluid.Thermodynamic analyses of authigenic minerals and downhole fluid indicate that the fluid maintains a state close to equilibrium with the secondary mineral phases chlorite, epidote, albite, quartz, calcite, prehnite, anhydrite, pyrite and magnetite, whereas remnant primary labradorite and augite are out of equilibrium with the fluid.Water/rock ratios for the system are determined under a variety of assumptions. However, the open nature of the system makes comparisons with experimental and theoretical closed system studies ambiguous.     

Ultra-high-pressure metamorphism of carbonate rocks in the Dabie Mountains, central China

Abstract Widespread ultra-high-P assemblages including coesite, quartz pseudomorphs after coesite, aragonite, and calcite pseudomorphs after aragonite in marble, gneiss and phengite schist are present in the Dabie Mountains eclogite terrane. These assemblages indicate that the ultra-high-P metamorphic event occurred on a regional scale during Triassic collision between the Sino-Korean and Yangtze cratons. Marble in the Dabie Mountains is interlayered with coesite-bearing eclogite and gneiss and as blocks of various size within gneiss. Discontinuous boudins of eclogite occur within marble layers. Marble contains an ultra-high-P assemblage of calcite/aragonite, dolomite, clinopyroxene, garnet, phengite, epidote, rutile and quartz/coesite. Coesite, quartz pseudomorphs after coesite, aragonite and calcite pseudomorphs after aragonite occur as fine-grained inclusions in garnet and omphacite. Phengites contain about 3.6 Si atoms per formula unit (based on 11 oxygens). Similar to the coesite-bearing eclogite, marble exhibits retrograde recrystallization under amphibolite–greenschist facies conditions generated during uplift of the ultra-high-P metamorphic terrane. Retrograde minerals are fine grained and replace coarse-grained peak metamorphic phases. The most typical replacements are: symplectic pargasitic hornblende + epidote after garnet, diopside + plagioclase (An₁₈) after omphacite, and fibrous phlogopite after phengite. Ferroan pargasite + plagioclase, and actinolite formed along grain boundaries between garnet and calcite, and calcite and quartz, respectively. The estimated peak P–T conditions for marble are comparable to those for eclogite: garnet–clinopyroxene geothermometry yields temperatures of 630–760°C; the garnet–phengite thermometer gives somewhat lower temperatures. The minimum pressure of peak metamorphism is 27 kbar based on the occurrence of coesite. Such estimates of ultra-high-P conditions are consistent with the coexistence of grossular-rich garnet + rutile, and the high jadeite content of omphacite in marble. The fluid for the peak metamorphism was calculated to have a very low X_CO2 (<0.03). The P–T conditions for retrograde metamorphism were estimated to be 475–550°C at <7 kbar.     

Meganodular anhydritization: a new mechanism of gypsum to anhydrite conversion (Palaeogene–Neogene,Ebro Basin,North‐east Spain)

A number of Palaeogene to Early Neogene gypsum units are located along the southern margins of the Ebro Basin (North‐east Spain). These marginal units, of Eocene to Lower Miocene age, formed and accumulated deposits of Ca sulphates (gypsum and anhydrite) in small, shallow saline lakes of low ionic concentration. The lakes were fed mainly by ground water from deep regional aquifers whose recharge areas were located in the mountain chains bounding the basin, and these aquifers recycled and delivered Ca sulphate and Na chloride from Mesozoic evaporites (Triassic and Lower Jurassic). In outcrop, the marginal sulphate units are largely secondary gypsum after anhydrite and exhibit meganodules (from 0·5 to >5 m across) and large irregular masses. In the sub‐surface these meganodules and masses are mostly made of anhydrite, which replaced the original primary gypsum. The isotopic composition (11·1 to 17·4‰ for δ¹⁸O_VSMOW; 10·7 to 15·3‰ for δ³⁴S_VCDT) of secondary gypsum in this meganodular facies indicates that the precursor anhydrite derived from in situ replacement of an initial primary gypsum. As a result of ascending circulation of deep regional fluid flows through the gypsum units near the basin margins, the gypsum was partly altered to anhydrite within burial conditions from shallow to moderate depths (from some metres to a few hundred metres?). At such depths, the temperatures and solute contents of these regional flows exceeded those of the ground water today. These palaeoflows became anhydritizing solutions and partly altered the subsiding gypsum units before they became totally transformed by deep burial anhydritization. The characteristics of the meganodular anhydritization (for example, size and geometry of the meganodules and irregular masses, spatial arrangement, relations with the associated lithologies and the depositional cycles, presence of an enterolithic vein complex and palaeogeographic distribution) are compared with those of the anhydritization generated both in a sabkha setting or under deep burial conditions, and a number of fundamental differences are highlighted.     

长岭凹陷深层天然气藏中CO_2及CH_4充注次序的流体包裹体证据

对长岭凹陷深层天然气藏储层——营城组火山岩中发育的流体包裹体进行了详细研究,结果表明在火山岩发育的石英、方解石细网脉中均存在较多的碳质流体包裹体,单个包裹体激光拉曼光谱分析结果表明其主要为CO2及CH4两种类型的碳质包裹体。其中方解石细网脉体中发育有原生及次生CH4包裹体,而含CO2包裹体多以原生包裹体产于石英细网脉中。很多含CO2包裹体的石英细脉中发现了含CH4包裹体的方解石脉体的角砾,这就表明石英细脉形成晚于方解石细脉。营城组火山岩储层中CO2及CH4包裹体的产状特征研究表明,松辽盆地深层天然气藏的形成系火山岩成岩后CO2及CH4等气体不同期次充注的结果,CH4气的充注时间早于CO2气,火山岩中发育的原生孔隙及次生裂隙为上述气体的充注和聚集提供了重要通道。     

Late diagenetic calcitization of anhydrite from the Mississippian of Saskatchewan, western Canada

Mississippian nodular anhydrites beneath an unconformity in the subsurface of southern Saskatchewan are locally replaced by calcite, pyrite and celestite. Triassic clastics above the unconformity are green, rather than red, and a usually developed subunconformity alteration zone (where carbonates are dolomitized, and porosity is filled with anhydrite) is absent. The unconformity lacks karstic features (unlike in the USA), and probably formed in a hyperarid climate. Mississippian anhydrites near the unconformity are not preferentially dissolved, nor were they extensively hydrated. Anhydrite calcitization occurred only after the unconformity was shallowly buried by redbeds, and it probably involved sulphate-reducing bacteria. Hydrogen sulphide, generated by bacteria, reduced redbed pigments. The replacement calcite contains pseudomorphs and relicts of anhydrite, and pseudomorphs of secondary gypsum. These indicate calcitization occurred only after original Mississippian gypsum was altered to anhydrite and this, in turn, was partially converted back to secondary gypsum beneath the unconformity. Replacement occurred concurrently with the formation elsewhere of the dolomitized zone beneath the unconformity. Sulphur isotopic ratios of replacement pyrite are depleted relative to Mississippian sulphate values, consistent with the activities of sulphate-reducing bacteria. Carbon isotopic ratios of replacive calcites, however, do not support this interpretation, and are identical to those of Mississippian limestones. Simple replacement of sulphate by pore-water bicarbonate (in equilibrium with host limestones) is unlikely because protons generated during the reaction should have created acidic conditions in which calcite would have dissolved. A full explanation of the calcitization remains elusive, but may involve replacement occurring in an active groundwater system and/or bacterial sulphate reduction occurring upstream of the site of calcitization.     

Compositional zoning of fluid inclusions in the Archaean Junction gold deposit,Western Australia: A process of fluid ‐ wall‐rock interaction?

The Junction gold deposit, in Western Australia, is an orogenic gold deposit hosted by a differentiated, iron‐rich, tholeiitic dolerite sill. Petrographic, microthermometric and laser Raman microprobe analyses of fluid inclusions from the Junction deposit indicate that three different vein systems formed at three distinct periods of geological time, and host four fluid‐inclusion populations with a wide range of compositions in the H₂O–CO₂–CH₄–NaCl ± CaCl₂ system. Pre‐shearing, pre‐gold, molybdenite‐bearing quartz veins host fluid inclusions that are characterised by relatively consistent phase ratios comprising H₂O–CO₂–CH₄ ± halite. Microthermometry suggests that these veins precipitated when a highly saline, >340°C fluid mixed with a less saline ≥150°C fluid. The syn‐gold mineralisation event is hosted within the Junction shear zone and is associated with extensive quartz‐calcite ± albite ± chlorite ± pyrrhotite veining. Fluid‐inclusion analyses indicate that gold deposition occurred during the unmixing of a 400°C, moderately saline, H₂O–CO₂ ± CH₄ fluid at pressures between 70 MPa and 440 MPa. Post‐gold quartz‐calcite‐biotite‐pyrrhotite veins occupy normal fault sets that slightly offset the Junction shear zone. Fluid inclusions in these veins are predominantly vapour rich, with CO₂?CH₄. Homogenisation temperatures indicate that the post‐gold quartz veins precipitated from a 310 ± 30°C fluid. Finally, late secondary fluid inclusions show that a <200°C, highly saline, H₂O–CaCl₂–NaCl–bearing fluid percolated along microfractures late in the deposit's history, but did not form any notable vein type. Raman spectroscopy supports the microthermometric data and reveals that CH₄–bearing fluid inclusions occur in syn‐gold quartz grains found almost exclusively at the vein margin, whereas CO₂–bearing fluid inclusions occur in quartz grains that are found toward the centre of the veins. The zonation of CO₂:CH₄ ratios, with respect to the location of fluid inclusions within the syn‐gold quartz veins, suggest that the CH₄ did not travel as part of the auriferous fluid. Fluid unmixing and post‐entrapment alteration of the syn‐gold fluid inclusions are known to have occurred, but cannot adequately account for the relatively ordered zonation of CO₂:CH₄ ratios. Instead, the late introduction of a CH₄–rich fluid into the Junction shear zone appears more likely. Alternatively, the process of CO₂ reduction to CH₄ is a viable and plausible explanation that fits the available data. The CH₄–bearing fluid inclusions occur almost exclusively at the margin of the syn‐gold quartz veins within the zone of high‐grade gold mineralisation because this is where all the criteria needed to reduce CO₂ to CH₄ were satisfied in the Junction deposit.     

Application of a new Raman microprobe spectrometer to nondestructive analysis of sulfate and other ions in individual phases in fluid inclusions in minerals

Rosascoet al. (1975), reported the first successful application of laser-excited Raman spectroscopy for the identification and nondestructive partial analysis of individual solid, liquid, and gaseous phases in selected fluid inclusions. We report here the results of the application of a new instrument, based on back-scattering, that eliminates many of the previous stringent sample limitations and hence greatly expands the range of applicability of Raman spectroscopy to fluid inclusions.Fluid inclusions in many porphyry copper deposits contain 5–10 μm ‘daughter’ crystals thought to be anhydrite but too small for identification by the previous Raman technique. Using the new instrument, we have verified that such daughter crystals in quartz from Bingham, Utah, are anhydrite. They may form by leakage of hydrogen causing internal autooxidation of sulfide ion. Daughter crystals were also examined in apatite (Durango, Mexico) and emerald (Muzo, Colombia).Valid analyses of sulfur species in solution in small fluid inclusions from ore deposits would be valuable, but are generally impossible by conventional methods. We present a calibration procedure for analyses for SO₄^2? in such inclusions from Bingham, Utah (12,000 ± 4000 ppm) and Creede, Colo. (probably < 500 ppm). A fetid Brazilian quartz, originally thought to contain liquid H₂S, is shown to contain only HS^? in major amounts.     

The application of fluid inclusions to migration of oil and diagenesis in petroleum reservoirs

Fluid inclusions can be used to interpret thermal history and petroleum maturation and migration relative to burial history. Temperature, pressure and composition data collected from fluid inclusions are used to determine the environment of diagenesis and the timing of cementation and migration. Cements in petroleum reservoirs contain both oil and aqueous fluid inclusions. Fluorescence spectroscopy is used to identify oil inclusions and to determine the maturity of entrapped oil. The lifetime of fluorescence induced by a pulsed laser is related to the API gravity of entrapped oil. Interpretation of fluid inclusion data depends on knowing the origin of fluid inclusions and the probability that they survive in the burial environment. Those aspects of fluid inclusion study are investigated by synthesizing oil and aqueous inclusions in calcite crystals in laboratory experiments. Examples of how fluid inclusions are used to determine the physico-chemical environments of diagenesis in petroleum reservoirs and the timing of cementation and migration are given for the Wealden Basin, England, the Mishrif Formation, Dubai, the Smackover Formation, Gulf Coast, U.S.A. and Jurassic sandstones, offshore Norway. In the Wealden Basin, temperature data from fluid inclusions are used to determine that oil migration occurred in the Cretaceous and that the reservoir rocks have been uplifted to varying degrees at a time after migration. Distribution of oil inclusions indicates that generation and migration of oil was principally in the western part of the basin. The geochemistry of oil inclusions in calcite cements from the Mishrif Formation, Dubai, are used to determine the type and maturity of entrapped oil. Temperature data from oil and water inclusions are used to relate reservoir diagenesis to burial history and the migration of oil. In deep Smackover reservoirs oil contains H₂S. The origin of the H₂S is examined by study of fluid inclusions containing H₂S. In Jurassic sandstones, offshore Norway, fluid inclusion studies show that silica cementation is related to burial depth whereas a later calcite cementation originated from invasion of a hot fluid.     

Mineral Paragenesis, Fluid Inclusions and Sulfur Isotope Systematics of the Lepanto Far Southeast Porphyry Cu-Au Deposit, Mankayan, Philippines

Abstract: The Lepanto Far Southeast porphyry Cu‐Au deposit is located beneath and to the southeast of the Lepanto enargite‐luzonite Cu–Au deposit in Mankayan, Benguet Province, Philippines. The principal orebody consists of potassic alteration subjected to partial retrograde chlorite alteration that rims stock‐work of quartz‐anhydrite veinlets. Fluid inclusions found in stockwork quartz and anhydrite in the biotitized orebody center are dominated by polyphase inclusions that homogenize at temperatures of >500C. Sulfur isotopic thermometry applied to the sulfides‐anhydrite pairs suggests around 500C. The principal ore minerals associated with quartz‐anhydrite stockworks are chalcopyrite and pyrite with minor bornite and Bi–Te–bearing tennantite, with trace of native gold. Rounded pyrite grains appear fractured and corroded and are interpreted as remnants of primary intermediate solid solution + pyrite assemblage. A breccia pipe truncates the deposit. Mineralization in the breccia pipe is brought by quartz‐anhydrite veinlets and infilling in the interstices between clasts. Chalcopyrite‐Au mineralization associated with molybdenite is recognized in the deeper zone in the breccia pipe. Fluid inclusion microthermometry on polyphase inclusions in veinlet quartz as well as sulfur isotope thermometry applied for the pair of anhydrite and sulfides suggests >450C. Fluid inclusions in veinlet quartz and anhydrite in the fringe advanced argillic alteration are chiefly composed of coexisting liquid‐rich inclusions and gas‐rich inclusions, in addition to coexisting polyphase inclusions and gas‐rich inclusions. These inclusions exhibit a wide range of homogenization temperatures, suggesting heterogeneous entrapping in the two‐fluid unmixing region. Sulfur isotopes of aqueous sulfide and sulfate exhibit a general trend from the smallest fractionation pairs (about 11%) in the biotitized orebody center to the largest fractionation (about 25%) pairs in the fringe advanced argillic alteration, suggesting a simple evolution of hydrothermal system. The slopes of arbitrary regression lines in δ³⁴S versus ³⁴S[SO₄ = –H₂S] diagram suggest that the abundance ratio of aqueous sulfate to sulfide in the hydrothermal fluid has been broadly constant at about 1:3 through temperature decrease. The intersection of these two regression lines at the δ³⁴S axis indicates that the bulk δ³⁴S is about +6%. Thus, the Lepanto FSE deposit is a further example which confirms enrichment in ³⁴S in the hydrous intermediate to silicic magmas and associated magmatic hydrothermal deposits in the western Luzon arc.     

Reconciling fluid inclusion types,fluid processes,and fluid sources in skarns: an example from the Bismark Deposit,Mexico

The Bismark deposit (8.5 Mt at 8% Zn, 0.5% Pb, 0.2% Cu, and 50 g/t Ag) located in northern Mexico is an example of a stock-contact skarn end member of a continuum of deposit types collectively called high-temperature, carbonate-replacement deposits. The deposit is hosted by massive sulfide within altered limestone adjacent to the Bismark quartz monzonite stock (~42 Ma) and the Bismark fault. Alteration concurrently developed in both the intrusion and limestone. The former contains early potassic alteration comprising K-feldspar and biotite, which was overprinted by kaolinite-rich veins and alteration and later quartz, sericite, and pyrite with minor sphalerite and chalcopyrite. Prograde exoskarn alteration in the limestone consists of green andradite and diopside, and transitional skarn comprising red-brown andradite, green hedenbergite and minor vesuvinite, calcite, fluorite, and quartz. The main ore stage post-dates calc-silicate minerals and comprises sphalerite and galena with gangue pyrite, pyrrhotite, calcite, fluorite, and quartz. The entire hydrothermal system developed synchronously with faulting. Fluid inclusion studies reveal several distinct temporal, compositional, and thermal populations in pre-, syn- and post-ore quartz, fluorite, and calcite. The earliest primary fluid inclusions are coexisting vapor-rich (type 2A) and halite-bearing (type 3A; type 3B contain sylvite) brine inclusions (32 to >60 total wt% salts) that occur in pre-ore fluorite. Trapping temperatures are estimated to have been in excess of 400 °C under lithostatic pressures of ~450 bar (~1.5 km depth). Primary fluid inclusions trapped in syn-ore quartz display critical to near critical behavior (type 1C), have moderate salinity (8.4 to 10.9 wt% NaCl equiv.) and homogenization temperatures (Th) ranging from 351 to 438 °C. Liquid-rich type 1A and 1B (calcite-bearing) inclusions occur as primary to secondary inclusions predominantly in fluorite and show a range in Th (104–336 °C) and salinity (2.7–11.8 wt% NaCl equiv.), which at the higher Th and salinity ranges overlap with type 1C inclusions. Oxygen isotope analysis was carried out on garnet, quartz, and calcite (plus carbon isotopes) in pre-, syn-, post-ore, and peripheral veins. Pre-ore skarn related garnets have a δ¹⁸O_mineral range between 3.9 and 8.4‰. Quartz from the main ore stage range between 13.6 and 16.0‰. Calcite from the main ore stage has δ¹³C values of –2.9 to –5.1‰ and δ¹⁸O values of 12.3 to 14.1‰, which are clearly distinct from post-ore veins and peripheral prospects that have much higher δ¹⁸O (16.6–27.3‰) and δ¹³C (1.3–3.1‰) values. Despite the numerous fluid inclusion types, only two fluid sources can be inferred, namely a magmatic fluid and an external fluid that equilibrated with limestone. Furthermore, isotopic data does not indicate any significant mixing between the two fluids, although fluid inclusion data may be interpreted otherwise. Thus, the various fluid types were likely to have formed from varying pressure–temperature conditions through faulting during exsolution of magmatic fluids. Late-stage hydrothermal fluid activity was dominated by the non-magmatic fluids and was post-ore.