Activity of Silica-Rich Hydrothermal Fluid and Its Impact on Deep Dolomite Reservoirs in the Sichuan Basin, Southern China

Well-developed dissolution pores occur in the dolomites of the Sinian Dengying Formation, which is an important oil and gas reservoir layer in the Sichuan Basin and adjacent areas in southern China. The pores are often filled with quartz, and some dolomites have been metasomatically altered to siliceous chert. Few studies have documented the characteristics, source or origin of silica-rich fluids and their effects on the dolomite reservoir. The peak homogenisation temperatures(T_h) of fluid inclusions in pore-filling quartz are between 150℃ and 190℃, with an average of 173.7℃. Gases in the inclusions are mainly composed of CO_2, CH_4 and N_2. Compared with host dolomite, pore-filling quartz and metasomatic chert contain higher amounts of Cr, Co, Mo, W and Fe, with average concentrations of 461.58, 3.99, 5.05, 31.43 and 6666.83 ppm in quartz and 308.98, 0.99, 1.04, 13.81 and 4703.50 ppm in chert, respectively. Strontium levels are lower than that in the host dolomite, with average concentrations in quartz and chert of 4.81 and 11.06 ppm, respectively. Rare earth element compositions in quartz and chert display positive Eu anomalies with a maximum δEu of 5.72. The δD_(SMOW) values of hydrogen isotopes in water from quartz inclusions vary from-85.1‰ to-53.1‰ with an average of-64.3‰, whereas the δ~(18)O_(SMOW) values range from 7.2‰ to 8.5‰ with an average of 8.2‰. The average ~(87)Sr/~(86)Sr ratios in quartz and chert are 0.711586 and 0.709917, respectively, which are higher than that in the host dolomite. The fluid inclusions, elemental and isotopic compositions demonstrate that the formation of quartz and chert was related to silica-rich hydrothermal fluid and that the fluid was the deep circulation of meteoric water along basement faults. Interactions with silica-rich hydrothermal fluids resulted in densification of dolomite reservoirs in the Dengying Formation through quartz precipitation and siliceous metasomatism. However, it increased the resistance of the host dolomite to compaction, improving the ability to maintain reservoir spaces during deep burial. Evidence for silica-rich hydrothermal activity is common in the Yangtze Platform and Tarim Basin and its influence on deep dolomite reservoirs should be thoroughly considered.     

Silicification of sulphate evaporites and their carbonate replacements in Eocene marine sediments, Tunisia: two diagenetic trends

Samples of chert nodules, diagenetic carbonates and evaporites (gypsum/anhydrite) collected from the gypsiferous limestones of the Kef Eddour Member (Ypressian‐Priabonian) near Metlaoui and Sehib (Tunisia) show selective silicification with great variety in the silicified by‐products. Based on δ¹³C values, which support an organic origin for the carbon, carbonates replaced evaporites microbially through bacterial sulphate reduction. Observations and results suggest two scenarios for chert formation that are related to the rate and timing of diagenetic carbonate replacement of the evaporites (anhydrite/gypsum). In the absence of early diagenetic carbonate phases, silica with δ¹⁸O values from +25 to +28·6‰ [standard mean ocean water (SMOW)] replaced the outer parts of anhydrite nodules at pH < 9. In contrast, pore‐fluid pH values > 9 in the innermost parts of the anhydrite nodules prevented silica precipitation. The record of this chemical barrier is preserved in the microquartz rims and geode features that formed in the inner parts of the nodules after dissolution of the anhydrite nucleus. The microbial diagenetic replacement of evaporites (bacterial sulphate reduction) by carbonates (calcite, aragonite and dolomite) favoured silica replacement of carbonates rather than evaporites. Silica, with δ¹⁸O signature of +21 to +26‰ (SMOW), replaced carbonates on a volume‐for‐volume basis, yielding a more siliceous groundmass, and accounting for 90–95% of the nodules. The relatively higher δ¹⁸O values of quartz replacing anhydrite can be explained by a diagenetic fluid in equilibrium with mixed (meteoric/marine) to marine water. The lower δ¹⁸O values of the quartz that replaced the diagenetic carbonates are ascribed to flushing by meteoric water in a later diagenetic stage. The silica supply for chert formation could be derived from the reworked bio‐siliceous deposits (diatomites) to the west of the basin [vestiges of an opal‐CT precursor undetectable by X‐ray diffraction (XRD) were revealed by δ²⁹Si magic‐angle‐spinning nuclear magnetic resonance investigations], diagenesis of the extraformational and overlying clay‐rich beds (the host limestones are clay‐poor as shown by XRD measurements), and minor volcanogenic and hydrothermal contributions during early diagenetic stages.     

Nodular chert from the Arbuckle Group, Slick Hills, SW Oklahoma: a combined field, petrographic and isotopic study

Nodular chert from the middle and upper Arbuckle Group (Early Ordovician) in the Slick Hills, SW Oklahoma, was formed by selective replacement of grainstones, burrow fillings, algal structures, and evaporite nodules. Chert nodules are dominantly microquartz with minor fibrous quartz (both quartzine and chalcedony), megaquartz, and microflamboyant quartz. Lepisphere textures of an opal-CT precursor are preserved in many (especially in finely-crystalline) chert nodules. The δ¹⁸O values of microquartz chert range from +23.4 to + 28.8^0/00 (SMOW), significantly lower than those of Cenozoic and Mesozoic microquartz chert formed both in the deep sea and from near-surface sea water. The δ¹⁸O values of chert decrease with increasing quartz crystal size. Silicification in the Arbuckle Group occurred during early diagenesis, with the timing constrained by the relative temporal relationships among silicification, burial compaction, and early dolomite stabilization. Silica for initial chert nucleation may have been derived from both dissolution of sponge spicules and silica-enriched sea water. Chert nucleation appears to have been controlled by the porosity, permeability, and organic matter content of precursor sediments. This conclusion is based on the fact that chert selectively replaced both porous grainstones and burrows and algal structures enriched in organic matter. Growth of chert probably occurred by a maturation process from opal-A(?), to opal-CT, to quartz, as indicated by the presence of opal-CT precursor textures in many chert nodules. Although field and petrographic evidence argues for an early marine origin for chert in the Arbuckle Group, the light δ¹⁸O values are inconsistent with this origin. Meteoric resetting of the δ¹⁸O values of the chert during exposure of the carbonate platform best explains the light δ¹⁸O values because: (i) the δ¹⁸O values of chert nodules decrease with decreasing δ¹⁸O values of host limestones, and (ii) chert nodules from early dolomite, which underwent more extensive meteoric modification than associated limestones, have lighter δ¹⁸O values than chert nodules from limestones. Increasing recrystallization of chert nodules by meteoric water resulted in progressive ¹⁸O depletion and (quartz) crystal enlargement.     

Diagenesis and reservoir quality of the Aldebaran Sandstone, Denison Trough, east-central Queensland, Australia

The Lower Permian Aldebaran Sandstone is the principal hydrocarbon reservoir in the Denison Trough (Bowen Basin), east-central Queensland, Australia. It accumulated in a wide range of fluvio-deltaic and nearshore marine environments. Detailed petrological study of the unit by thin section, X-ray diffraction, scanning electron microscopy, electron microprobe and isotopic analysis reveals a complex diagenetic history which can be directly related to depositional environment, initial composition and burial-temperature history. Early diagenetic effects included the precipitation of pyrite, siderite and illite-smectite rims (δ¹⁸O (SMOW) =+8.9 to + 11.3‰). Deep burial effects included physico-chemical compaction and the formation of quartz overgrowths, siderite (δ¹³C(PDB) =?34.0 to + 11.5‰, δ¹⁸O =?0.7 to +22.7‰), illite/illite-smectite and ankerite (δ¹³C=?9.3 to ?4.9‰) δ¹⁸O=+ 7.6 to + 14.4‰). Involved fluids were in part ‘connate meteoric’ water derived from compaction of the underlying freshwater Reids Dome beds. Important post-maximum burial effects, controlled by deep meteoric influx from the surface, were ankerite and labile grain dissolution and formation of kaolinite (δ¹⁸O=+7.8 to +8.9‰, δD=?115 to ?99‰), calcite (δ¹³C=?9.5 to +0.9‰, δ¹⁸O=+9.0 to +20.0‰) and dawsonite (δ¹³C=?4.0 to +2.3‰, δ¹⁸O=+9.8 to +19.8‰), the formation of dawsonite reflecting eventual stagnation of the aquifer. Entrapment of contained hydrocarbons was a relatively recent event which may be continuing today. Reservoir quality varies from marginal to good in the west to poor in the east, with predictable trends being directly linked to depositional environment and diagenesis.     

Changes to depositional palaeoenvironments within the Qikou depression (Bohaiwan Basin,China): carbon and oxygen isotopes in lacustrine carbonates of the Palaeogene Shahejie Formation

This paper reports the carbon and oxygen isotope compositions of lacustrine carbonate sediments from the Palaeogene Shahejie Formation, Qikou depression, Bohaiwan Basin, with the aim of determining the palaeoenvironmental conditions in the region. Results from Es₂, the second member of the Shahejie Formation, showed values of δ¹³C and δ¹⁸O from –1.2‰ to +2.4‰ (average +0.6‰) and from –6.8‰ to –4.7‰ (average –5.7‰), respectively, suggesting a relatively hot climate attending deposition. The slightly closed nature of the lake, which contains brackish water, resulted in higher carbonate δ¹³C and δ¹⁸O values than in a meteoric environment. The values of δ¹³C and δ¹⁸O preserved within the carbonates of the overlying lower Shahejie I (Es₁) varied between +1.3‰ and +4.9‰ (average +3.2‰) and from ?4.4‰ to ?1.8‰ (average ?3.1‰), respectively, indicating that the climate became colder at that time. Subsequently, a marine transgression caused the salinity of the lake water to increase. The values of δ¹³C and δ¹⁸O were controlled by salinity. The high δ¹³C values were also influenced by the rapid burial of the lake organisms and by algal photosynthesis. Values of δ¹³C and δ¹⁸O from carbonates in upper Es₁ ranged from ?8.0‰ to +11.0‰ (average +10.1‰) and from ?5.0‰ to ?1.5‰ (average ?3.4‰), respectively, indicating a slight increase in the temperature over time. In the closed and reducing environment, extremes in δ¹³C values resulted from biochemical fermentation. The positive δ¹³C excursion recorded in the carbonates of the Shahejie Formation in the Qikou depression indicates that the palaeoclimate underwent a significant transformation during the Eocene and the Oligocene.     

Hydrogen and Oxygen Isotope Study on the Water-Rock Interaction of the Yinshan (Cu-) Pb-Zn-Ag Ore Deposit, Jiangxi Province

The δ18O values of vein quartz of different stages from the Yinshan ore deposit are constant around 16‰ and the calculated δ18OH2O values attain 8‰± ; the δDH2O values of fluid inclu-sions in vein quartz are constant at about-60‰. From the surface down to 1200 m below the δ18O values of altered rocks gradually decrease from 15‰± to 11‰± . Various water-rock inversion calculations indicate that the ore fluids were formed by the interaction between meteoric water and phyllite at 350℃ and the effective W/ R value of around 0.1. When the water-rock exchange in the upper mineralization system took place, the effective W / R value increased to 5.0 or more. As a result, an evolution and mineralization model of a buffered open system with two-stage water-rock interactions is proposed in this study.     

Antiphase hydrogen and oxygen isotope periodicity in chert nodules

Oxygen and hydrogen isotope analyses were made of Jurassic-age chert nodules from the Holy Cross Mountains, SE Poland, along radial transects at high spatial resolution. There is a radial “sigmoidal” periodicity for both isotope ratios, but the two are out of phase, with high δD values corresponding to low δ¹⁸O values. Periodicity for a 100- to 120-mm diameter nodule is approximately 16 mm, increasing slightly toward the rim, with amplitudes approaching 20 and 3.0‰ for hydrogen and oxygen, respectively. The combined hydrogen-oxygen isotope data for one nodule fall on a published curve for chert forming in equilibrium with seawater (Knauth and Epstein, 1976); the range of delta values corresponds to temperature variations of ∼10°C. Data for a second chert fall on a subparallel δD-δ¹⁸O line with δD values that are almost 50‰ lower. The δD-δ¹⁸O patterns for the nodules cannot be explained by periodic mixing of meteoric and ocean water because the hydrogen and oxygen isotope data are out of phase. Two possible explanations for the antiphase periodicity are (a) cyclical temperature variations, perhaps related to an unstable convection system (e.g., Bolton et al., 1999), and (b) self-organizing catalytic precipitation (e.g., Wang and Merino, 1990). The systematic isotopic variations are difficult to explain by diagenesis and strongly suggest that primary isotopic compositions are preserved. The isotopic data provide important information on the thermal history of the sedimentary basin, if temperature variations are the cause of the isotopic periodicity.     

Anatomy of a large Ag–Pb–Zn deposit in the Great Xing'an Range,northeast China: metallogeny associated with Early Cretaceous magmatism

The Bairendaba vein-type Ag–Pb–Zn deposit, hosted in a Carboniferous quartz diorite, is one of the largest polymetallic deposits in the southern Great Xing'an Range. Reserves exceeding 8000 tonnes of Ag and 3 million tonnes of Pb?+?Zn with grades of 30 g/t and 4.5% have been estimated. We identify three distinct mineralization stages in this deposit: a barren pre-ore stage (stage 1), a main-ore stage with economic Ag–Pb–Zn mineralization (stage 2), and a post-ore stage with barren mineralization (stage 3). Stage 1 is characterized by abundant arsenopyrite?+?quartz and minor pyrite. Stage 2 is represented by abundant Fe–Zn–Pb–Ag sulphides and is further subdivided into three substages comprising the calcite–polymetallic sulphide stage (substage 1), the fluorite–polymetallic sulphide stage (substage 2), and the quartz–polymetallic sulphide stage (substage 3). Stage 3 involves an assemblage dominated by calcite with variable pyrite, galena, quartz, fluorite, illite, and chlorite. Fluid inclusion analysis and mineral thermometry indicate that the three stages of mineralization were formed at temperatures of 320–350°C, 200–340°C, and 180–240°C, respectively. Stage 1 early mineralization is characterized by low-salinity fluids (5.86–8.81 wt.% NaCl equiv.) with an isotopic signature of magmatic origin (δ¹⁸O_fluid = 10.45–10.65‰). The main ore minerals of stage 2 precipitated from aqueous–carbonic fluids (4.34–8.81 wt.% NaCl equiv.). The calculated and measured oxygen and hydrogen isotopic compositions of the ore-forming aqueous fluids (δ¹⁸O_fluid = 3.31–8.59‰, δD_fluid?=??132.00‰ to??104.00‰) indicate that they were derived from a magmatic source and mixed with meteoric water. Measured and calculated sulphur isotope compositions of hydrothermal fluids (δ³⁴S_∑S?=??1.2–3.8‰) indicate that the ore sulphur was derived mainly from a magmatic source. The calculated carbon isotope compositions of hydrothermal fluids (δ¹³C_fluid?=??26.52‰ to??25.82‰) suggest a possible contribution of carbon sourced from the basement gneisses. The stage 3 late mineralization is dominated (1.40–8.81 wt.% NaCl equiv.) by aqueous fluids. The fluids show lower δ¹⁸O_fluid (?16.06‰ to??0.70‰) and higher δD_fluid (?90.10‰ to??74.50‰) values, indicating a heated meteoric water signature. The calculated carbon isotope compositions (δ¹³C_fluid?=??12.82‰ to??6.62‰) of the hydrothermal fluids in stage 3 also suggest a possible contribution of gneiss-sourced carbon. The isotopic compositions and fluid chemistry indicate that the ore mineralization in the Bairendaba deposit was related to Early Cretaceous magmatism.     

Mineral compositions and fluid evolution of the Tonglushan skarn Cu–Fe deposit,SE Hubei,east-central China

The Tonglushan Cu–Fe deposit (1.12 Mt at 1.61% Cu, 5.68 Mt at 41% Fe) is located in the westernmost district of the Middle–Lower Yangtze River metallogenic belt. As a typical polymetal skarn metallogenic region, it consists of 13 skarn orebodies, mainly hosted in the contact zone between the Tonglushan quartz-diorite pluton (140 Ma) and Lower Triassic marine carbonate rocks of the Daye Formation. Four stages of mineralization and alterations can be identified: i.e. prograde skarn formation, retrograde hydrothermal alteration, quartz-sulphide followed by carbonate vein formation. Electron microprobe analysis (EMPA) indicates garnets vary from grossular (Ad_20.2–41.6Gr_49.7–74.1) to pure andradite (Ad_47.4–70.7Gr_23.9–45.9) in composition, and pyroxenes are represented by diopsides. Fluid inclusions identify three major types of fluids involved during formation of the deposit within the H₂O–NaCl system, i.e. liquid-rich inclusions (Type I), halite-bearing inclusions (Type II), and vapour-rich inclusions (Type III). Measurements of fluid inclusions reveal that the prograde skarn minerals formed at high temperatures (>550°C) in equilibrium with high-saline fluids (>66.57 wt.% NaCl equivalent). Oxygen and hydrogen stable isotopes of fluid inclusions from garnets and pyroxenes indicate that ore-formation fluids are mainly of magmatic-hydrothermal origin (δ¹⁸O = 6.68‰ to 9.67‰, δD = –67‰ to –92‰), whereas some meteoric water was incorporated into fluids of the retrograde alteration stage judging from compositions of epidote (δ¹⁸O = 2.26‰ to 3.74‰, δD= –31‰ to –73‰). Continuing depressurization and cooling to 405–567°C may have resulted in both a decrease in salinity (to 48.43–55.36 wt.% NaCl equivalent) and the deposition of abundant magnetite. During the quartz-sulphide stage, boiling produced sulphide assemblage precipitated from primary magmatic-hydrothermal fluids (δ¹⁸O = 4.98‰, δD = –66‰, δ³⁴S values of sulphides: 0.71–3.8‰) with an extensive range of salinities (4.96–50.75 wt.% NaCl equivalent), temperatures (240–350°C), and pressures (11.6–22.2 MPa). Carbonate veins formed at relatively low temperatures (174–284°C) from fluids of low salinity (1.57–4.03 wt.% NaCl equivalent), possibly reflecting the mixing of early magmatic fluids with abundant meteoric water. Boiling and fluid mixing played important roles for Cu precipitation in the Tonglushan deposit.     

Genesis of the Ciemas Gold Deposit and Relationship with Epithermal Deposits in West Java, Indonesia: Constraints from Fluid Inclusions and Stable Isotopes

The Ciemas gold deposit is located in West Java of Indonesia,which is a Cenozoic magmatism belt resulting from the Indo-Australian plate subducting under the Eurasian plate.Two different volcanic rock belts and associated epithermal deposits are distributed in West Java:the younger late Miocene-Pliocene magmatic belt generated the Pliocene-Pleistocene epithermal deposits,while the older late Eocene-early Miocene magmatic belt generated the Miocene epithermal deposits.To constrain the physico-chemical conditions and the origin of the ore fluid in Ciemas,a detailed study of ore petrography,fluid inclusions,laser Raman spectroscopy,oxygen-hydrogen isotopes for quartz was conducted.The results show that hydrothermal pyrite and quartz are widespread,hydrothermal alteration is well developed,and that leaching structures such as vuggy rocks and extension structures such as comb quartz are common.Fluid inclusions in quartz are mainly liquid-rich two phase inclusions,with fluid compositions in the NaCl-H20 fluid system,and contain no or little CO_2.Their homogenization temperatures cluster around 240℃-320℃,the salinities lie in the range of 14-17 wt.%NaCl equiv,and the calculated fluid densities are 0.65-1.00 g/cm~3.The values of δ~(18)O_(H2O-VSMOW)for quartz range from +5.5‰ to +7.7‰,the δD_(VSMOW) of fluid inclusions in quartz ranges from-70‰ to-115‰.All of these data indicate that mixing of magmatic fluid with meteoric water resulted in the formation of the Ciemas deposit.A comparison among gold deposits of West Java suggests that Miocene epithermal ore deposits in the southernmost part of West Java were more affected by magmatic fluids and exhibit a higher degree of sulfldation than those of Pliocene-Pleistocene.     

Carbon and oxygen isotopic constraints on paleoclimate and paleoelevation of the southwestern Qaidam basin,northern Tibetan Plateau

We investigate the growth of the northern Tibetan Plateau and associated climate change by applying oxygen and carbon isotopic compositions in Cenozoic strata in the southwestern Qaidam basin. The X-ray diffraction and isotopic studies reveal that the carbonate minerals are mainly authigenic and they do not preserve any evidence for detrital carbonate and diagenesis. The isotope data show large fluctuations in the δ¹⁸O and δ¹³C values in the middle–late Eocene, indicating relatively warm and seasonal dry climate. The positive correlation of the δ¹⁸O and δ¹³C values in the Oligocene and the positive shift of the δ¹³C values from the Eocene to Oligocene suggest that the climate changed to arid in the Oligocene. However, the δ¹⁸O values show negative shift, which is closely related to the global cooling event. During the Miocene, the δ¹³C values vary between –2‰ and –4‰, whereas the δ¹⁸O values show continuous negative shift. The mean δ¹⁸O values decrease from –8.5‰ in the early Miocene to –10.0‰ in the late Miocene. The stable isotope-based paleoaltimetry results suggest that the elevation of the southwestern Qaidam basin was approximately 1500 m in the middle–late Eocene and Oligocene. Subsequently, during Miocene the crustal uplift process started and the elevation reached approximately 2000 m in the early Miocene and 2500 m in the late Miocene, which suggests large-scale growth of the northern Tibet Plateau during the Miocene.     

Hydrogen and oxygen isotope ratios in nodular and bedded cherts

Hydrogen and oxygen isotopic compositions of cherts (δD for hydroxyl hydrogen in the chert, δ¹⁸O for the total oxygen) have been determined for a suite of samples from the central and western United States. When plotted on a δD-δ¹⁸O diagram, Phanerozoic cherts define domains parallel to the meteoric water line which are different for different periods of geologic time. The elongation parallel to the meteoric water line suggests that meteoric waters were involved in the formation of many cherts.The existence of different chert δ-values for different geologic times indicates that once the granular microcrystalline quartz of cherts crystallizes its isotopic composition is preserved with time. An explanation for the change with time of the isotopic composition of cherts involving large changes with time in the isotopic composition of ocean water is unlikely since δ¹⁸O of the ocean would have had to decrease by about 3‰between Carboniferous and Triassic time and then increase about 5%.` from Triassic to Cretaceous time. Such isotopic changes cannot be accounted for by extensive glaciation, sedimentation of hydrous minerals, or input of water from the mantle into the oceans.The variation with time of the chert δ-values can be satisfactorily explained in terms of past climatic temperature fluctuations if the chert-water isotope fractionation with temperature is approximated by 1000 lnα = 3.09 × 10⁶T^?2 – 3.29. Crystallization temperatures so inferred suggest that the average climatic temperatures for the central and western U.S. decreased from about 34 to 20°C through the Paleozoic, increased to 35–40°C in the Triassic, and then decreased through the Mesozoic to Tertiary values of about 17°C. A few data for the Precambrian suggest the possibility that Earth surface temperatures may have reached about 52°C at 1.3 b.y. and about 70°C at 3 b.y.     

Ore Genesis of the Lunwei Granite‐Related Scheelite Deposit in the Wuyi Metallogenic Belt,Southeast China: Constraints from Geochronology,Fluid Inclusions,and H–O–S Isotopes

A granite‐related scheelite deposit has been recently discovered in the Wuyi metallogenic belt of southeast China. The veinlet–disseminated scheelite occurs mainly in the inner and outer contact zones of the porphyritic biotite granite, spatially associated with potassic feldspathization and silicification. Re–Os dating of molybdenite intergrowths with scheelite yield a well‐constrained isochron age of 170.4 ± 1.2 Ma, coeval with the LA–MC–ICP–MS concordant zircon age of porphyritic biotite granite (167.6 ± 2.2 Ma), indicating that the Lunwei W deposit was formed in the Middle Jurassic (~170 Ma). We identify three stages of ore formation (from early to late): (I) the quartz–K‐feldspar–scheelite stage; (II) the quartz–polymetallic sulfide stage; and (III) the quartz–carbonate stage. Based on petrographic observations and microthermometric criteria, the fluid inclusions in the scheelite and quartz are determined to be mainly aqueous two‐phase (liquid‐rich and gas‐rich) fluid inclusions, with minor gas‐pure and CO₂‐bearing fluid inclusions. Ore‐forming fluids in the Lunwei W deposit show a successive decrease in temperature and salinity from Stage I to Stage III. The homogenization temperature decreases from an average of 299 °C in Stage I, through 251 °C in Stage II, to 212 °C in Stage III, with a corresponding change in salinity from an average of 5.8 wt.%, through 5.2 wt.%, to 3.4 wt.%. The ore‐forming fluids have intermediate to low temperatures and low salinities, belonging to the H₂O–NaCl ± CO₂ system. The δ¹⁸O_H2O values vary from 1.8‰ to 3.3‰, and the δD_V‐SMOW values vary from –66‰ to –76‰, suggesting that the ore‐forming fluid was primarily of magmatic water mixed with various amounts of meteoric water. Sulfur isotope compositions of sulfides (δ³⁴S ranging from –1.1‰ to +2.4‰) and Re contents in molybdenite (1.45–19.25 µg/g, mean of 8.97 µg/g) indicate that the ore‐forming materials originated mainly in the crust. The primary mechanism for mineral deposition in the Lunwei W deposit was a decrease in temperature and the mixing of magmatic and meteoric water. The Lunwei deposit can be classified as a porphyry‐type scheelite deposit and is a product of widespread tungsten mineralization in South China. We summarize the geological characteristics of typical W deposits (the Xingluokeng, Shangfang, and Lunwei deposits) in the Wuyi metallogenic belt and suggest that porphyry and skarn scheelite deposits should be considered the principal exploration targets in this area.     

A Study of Ore-forming Fluids in the Shimensi Tungsten Deposit, Dahutang Tungsten Polymetallic Ore Field, Jiangxi Province, China

The Dahutang tungsten polymetallic ore field is located north of the Nanling W-Sn polymetallic metallogenic belt and south of the Middle—Lower Yangtze River Valley Cu-Mo-Au-Fe porphyry-skarn belt.It is a newly discovered ore field,and probably represents the largest tungsten mineralization district in the world.The Shimensi deposit is one of the mineral deposits in the Dahutang ore field,and is associated with Yanshanian granites intruding into a Neoproterozoic granodiorite batholith.On the basis of geologic studies,this paper presents new petrographic,microthermometric,laser Raman spectroscopic and hydrogen and oxygen isotopic studies of fluid inclusions from the Shimensi deposit.The results show that there are three types of fluid inclusions in quartz from various mineralization stages:liquid-rich two-phase fluid inclusions,vapor-rich two-phase fluid inclusions,and three-phase fluid inclusions containing a solid crystal,with the vast majority being liquid-rich two-phase fluid inclusions.In addition,melt and melt-fluid inclusions were also found in quartz from pegmatoid bodies in the margin of the Yanshanian intrusion.The homogenization temperatures of liquid-rich two-phase fluid inclusions in quartz range from 162 to 363℃ and salinities are 0.5wt%-9.5wt%NaCI equivalent.From the early to late mineralization stages,with the decreasing of the homogenization temperature,the salinity also shows a decreasing trend.The ore-forming fluids can be approximated by a NaCl-H_2O fluid system,with small amounts of volatile components including CO_2,CH_4 and N_2,as suggested by Laser Raman spectroscopic analyses.The hydrogen and oxygen isotope data show that δ5D_(V-smow) values of bulk fluid inclusions in quartz from various mineralization stages vary from-63.8‰ to-108.4‰,and the δ~(18)O_(H2O) values calculated from the δ~(18)O_(V-)smow values of quartz vary from-2.28‰ to 7.21‰.These H-O isotopic data are interpreted to indicate that the ore-forming fluids are mainly composed of magmatic water in the early stage,and meteoric water was added and participated in mineralization in the late stage.Integrating the geological characteristics and analytical data,we propose that the ore-forming fluids of the Shimensi deposit were mainly derived from Yanshanian granitic magma,the evolution of which resulted in highly differentiated melt,as recorded by melt and melt-fluid inclusions in pegmatoid quartz,and high concentrations of metals in the fluids.Cooling of the ore-forming fluids and mixing with meteoric water may be the key factors that led to mineralization in the Dahutang tungsten polymetallic ore field.     

Diagenesis of spiculites and carbonates in a Permian temperate ramp succession – Tempelfjorden Group,Spitsbergen, Arctic Norway

This paper explores little investigated diagenesis of spicule‐dominated sediments, based on Permian spiculites and cool‐water carbonates of the Tempelfjorden Group in central Spitsbergen. Field observations, petrography, stable isotope geochemistry, and mineralogical and chemical analyses reveal that the strata have been subjected to multistage diagenesis as the result of silica phase transitions at medium burial depths and deep‐burial overprinting. The growth of silica concretions occurred during the opal‐A/opal‐CT conversion and was controlled by the content and distribution of clay and spicules in the sediment, resulting in a variety of megascopic silica fabrics. Opal‐CT was subsequently dissolved, and all silica is now in a stable quartz stage. Petrographically, the rocks are characterized by a variety of chalcedony and quartz cements which perfectly preserve precursor textures. Most cements precipitated from silica‐oversaturated fluids, and their shapes reflect the silica saturation state and geometry of the pore space. Some microquartz and cryptoquartz also formed by a solid–solid inversion (recrystallization) of chalcedony. The cements have δ ¹⁸O values between +30‰ and +20‰ Standard Mean Ocean Water and display a systematic depletion in ¹⁸O from the first to the last crystallized, interpreted to reflect a gradual increase in temperature during burial. The precipitation of quartz cements started in the Middle Triassic when the strata passed the 19°C isotherm at burial depths of ca 600 m, and was completed in the mid‐Cretaceous, 2·3 km beneath the sea floor at temperatures of 75°C. Late diagenetic overprinting of the chert includes fracturing, brecciation and cementation with carbonate cements having δ ¹⁸O values between +2‰ and −30‰ Pee Dee Belemnite and δ ¹³C values between +4‰ and −14‰ Pee Dee Belemnite; they are linked to hot solutions introduced during Cretaceous volcanism or Palaeogene tectonism. This study illustrates the diagenetic pathway during burial of spicule‐rich sediments in a closed system and thereby provides a baseline for studies of more complexly altered chert deposits.     

Origin of Paleofluids in Dabashan Foreland Thrust Belt:Geochemical Evidence of 13C,18O and 87Sr/86Sr in Veins and Host Rocks

In the last ten years, with important discoveries from oil and gas exploration in the Dabashan foreland depression belt in the borderland between Shanxi and Sichuan provinces, the relationship between the formation and evolution of, and hydrocarbon accumulation in, this foreland thrust belt from the viewpoint of basin and oil and gas exploration has been studied. At the same time, there has been little research on the origin of fluids within the belt. Based on geochemical system analysis including Z values denoting salinity and research on δ13C, δ18O and 87Sr/86Sr isotopes in the host rocks and veins, the origin of paleofluids in the foreland thrust belt is considered. There are four principal kinds of paleofluid, including deep mantle-derived, sedimentary, mixed and meteoric. For the deep mantle-derived fluid, the δ13C is generally less than ?5.0‰PDB, δ18O less than -10.0‰PDB, Z value less than 110 and 87Sr/86Sr less than 0.70600; the sedimentary fluid is mainly marine carbonate-derived, with the δ13C generally more than ?2.0‰PDB, δ18O less than ?10.0‰PDB, Z value more than 120 and 87Sr/86Sr ranging from 0.70800 to 0.71000; the mixed fluid consists mainly of marine carbonate fluid (including possibly a little mantle-derived fluid or meteoric water), with the δ13C generally ranging from ?2.0‰ to ?8.0‰PDB, δ18O from ?10.0‰ to ?18.0‰ PDB, Z value from 105 to 120 and 87Sr/86Sr from 0.70800 to 0.71000; the atmospheric fluid consists mainly of meteoric water, with the δ13C generally ranging from 0.0‰ to ?10.0‰PDB, δ18O less than ?8.0‰PDB, Z value less than 110 and 87Sr/86Sr more than 0.71000. The Chengkou fault belt encompasses the most complex origins, including all four types of paleofluid; the Zhenba and Pingba fault belts and stable areas contain a simple paleofluid mainly of sedimentary type; the Jimingsi fault belt contains mainly sedimentary and mixed fluids, both consisting of sedimentary fluid and meteoric water. Jurassic rocks of the foreland depression belt contain mainly meteoric fluid.     

Fluid Inclusion, Rare-Earth Element and Stable Isotope Study of Carbonate Minerals from the Pongkor Epithermal Gold–Silver Deposit, West Java, Indonesia

The Pongkor gold–silver deposit is the largest low‐sulfidation epithermal precious metal deposit in Indonesia, and is of Pliocene age. The deposit consists of nine major subparallel quartz–adularia–carbonate veins with very low sulfide content. Vein infill records five paragenetic sequences, dominated by calcite in the early stage and quartz in the later stage of the hydrothermal evolution. Fluid inclusions in hydrothermal calcite and quartz of all stages indicate a temperature ranging from 180 to 220°C and a meteoric water origin (very low salinity close to 0 wt% NaCl equivalent). Carbon isotope data on calcite display a narrow range from ?6.5 to ?3.0‰δ¹³C. The oxygen isotope values have a wider range of +4.6 to +10.1‰δ¹⁸O. The broadly positive correlation of the δ¹³C versus δ¹⁸O plot suggests that the carbon species, which equilibrated during the formation of calcite, is dominated by H₂CO₃ not far from equilibrium with HCO₃^?. The abundance of rare earth and yttrium (REY) in carbonate samples is very low (>REY mostly <2 ppm). However, there is always a positive Eu anomaly, which indicates a deeper fluid reservoir at >250°C.     

Multi-stage fluid incursion in the Palaeozoic basement-hosted Saint-Salvy ore deposit (NW Montagne Noire,southern France)

The Saint-Salvy vein-hosted Zn (+Ge) deposit occurs in an E–W fault system which flanks the southern margin of the late Variscan Sidobre granite, and cross-cuts Cambrian black shales of the Palaeozoic basement. Comprehensive mineralogical and geochemical studies of vein samples have revealed four mineralizing events (M1–M4) related to late and post-Variscan tectonic events. A further late-stage event may be related to weathering.M1 (=skarn deposits) and M2 (=patchily mineralized quartz veinlets) are associated with granite emplacement. Quartz contains low salinity, H₂OCO₂(NaCl)-dominated fluids(⩽6wt% NaCl equiv.) of relatively high temperature (300–580°C), trapped under moderate to high pressure. Estimated M1 fluid δD and calculated fluidδ¹⁸O plot within the metamorphic water field. There appears to be no involvement of magmatic fluids.By contrast, M3 (= barren quartz) and M4 (= zinciferous economic mineralization) stages have H₂OCO₂NaClCaCl₂ fluid inclusions with high salinities (23–25 wt% NaCl equiv.) and low temperatures(∼ 80–140°C), which were trapped under low-pressure conditions. The high salinity and NaCl + CaCl₂ content of both M3 and M4 indicates that their parent fluids leached evaporitic salts. M3 fluids are meteoric water dominated, falling close to the meteoric water line (δD andδ¹⁸O averaging −64 and −8‰, respectively). M4 fluids have highly distinctive δD averaging −101‰, and calculated fluidδ¹⁸O varying from−1.2to+7.1‰. The unusually low δD composition of M4 suggests the involvement of “organic” fluids, in which H is derived directly or indirectly from organic matter. The relatively highδ¹⁸O of M4 fluids indicates that considerable isotopic exchange with sedimentary material took place, displacing theδ¹⁸O from the meteoric water line. The data imply interaction of meteoric waters with evaporite and hydrocarbon-bearing sedimentary sequences, most probably the adjacent Aquitain Basin.The main economic mineralization (M4 stage) took place during a tensional event, probably coincident with the Lias-Dogger transition.Calculatedδ³⁴S_H2S of M4 sulphide(+5.4to+8.2‰) is almost identical toδ³⁴S of local Cambrian sulphides(+4.7to+9.4‰) suggesting a genetic link. Abundant siderite associated with M4 sphalerite hasδ¹³C ranging from−2.6to−4.4‰ indicating that carbon was sourced from sedimentary carbonate mobilized by, or equilibrated with the hydrothermal fluid.Late-stage sulphides exhibit extraordinary and highly distinctiveδ³⁴S. Sphalerite has extremely low δ³⁴S(−42.5to−50.5‰), whereas pyrite has an extraordinary large range from−33.2‰to+74.3‰. Closed system sulphate reduction is held to be responsible for the extremely highδ³⁴S: whereas more open system reduction produces the very low values. The coincidence of isotopically lowδ¹³C(−7.6to−11.9‰) for co-genetic calcite suggests the involvement of organic matter in the reduction process.     

Diagenesis and formation water chemistry of Triassic reservoir sandstones from southern Tunisia

The fluvial Triassic reservoir subarkoses and arkoses (2409·5–2519·45 m) of the El Borma oilfield, southern Tunisia, were subjected to cementation by haematite, anatase, infiltrated clays, kaolinite and K-feldspar at shallow burial depths from meteoric waters. Subsequently, basinal brines controlled the diagenetic evolution of the sandstones and resulted initially in the precipitation of quartz overgrowths, magnesian siderite, minor ferroan magnesite and anhydrite. The enrichment of siderite in ¹²C isotope (δ¹³C_PDB= - 14·5 to - 9‰) results from derivation of carbon from the thermal decarboxylation of organic matter. During further burial, the precipitation of dickite and pervasive transformation of kaolinite into dickite occurred, followed by the formation of microcrystalline K-feldspar and quartz, chlorite and illite, prior to the emplacement of oil. Present day formation waters are Na-Ca-Cl brines evolved by the evaporation of seawater and water/mineral interaction and are in equilibrium with the deep burial (≤ 3·1 km) minerals. These waters are suggested to be derived from the underlying Silurian and Devonian dolomitic mudstones.     

Stable isotope evidence for the origin of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel

The oxygen isotope compositions of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel, have been used to identify porewater types during diagenesis. Changes in porewater composition can be related to major geological events within southern Israel. In particular, saline brines played an important role in late (Pliocene-Pleistocene) dolomitization of these rocks. Diagenetic carbonates included early siderite (δ¹⁸O_SMOW=+24.4 to +26.5‰δ¹³C_PDB=?1.1 to +0.8‰), late dolomite, ferroan dolomite and ankerite (δ¹⁸O_SMOW=+18.4 to +25.8‰; δ¹³C_PDB=?2.1 to +0.2‰), and calcite (δ¹⁸O_SMOW=+21.3 to +32.6‰; δ¹³C_PDB=?4.2 to + 3.2‰). The petrographic and isotopic results suggest that siderite formed early in the diagenetic history at shallow depths. The dolomitic phases formed at greater depths late in diagenesis. Crystallization of secondary calcite spans early to late diagenesis, consistent with its large range in isotopic values. A strong negative correlation exists between burial depth (temperature) and the oxygen isotopic compositions of the dolomitic cements. In addition, the δ¹⁸O values of the dolomitic phases in the northern Negev and Judea Mountains are in isotopic equilibrium with present formation waters. This behaviour suggests that formation of secondary dolomite post-dates the tectonic activity responsible for the present relief of southern Israel (Upper Miocene to Pliocene) and that the dolomite crystallized from present formation waters. Such is not the case in the Central Negev. In that locality, present formation waters have much lower salinities and δ¹⁸O values, indicating invasion of freshwater, and are out of isotopic equilibrium with secondary dolomite. Recharge of the Inmar Formation by meteoric water in the Central Negev occurred in the Pleistocene, and halted formation of dolomite.