Genetic investigation and comparison of Kartaldağ and Madendağ epithermal gold deposits in Çanakkale,NW Turkey

Two epithermal gold deposits (Kartaldağ and Madendağ) located in NW Turkey have been characterized through the detailed examinations involving geologic, mineralogical, fluid inclusion, stable isotope, whole-rock geochemistry, and geochronology data.The Kartaldağ deposit (0.01–17.65 ppm Au), hosted by Eocene dacite porphyry, is associated with four main alteration types with characteristic assemblage of: i) chlorite/smectite–illite ± kaolinite, ii) quartz–kaolinite, iii) quartz–alunite–pyrophyllite, iv) quartz–pyrite, the last being characterized by three distinct quartz generations comprising massive/vuggy (early), fine–medium grained, vug-lining (early), and banded, colloform, comb (late) textures. Observed sulfide minerals are pyrite, covellite, and sphalerite. Oxygen and sulfur isotope analyses, performed on quartz (δ¹⁸O_(quartz): 7.93 to 8.95‰ and calculated δ¹⁸O_(H2O): − 7.95 to 1.49‰) and pyrite (δ³⁴S_(pyrite): − 4.8‰ and calculated δ³⁴S_(H2S): − 6.08 to − 7.20‰) separates, suggest a meteoric water source for water in the hydrothermal fluid, and an igneous source for the sulfur dissolved in ore-related fluids. Microthermometric analyses of primary fluid inclusion assemblages performed on quartz (late quartz generation) yield temperatures (Th) dominantly in the range of 245–285 °C, and generally low salinity values at 0 to 1.7 wt.% NaCl eq. Based on the quartz textures and the associated base metal concentrations, along with fluid inclusion petrography, the early vug-lining quartz is considered to have been associated with the mineralization possibly through a boiling and a late mixing process at > 285 °C.The Madendağ deposit (0.27–20.60 ppm Au), hosted by Paleozoic mica schists, is associated with two main alteration types: sericite–illite–kaolinite, and quartz–pyrite dominated by two distinct quartz generations i) early colloform, comb and banded quartz and ii) late quartz, forming the cement in hydrothermal breccia. Whereas oxygen isotope analyses of quartz (δ¹⁸O_(quartz): 9.55 to 18.19‰ and calculated δ¹⁸O_(H2O): − 2.97 to 5.54‰) suggest varying proportions of meteoric and magmatic sources for the ore bearing fluid, sulfur isotope ratios (δ³⁴S_(pyrite): − 2.2‰ and calculated δ³⁴S_(H2S): (− 3.63) to (− 3.75) ‰) point to an essentially magmatic source for sulfur with or without contribution from sedimentary sources. Microthermometric analysis carried out on primary fluid inclusion populations of a brecciated sample (early quartz), give a temperature (Th) range of 235–255 °C and 0.0 to 0.7 wt.% NaCl eq. salinity. Based on the textural relationship, base metal and high gold contents, the ore precipitation stage is associated with late stage quartz formation via a possible boiling process.The presence of alunite, pyrophyllite and kaolinite, vuggy quartz and covellite suggest a high-sulfidation type of epithermal deposit for Kartaldağ. On the other hand, Madendağ is identified as an adularia-sericite type owing to the presence of significant sericite, neutral pH clays (mostly illite, chlorite/smectite, and kaolinite), low temperature quartz textures (e.g., colloform, comb, and banded quartz), and limited sulfide minerals.Given the geographical proximity of Kartaldağ and Madendağ deposits, the similar temperature and salinity ranges obtained from their fluid inclusions, and the similar ages of igneous rocks in both deposits (Kartaldağ: 40.80 ± 0.36 to 42.19 ± 0.45 Ma, Madendağ: 43.34 ± 0.85 Ma) the mineralizing systems in both deposits are considered to be genetically related.     

Argillization processes at the El Berrocal analogue granitic system (Spain): mineralogy,isotopic study and implications for the performance assessment of radwaste geological disposal

The El Berrocal granite/U-bearing quartz vein (UQV) system has been studied as a natural analogue of a high-level radioactive waste repository. The main objective was to understand the geochemical behaviour of natural nuclides under different physicochemical conditions. Within this framework, the argillization processes related to fracturing and formation of the uranium–quartz vein were studied from a mineralogical and isotopic standpoint in order to establish their temperatures of formation and thus complete the geothermal history of the system. For this purpose, δ¹⁸O values were determined for pure mineral from the unaltered granite and quartz from the uranium–quartz vein, as well as for mixture samples from the hydrothermally altered granite (sericitised granite) and clayey samples from fracture fillings, including the clayey walls of the uranium–quartz vein. The isotopic signature of quartz from the uranium–quartz vein and the monophasic nature of its fluid inclusions led us to conclude that the isotopic signature of water in equilibrium with quartz was approximately in the range from −8.3‰ to −5.7‰ V-SMOV, its temperature of formation being around 85–120 °C. The δ¹⁸O values of pure sericite from the hydrothermally altered granite, calculated by means of the oxygen fraction molar method, indicate that its temperature of formation, in equilibrium with the aforementioned waters, is also in the range from 70 °C to approximately 120 °C. Clays from fracture fillings and clayey walls of the uranium–quartz vein are usually mixtures, in different proportions, of illite, approximately formed between 70 and 125 °C; two generations of kaolinite formed at approximately 90–130 °C and at around 25 °C, respectively; smectite, formed at ≤25 °C; and occasionally palygorskite, formed either between 30 and 45 °C or 19 and 32 °C, depending on the fractionation equation used. These data suggest that sericite from the hydrothermally altered granite, quartz from the uranium–quartz vein, illite and the first generation of kaolinite from the fracture fillings resulted from the same hydrothermal process affecting the El Berrocal granite in relation to fracturing. Under certain physicochemical conditions (T≈100 °C, pH≈8 and log [H₄SiO₄] between −4 and −3), illite and kaolinite can be paragenetic. As a result of weathering processes, smectite was formed from hydrothermal illite and inherited albite under alkaline weathering, while the second generation of kaolinite was formed from smectite, under acid conditions and close to the sulphide-rich uranium–quartz vein. Palygorskite is an occasional mineral formed probably either during the thermal tail of the above-described hydrothermal process or during weathering processes. In both cases, palygorskite must have formed from alkaline Si–Mg-rich solutions. Finally, these data and processes are discussed in terms of natural analogue processes, drawing some implications for the performance assessment of a deep geological radwaste repository (DGRR).     

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.     

A fluid inclusion and light element stable isotope study of the gold-bearing quartz vein system,Falun, Sweden

The Falun gold quartz vein mineralization is located ca 230 km NW of Stockholm, Sweden, within the Early Proterozoic volcano-sedimentary sequence of Bergslagen. The mineralization consists of a system with subparallel quartz veins that crosscut the alteration zone to the Falun massive sulphide deposit. Early barren and late gold-bearing quartz veins follow tectonic structures postdating the formation of the massive sulphide ore. Both generations of veins are epigenetic to the massive sulphide ore and were formed by hydrothermal processes. Fluid inclusion study of the gold-bearing quartz veins indicates a low-moderately saline fluid (0.3 to 17.4 equiv wt% NaCl). Heterogeneous trapping is indicated by coexisting inclusions showing a variable CO₂ content from 100% CO₂ ± CH₄ to 100% aqueous fluid. Temperatures of total homogenization also show a wide spread from 116–350°C with a slightly bimodal distribution with peaks at ca 180°C and 280°C. MeasuredδD values — 69 to — 63%0 (SMOW), of inclusion fluid and calculatedδ ¹⁸O values of hydrothermal fluids — 7.5 to — 1.4%0 (SMOW), strongly suggest a meteoric origin for the fluids. The quite consistentδD values and the range inδ ¹⁸O values indicate that major water-rock interaction led to the evolution inδ18O of the hydrothermal fluids.     

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.     

Origin and migration of palaeofluids in the Upper Visean of the Campine Basin, northern Belgium

Upper Visean limestones in the Campine Basin of northern Belgium are intensively fractured. The largest and most common fractures are cemented by non-ferroan, dull brown-orange luminescent blocky calcite. First melting temperatures of fluid inclusions in these calcites are around -57°C, suggesting that precipitation of the cements occurred from NaCl-CaCl₂-MgCl₂ fluids. The final melting temperatures (T_m^ice) are between -5 and -33°C. The broad range in the T_m^ice data can be explained by the mixing of high salinity fluids with meteoric waters, but other hypotheses may also be valid. Homogenization temperatures from blocky calcite cements in the shelf limestones are interpreted to have formed between 45 and 75°C. In carbonates which were deposited close to and at the shelf margin, precipitation temperatures were possibly in the range 70-85°C and 72-93°C, respectively. On the shelf, the calcites have a δ¹⁸O around -9.3‰ PDB and they are interpreted to have grown in a fluid with a δ¹⁸O between −3.5 and +1.0‰ SMOW. At the shelf margin, blocky calcites (δ¹⁸O∼ - 13.5‰ PDB) could have precipitated from a fluid with a δ¹⁸O betweenn -4.0 and -1.1‰ SMOW. The highest oxygen isotopic compositions are comparable to those of Late Carboniferous marine fluids (δ¹⁸O= - 1‰ SMOW). The lowest values are more positive than a previously reported composition for Carboniferous meteoric waters (δ¹⁸O= -7‰ SMOW). Precipitation is likely to have occurred in marine-derived fluids, which mixed with meteoric waters sourced from near the Brabant Massif. Fluids with a similar negative oxygen isotopic composition and high salinity are actually present in Palaeozoic formations. The higher temperature range in the limestones near the shelf margin is explained by the upward migration of fluids from the ‘basinal’ area along fractures and faults into the shelf.     

The Cipoeiro gold deposit,Gurupi Belt,Brazil: Geology,chlorite geochemistry,and stable isotope study

The Cipoeiro gold deposit, located in the Gurupi Belt, northern Brazil, is hosted by tonalites of 2148 Ma. The deposit is controlled by splays related to the major strike-slip Tentugal shear zone, and at the deposit scale, the mineralization is confined to ductile–brittle shear zones. Mineralization style comprises thick quartz veins and narrow and discontinuous quartz-carbonate veinlets associated with disseminations in altered host rocks. The postmetamorphic hydrothermal paragenesis is composed of quartz, calcite, chlorite, white mica (phengite), pyrite, and minor albite. Electron microprobe analysis of chlorites reveals a relatively uniform chemical composition at depths of more than 100 m. The chlorites are characterized by (Fe + Mg) ratios between 0.37 and 0.47 and Al^IV ranging between 2.22 and 2.59 a.p.f.u. and are classified as Fe-chlinochlore. Temperatures calculated by applying the Al^IV contents of chlorites yield a relatively narrow interval of 305 ± 15°C. Stable isotope (O, H, C, S) compositions have been determined in silicate, carbonate, and sulfide minerals. The δ¹⁸O and δD values of the mineralizing fluid range from +2.4 to +5.7 and from −43‰ to −20‰, respectively, and are interpreted as having a metamorphic origin. The δ¹³C values of fluid CO₂ are in the range −10.7‰ to −3.9‰, whereas the fluid δ³⁴S is around 0‰. Carbon and sulfur compositions are not diagnostic of their sources, compatible as they are with mantle, magmatic, or average crustal reservoirs. The hydrothermal paragenesis, chlorite–pyrite coexistence, temperature of ore formation, and sulfur isotope evidence indicate relatively reduced fO₂ conditions for the mineralizing fluid. Geologic, chemical, and isotopic characteristics of the Cipoeiro deposit are compatible with the class of orogenic gold deposits.     

Geological,geochemical, stable isotope,and fluid inclusion characteristics of epithermal gold mineralization,Velvet District,Nevada

Gold mineralization in the Velvet District occurs in an eastward dipping sequence of late Tertiary rhyolitic ash-flow tuffs, flows, and tuffaceous sediments in northwestern Nevada. Minor gold and silver concentrations are associated with irregular zones of brecciation, argillic alteration, and quartz veining along north-northeast trending normal faults. Reaction of mineralizing fluids with wallrock produced an argillic alteration assemblage of illite, mixed-layer clays, smectite, and kaolinite. Illite alteration and highest gold concentrations appear to be associated with zones of high water/rock ratios. Kaolinite, smectite, alunite, and opal are postulated to have formed during a steam-dominated episode of alteration.Fluid inclusion studies indicate that the quartz veins were deposited in the temperature range 230 to 280°C from fluids which had salinities equivalent to 0.2–0.8 weight percent NaCl. δ ¹⁸O of quartz veins varies from ?2.5 to $\text{+6.7 ‰}$ and indicates that the ore fluid must have been Tertiary meteroric water. Stable isotope data appear to define a zone of concentrated fluid flow and potential subsurface mineralization in the southeastern part of the district. Fluid inclusion and isotope studies can be used in combination with more standard geochemical, geophysical, and geological information to provide site-specific targets for epithermal metal concentrations.     

Fluid evolution and ore genesis of the A'gui Cu deposit in southern Great Xing'an Range,Northeast China: Evidence from fluid inclusion and C–H–O–S–Pb isotopes

The A'gui Cu deposit is located in the eastern slope of the southern Great Xing'an Range (SGXR), and it is a vein-type Cu deposit spatially and temporally related to the Cretaceous monzogranite which intruded Pingshan Formation. Vein-type Cu orebodies are mainly hosted in the NE and nearly EW faults. Previous studies on the A'gui deposit mainly focused on geological exploration, and there was no study on its fluid evolution and genesis. Therefore, we carried out conducted fluid inclusion and stable isotope (C–H–O–S–Pb) analysis to study the fluid evolution, fluid and ore-forming material sources and genesis of the A'gui deposit. According to the field investigations and mineral crosscutting relationships, four paragenetic stages were identified: quartz–pyrite–chalcopyrite–pyrrhotite–arsenopyrite ± magnetite (Stage I), quartz–pyrite–chalcopyrite (Stage II), quartz–chalcopyrite ± pyrite–sphalerite–galena (Stage III) and carbonate ± quartz (Stage IV). From Stage I to Stage II, the assemblage of fluid inclusions (FIs) in quartz is characterized by the development of daughter mineral–bearing three–phase FIs (SL–type), vapour FIs (V–type), vapour–rich two–phase aqueous FIs (LV–type) and liquid–rich two–phase aqueous FIs (VL–type). Only VL–type FIs appeared in the Stage III quartz and Stage IV calcite. The homogenization temperatures of FIs in stages I, II, III and IV are 329–390 °C, 255–336 °C, 166–244 °C and 120–157 °C, with salinities of 3.37–45.33 wt%, 3.53–39.76 wt%, 4.17–7.86 wt% and 3.37–7.15 wt% NaCl eqv., respectively. The fluid inclusion type assemblage suggested that obvious fluid boiling occurred in the Stage I and Stage II. Fluid boiling may be the reason for the precipitation of useful minerals. According to the HO isotope analysis of stages I–II quartz (δ¹⁸O_H2O = −2.1 to 3.2 ‰, δD_V–SMOW = −128.4 ‰ to −110.6 ‰), the fluid was originally magmatic water. From Stage III to Stage IV (δ¹⁸O_H2O = −12.3 to −2.3 ‰, δD_V–SMOW = −129.6 ‰ to −104.2 ‰), the HO isotope value is obviously close to the meteoric water line, indicating that meteoric water is mixed with evolved magmatic solutions. The ore–forming fluid of the A'gui deposit represents a medium–high temperature NaCl-H₂O magmatic hydrothermal system. The C isotope compositions (δC_V–PDB = −5.74 ‰ to −4.76 ‰) in stage IV indicate that the C in the fluid was derived from a magmatic source and was affected by meteoric water. In addition, the measured S isotope compositions in stages I–III of the hydrothermal fluids (δ³⁴S_V–CDT = 2.2 to 3.7 ‰) indicate that S mainly comes from granitic magma. Further, the Pb isotope (²⁰⁶Pb/²⁰⁴Pb = 18.276–18.367, ²⁰⁷Pb/²⁰⁴Pb = 15.52–15.556, ²⁰⁸Pb/²⁰⁴Pb = 38.157–38.193) in stages I–III indicate that the ore-forming materials are derived from the mixture of mantle and orogenic material. In summary, this study showed the A'gui is a typical magmatic hydrothermal vein-type Cu deposit that related to Cretaceous monzogranite formed under the joint constraints of Mongolia-Okhotsk Ocean and Paleo-Pacific Ocean tectonic system. Fluid boiling and mixing are the main ore-forming mechanism.     

A Fluid Inclusion Study of Vein-type Copper Mineralization in the East Wulasigou Pb–Zn–Cu Deposit, Altay, Northwestern China

The Wulasigou Cu-Pb-Zn deposit,located 15 km northwest of Altay city in Xinjiang,is one of many Cu-Pb-Zn polymetallic deposits in the Devonian Kelan volcanic-sedimentary basin in southern Altaids.Two mineralizing periods can be distinguished:the marine volcanic sedimentary PbZn mineralization period,and the metamorphic hydrothermal Cu mineralization period,which is further divided into an early bedded foliated quartz vein stage(Q1) and a late sulfide-quartz vein stage(Q2) crosscutting the foliation.Four types of fluid inclusions were recognized in the Q1 and Q2 quartz from the east orebodies of the Wulasigou deposit:H_2O-CO_2 inclusions,carbonic fluid inclusions,aqueous fluid inclusions,and daughter mineral-bearing fluid inclusions.Microthermometric studies show that solid CO_2 melting temperatures(T_(m,CO2)) of H_2O-CO_2 inclusions in Ql are from-62.3℃ to-58.5C,clathrate melting temperatures(T_(m,clath)l) are from 0.5 C to 7.5 C,partial homogenization temperatures(T_(h,CO2)) vary from 3.3℃ to 25.9℃(to liquid),and the total homogenization temperatures(T_(h,tot)) vary from 285℃ to 378℃,with the salinities being 4.9%-15.1%NaCl eqv.and the CO_2-phase densities being 0.50-0.86 g/cm~3.H_2O-CO_2 inclusions in Q2 have T_(m,CO_2) from-61.9℃ to-56.9℃,T_(m,clath)from 1.3℃ to 9.5℃,T_(h,CO2) from 3.4℃ to 28.7℃(to liquid),and T_(h,tot) from 242℃ to 388℃,with the salinities being 1.0%-15.5%NaCl eqv.and the CO_2-phase densities being 0.48-0.89 g/cm~3.The minimum trapping pressures of fluid inclusions in Q1 and Q2 are estimated to be 260-360 MPa and180-370 MPa,respectively.The δ~(34)S values of pyrite from the volcanic sedimentary period vary from2.3‰ to 2.8‰(CDT),and those from the sulfide-quartz veins fall in a narrow range of-1.9‰ to 2.6‰(CDT).The δD values of fluid inclusions in Q2 range from-121.0‰ to-100.8‰(SMOW),and theδ~(18)O_(H2O) values calculated from δ~(18)O of quartz range from-0.2‰ to 8.3‰(SMOW).The δD-δ~(18)O_(H2O)data are close to the magmatic and metamorphic fields.The fluid inclusion and stable isotope data documented in this study indicate that the vein-type copper mineralization in the Wulasigou Pb-Zn-Cu deposit took place in an orogenic-metamorphic enviroment.     

Characteristics and distribution of clay minerals and their effects on reservoir quality: Huagang Formation in the Xihu Sag,East China Sea Basin

Abstract

The characteristics and distribution of clay minerals and their effects on reservoir quality in the Huagang sandstones in the Xihu Sag, East China Sea Basin were studied by using X-ray diffraction, casting thin-sections, scanning electron microscopy, electron microprobe analysis, fluid inclusion analysis, constant-rate mercury injection and nuclear magnetic resonance. Clay minerals consist of kaolinite, chlorite, illite and illite–smectite mixed layer (I/S); kaolinite forms from dissolved feldspars, chlorite occurs as clay coatings that are transformed from clay precursors owing to the flocculation of suspended detrital clays or the crystallisation of pore fluids, and illite forms from the illitisation of detrital smectite, authigenic kaolinite and K-feldspars. Clay distribution is controlled by sedimentary environments, burial history and lithologies. Typical reservoirs in the western sub-sag are thin and developed in braided river facies at relatively shallow burial depths with clays dominated by kaolinite. However, typical reservoirs in the central inversion tectonic zone are thicker and developed in a braided delta front facies at deeper burial depths with clays mainly consisting of chlorite, illite and I/S. High-quality reservoirs are characterised by coarse granularity, high quartz content and low clay content with widespread development of chlorite coatings that inhibit quartz cements at low temperatures. At higher temperatures, the high-quality reservoirs develop more pores providing growth space for quartz cements and result in the coexistence of chlorite coatings and quartz cements. The high-quality reservoirs are controlled by their lithological characteristics rather than chlorite coatings. Illite and I/S clays create severe damage to reservoirs by reducing the size and connectivity of pore-throats.     

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.     

Intermediate sulfidation epithermal gold-base metal deposits in Tertiary subaerial volcanic rocks,Sahinli/Tespih Dere (Lapseki/Western Turkey)

Gold in the Sahinli and Tespih Dere intermediate sulfidation gold-base metal deposits in Western Turkey occurs in relatively deep epithermal quartz veins along with base metal minerals which have epithermal textures, including plumose quartz, vug infills, comb and cockade textures and matrix-supported milled breccias. The total sulfide content of the veins in the area is variable ranging from < 1% to 60% and is dominated by pyrite, galena, sphalerite and chalcopyrite. Sphalerite is Fe-poor (0.6 to 1.4 mol% FeS). Minor amounts of Ag-rich tetrahedrite are present. Primary hydrothermal alteration minerals include illite/muscovite, mixed-layer illite/smectite (11.6 Å) and clinochlore towards the east and, alunite, dickite/nacrite and pyrophyllite towards the west at Sahinli; major illite/muscovite and dickite occur at Tespih Dere and Sarioluk, respectively.Fluid inclusions in main-stage quartz at Sahinli are only liquid-rich, with homogenization temperatures ranging from 220 to 322 °C and the majority of T_h values between 250 and 300 °C. Salinity ranges from 4.3 to 6.9 wt.% NaCl equiv. First ice-melting temperatures (T_mf) between ?24.5 and ?19.0 °C indicate that the fluids were dominated by NaCl – H₂O during mineralization. The relatively higher average T_h at the Tespih Dere deposit (295 °C) is attributed to a relatively deeper level of exposure.Calculated δ¹⁸O values indicate that ore-forming hydrothermal fluids in the study area had δ¹⁸O_H2O ranging from + 1.1 to + 9.7‰ (average = 3.8‰), strongly ¹⁸O-enriched compared with present-day hydrothermal meteoric water in the area (δ¹⁸O = ?8.5‰). δD values of fluid inclusions in quartz range from ?58 to ?93‰ and δD values of clay minerals and alunite from ?40 to ?119‰. δD values from intermediate argillic alteration (average = ?68‰) in the study area are very similar to δD values of the present-day local geothermal system (average δD = ?54‰) whereas δD values from advanced-argillic alteration (average δD = ?33‰) are very different from the present-day local geothermal system.The δ³⁴S values in samples from the Sahinli and Tespih Dere deposits average ?2.9‰ for pyrite; ?3.3‰ for chalcopyrite; ?5.4‰ for sphalerite and ?7.6‰ for galena. These data are consistent with derivation of the sulfur from either igneous rocks or possibly from local wallrock.     

Alteration mineralogy,lithochemistry and stable isotope geochemistry of the Murgul (Artvin,NE Turkey) volcanic hosted massive sulfide deposit: Implications for the alteration age and ore forming fluids

The Murgul (Artvin, NE Turkey) massive sulfide deposit is hosted dominantly by Late Cretaceous calc-alkaline to transitional felsic volcanics. The footwall rocks are represented by dacitic flows and pyroclastics, whereas the hanging wall rocks consist of epiclastic rocks, chemical exhalative rocks, gypsum-bearing vitric tuff, purple vitric tuff and dacitic flows. Multi-element variation diagrams of the hanging wall and footwall rocks exhibit similar patterns with considerable enrichment in K, Rb and Ba and depletion in Nb, Sr, Ti and P. The chondrite-normalized rare earth element (REEs) patterns of all the rocks are characterized by pronounced positive/negative Eu anomalies as a result of different degrees of hydrothermal alteration and the semi-protected effects of plagioclase fractionation.Mineralogical results suggest illite, illite/smectite + chlorite ± kaolinite and chlorite in the footwall rocks and illite ± smectite ± kaolinite and chlorite ± illite in the hanging wall rocks. Overall, the alteration pattern is represented by silica, sericite, chlorite and chlorite–carbonate–epidote–sericite and quartz/albite zones. Increments of Ishikawa alteration indexes, resulting from gains in K₂O and losses in Na₂O and the chlorite–carbonate–pyrite index towards to the center of the stringer zone, indicate the inner parts of the alteration zones. Calculations of the changes in the chemical mass imply a general volume increase in the footwall rocks. Abnormal volume increases are explained by silica and iron enrichments and a total depletion of alkalis in silica zone. Relative K increments are linked to the sericitization of plagioclase and glass shards and the formation of illite/smectite in the sericite zone. In addition, Fe enrichment is always met by pyrite formation accompanied by quartz and chlorite. Illite is favored over chlorite, smectite and kaolinite in the central part of the ore body due to the increase in the (Al + K)/(Na + Ca) ratio. Although the REEs were enriched in the silicification zone, light REEs show depletion in the silicification zone and enrichment in the other zones in contrast to the heavy REEs' behavior. Hydrothermal alteration within the hanging wall rocks, apart from the gypsum-bearing vitric tuffs, is primarily controlled by chloritization with proportional Fe and Mg enrichments and sericitization.The δ¹⁸O and δD values of clay minerals systematically change with increasing formation temperature from 6.6 to 8.7‰ and − 42 to − 50‰ for illites, and 8.6 and − 52‰ for chlorite, respectively. The O- and H-stable isotopic data imply that hydrothermal-alteration processes occurred at 253–332 °C for illites and 136 °C for chlorite with a temperature decrease outward from the center of the deposit. The positive δ³⁴S values (20.3 to 20.4‰) for gypsum suggest contributions from seawater sulfate reduced by Fe-oxide/-hydroxide phases within altered volcanic units. Thus, the hydrothermal alteration possibly formed via a dissolution–precipitation mechanism that operated under acidic conditions. The K–Ar dating (73–62 Ma) of the illites indicates an illitization process from the Maastrichtian to Early Danian period.     

Columnar calcites as testimony of diagenetic overprinting at the boundary between Upper Tournaisian dolomites and limestones (Belgium): multiple origins for apparently similar features

In topographic flat areas, sedimentary settings may vary from one outcrop to another. In these settings, calcite precipitates may yield macroscopically similar columnar features, although they are products of different sedimentary or diagenetic processes. Three columnar calcite crystal fabrics, i.e. rosettes, palisade crusts and macro-columnar crystal fans, have been differentiated near and at the contact between Upper Tournaisian dolomites and limestones along the southern margin of the Brabant-Wales Palaeohigh. Their petrographic characteristics, and geochemical and fluid inclusion data provide information on the (dia)genetic processes involved. Rosettes composed of non-luminescent columnar calcite crystal fans (1–5 cm in diameter) developed on top of one another, forming discrete horizons in repetitive sedimentary cycles. The cycles consist of three horizons: (I) a basal horizon with fragments from the underlying horizon, (II) a micrite/microspar horizon with incipient glaebules, (III) an upper horizon consisting of calcite rosettes, with desiccation features. The petrographical features and δ¹⁸O signatures of −10·0 to −5·5‰ and δ¹³C values of −5·5 to −3·2‰ support either evaporative growth, an evaporative pedogenic origin, or overprinting of marine precipitates. Palisade crusts, composed of a few to 10 mm long non-luminescent calcite crystals, coat palaeokarst cavities. Successive palisade growth-stages occur which are separated by thin laminae of micrite or detrital quartz, displaying a geopetal arrangement. Palisade crusts are interpreted as intra-Mississippian speleothems. This interpretation is supported by their petrographic characteristics and isotopic signature (δ¹⁸O = −8·7 to −6·5‰ and δ¹³C = −4·8 to −2·5‰). Macro-columnar crystals, 1–50 cm long, developed mainly perpendicular to cavity walls and dolomite clasts. Crystal growth stages in the macro-columnar crystals are missing. δ¹⁸O values vary between −16·4 and −6·8‰ and δ¹³C values between −5·2 and −0·9‰. These features possibly support a late diagenetic high temperature precipitation in relation to hydrothermal karstification.     

Geochemical Characteristics and Sources of Ore-forming Fluids of the Mayuan Pb-Zn Deposit, Nanzheng, Shaanxi, China

The Mayuan stratabound Pb-Zn deposit in Nanzheng,Shaanxi Province,is located in the northern margin of the Yangtze Plate,in the southern margin of the Beiba Arch.The orebodies are stratiform and hosted in breciated dolostone of the Sinian Dengying Formation.The ore minerals are primarily sphalerite and galena,and the gangue minerals comprise of dolomite,quartz,barite,calcite and solid bitumen.Fluid inclusions from ore-stage quartz and calcite have homogenization tempreatures from 98 to 337℃ and salinities from 7.7 wt%to 22.2 wt%(NaCl equiv.).The vapor phase of the inclusions is mainly composed of CH_4 with minor CO_2 and H_2S.The δD_(fluid) values of fluid inclusions in quartz and calcite display a range from-68‰ to-113‰(SMOW),and the δ~(18)O_(fluid)values calculated from δ~(18)O_(quartz) and δ~(18)O_(calcite) values range from 4.5‰ to 16.7‰(SMOW).These data suggest that the ore-forming fluids may have been derived from evaporitic sea water that had reacted with organic matter.The δ~(13)C_(CH4) values of CH_4 in fluid inclusions range from-37.2‰ to-21.0‰(PDB),suggesting that the CH_4 in the ore-forming fluids was mainly derived from organic matter.This,together with the abundance of solid bitumen in the ores,suggest that organic matter played an important role in mineralization,and that the thermochemical sulfate reduction(TSR) was the main mechanism of sulfide precipitation.The Mayuan Pb-Zn deposit is a carbonate-hosted epigenetic deposit that may be classified as a Mississippi Valley type(MVT) deposit.     

Origin of blocky aragonite cement in Cenozoic glaciomarine sediments,McMurdo Sound,Antarctica

Inorganic aragonite occurs in a wide spectrum of depositional environments and its precipitation is controlled by complex physio-chemical factors. This study investigates diagenetic conditions that led to aragonite cement precipitation in Cenozoic glaciomarine deposits of McMurdo Sound, Antarctica. A total of 42 sandstones that host intergranular cement were collected from the CIROS-1 core, located proximal to the terminus of Ferrar Glacier. Standard petrography, Raman spectroscopy and electron microprobe analysis reveal a prominent aragonite cement phase that occurs as a pore-filling blocky fabric throughout the core. Oxygen isotope compositions (δ¹⁸O = −30·0 to −8·6‰ Vienna Pee-Dee Belemnite) and clumped isotope temperatures (TΔ₄₇ = 13·1 to 31·5°C) determined from the aragonite cements provide precise constraints on isotopic compositions (δ¹⁸O_w) of the parent fluid, which mostly range from −10·8 to −7·2‰ Vienna Standard Mean Ocean Water. The fluid δ¹⁸O_w values are consistent with those of pore water, previously identified as cryogenic brine in the nearby AND-2A core. Petrographic and geochemical data suggest that aragonite cement in the CIROS-1 core precipitated from a similar brine. The brine likely formed and infiltrated sediments in flooded glacial valleys along the western margin of McMurdo Sound during the middle Miocene Climatic Transition, and subsequently flowed basinward in the subsurface. Consequently, the brine forms as a longstanding subsurface fluid that has saturated Cenozoic sediments below southern McMurdo Sound since at least the middle Miocene. Aragonite cementation in the CIROS-1 core is interpreted to reflect its proximal position to sites of brine formation and greater likelihood of experiencing brines with sustained high carbonate saturation states and Mg/Ca ratios. This unusual occurrence expands the range of known natural occurrences of aragonite cement. Given the potential for cryogenic brine formation in glaciomarine settings, blocky aragonite, as the end member of the spectrum of aragonite cement morphology, may be more widespread in glaciomarine sediments than currently thought.     

Fluid Inclusion,H-O,S, Pb and noble gas isotope studies of the Aerhada Pb-Zn-Ag deposit,Inner Mongolia,NE China

The Aerhada Pb-Zn-Ag deposit is located in the western segment of the Great Hinggan Range Ag-Pb-Zn-Cu-Mo-Au-Fe metallogenic belt in NE China. Orebodies occur mainly as vein type and are hosted by sandstone and siliceous slate. Three stages of primary mineralization, including an early arsenopyrite-pyrite-quartz, a middle polymetallic and silver sulfides-quartz and a late sphalerite-pyrite-calcite-fluorite are recognized. Four types of fluid inclusions have been identified in the ore-bearing quartz and fluorite veins, i.e., liquid-rich, gas-rich, three-phase CO₂ aqueous inclusions, and pure gas or liquid aqueous inclusions. Microthermometric studies on fluid inclusions reveal that homogenization temperatures from early to late stages range from 253° to 430 °C, 195° to 394 °C and 133° to 207 °C, respectively. Fluid salinities range from 2.9 to 14.0 wt.% NaCl equiv. The vapor composition of the ore fluid is dominated by H₂O, CO₂ and CH₄, with minor proportions of N₂. The fluid δ¹⁸O_H2O and δD_H2O values vary from +1.6 to +9.3‰ and −122 to −56‰, respectively, and reflect a magmatic fluid and a meteoric fluid dominant hydrothermal system for the early and late stages of mineralization, respectively. The calculated δ³⁴S_H2S values of hydrothermal fluids in equilibrium with sulfides range from +5.2 to +7.1‰, suggesting a mixed source for sulfur, i.e., the local magmatic and sedimentary rocks. The Pb isotope compositions of sulfides are similar to those of the local magmatic and sedimentary rocks, implying that lead and possibly silver relate to these sources. The noble gas isotope compositions of fluid inclusions hosted in ore minerals suggest that the ore-forming fluids were dominantly derived from a deep mantle source. Fluid mixing and dilution are inferred as the dominant mechanisms for ore deposition. The Aerhada Pb-Zn-Ag deposit can be classified as a medium to low temperature hydrothermal vein type deposit.     

Saddle-Dolomite-Bearing Fracture Fillings and Records of Hot Brine Activity in the Jialingjiang Formation, Libixia Section, Hechuan Area of Chongqing City

Most vein minerals deposited in fractures of the Jialingjiang Formation from Libixia section,Hechan area include a large amount of saddle dolomite and accompanying celestite,calcite and fluorite.This study analyzed the nature,source,evolution of the fluids by plane-light petrography,fluid-inclusion methods,cathodoluminescence images,and stable isotopic compositions.The homogenization temperatures of two-phase aqueous fluid inclusions in dolomite range between100 and 270℃.Combined with theδ~(18)O data,it is suggested that the fluid responsible for the precipitation of fracture fillings haveδ~(18)O values between 10‰and 18‰(relative to SMOW).The saddle dolomite and the accompanying minerals were the result of activity of dense brines at elevated temperatures.Moreover,analysis shows that the fluid was derived from a mixture of marine-derived brine and deeper circulating flow.This fluid was enriched in Sr during diagenesis and formed celestite in fracture and for regional mineralization.Dissolution of saddle dolomite was attributed to the cooling of Mg/Ca-decreased fluids,which may relate to a leaching of gypsum to celestite in surrounding carbonates.     

Metallogenesis and ore-forming time of the Changtuxili Mn–Ag–Pb–Zn deposit in Inner Mongolia: Evidence from C–O–S isotopes and U–Pb geochronology

This paper reports new geochronological (U–Pb) and isotope (C, O, and S) data to investigate the timing of mineralization and mode of ore genesis for the recently discovered Changtuxili Mn–Ag–Pb–Zn deposit, located on the western slopes of the southern Great Hinggan Range in NE China. The mineralization is hosted by intermediate–acidic lavas and pyroclastic rocks of the Baiyingaolao Formation. Three stages of mineralization are identified: quartz–pyrite (Stage I), galena–sphalerite–tetrahedrite–rhodochrosite (Stage II), and quartz–pyrite (Stage III). δ¹³C and δ¹⁸O values for carbonate from the ore vary from −8.51‰ to −4.96‰ and 3.97‰ to 15.90‰, respectively, which are indicative of a low-temperature alteration environment. δ³⁴S_V-CDT values of sulfides range from −1.77‰ to 4.16‰ and show a trend of equilibrium fractionation (δ³⁴S_Py ​> ​δ³⁴S_Sp ​> ​δ³⁴S_Gn). These features indicate that pyrite, sphalerite, and galena precipitated during the period of mineralization. The alteration mineral assemblage and isotope data indicate that the weakly acidic to weakly alkaline ore-forming fluid was derived largely from meteoric water and the ore-forming elements C and S originated from magma. During the mineralization, a geochemical barrier was formed by changes in the pH of the ore-forming fluid, leading to the precipitation of rhodochrosite. On the basis of the mineralization characteristics, new isotope data, and comparison with adjacent deposits, we propose that the Changtuxili Mn–Ag–Pb–Zn deposit is an intermediate-to low-sulfidation epithermal deposit whose formation was controlled by fractures and variability in the pH of the ore-forming fluid. The surrounding volcanic rocks yield zircon U–Pb ages of 160−146 ​Ma (Late Jurassic), indicating that the mineralization is younger than 146 ​Ma.