Origin of coarse-crystalline calcite cement in Early Ordovician carbonate rocks, Ordos basin, northern China: Insights from oxygen and carbon isotopes and fluid inclusion microthermometry

The calcite cement in the Lower Ordovician Majiagou Formation in the Ordos basin in northern China can be subdivided into three groups based on preliminary results of oxygen and carbon isotopes and fluid inclusion microthermometry. Group 1 has low oxygen isotopes (− 14‰ to − 18‰), low T_h values (92–103 °C), and low salinities (1.7–4.9 wt.% NaCl equivalent) and is interpreted to have precipitated during early burial from porewater influenced by meteoric water. Group 2 has much higher oxygen isotope values (− 5‰ to − 8‰), which, coupled with the higher T_h values (136–151 °C), suggest that the calcite was precipitated from fluids that were significantly enriched in ¹⁸O, possibly resulting from fluid–rock reaction during burial. Group 3 occurring along fractures is characterized by high salinities (21–28 wt.% NaCl equivalent) and is interpreted to have been precipitated from locally preserved residual evaporitic brines. The occurrence of primary hydrocarbon inclusions and its low carbon isotopes (− 11‰ to − 15‰) suggest that precipitation of group 3 calcite took place in the presence of hydrocarbons.     

Fluid–rock interaction at the roots of an Eopaleozoic epithermal system, Sierra Norte de Córdoba, Argentina: Paragenesis, thermometry and fluid sources

A deep epithermal vein system hosted in Late Proterozoic to Cambrian granodiorite has been identified in the Sierra Norte de Córdoba, the easternmost range of the Sierras Pampeanas Orientales of Argentina. The vein swarm extends over an area of 3 km² parallel to a mylonitic belt and formed in fractured granodiorite. Thicknesses of veins are less than 0.5 m and their visible strike length is less than 100 m. Veins are either barren or weakly mineralized in base-metal sulfides. Most veins have mineral associations dominated by calcite and quartz with lesser amounts of chlorite, sericite, pyrite, and minor illite. In other less exposed albite-rich, adularia-bearing veins, chalcopyrite, bornite, galena, sphalerite, chalcocite and covellite may occur. The widespread occurrence of bladed calcite without any petrographic or microthermometric evidence of boiling implies that this particular habit of calcite may also develop under sub-near boiling fluid conditions. Thermometric calculations based on fluid inclusion data, chlorite composition and oxygen isotopes in the quartz–calcite pair, constrain the formation of the system between 300 and 350 °C, at pressures between 42 and 64 MPa (1.5–2.3 km). Stable isotope data suggest that W/R interaction might have been the most probable mechanism of alteration, involving the participation of meteoric fluids; nevertheless, the metallic signature of some weakly mineralized veins as well as intermediate fluid inclusion salinities favor a magmatic input and a mixed origin for the fluids. Textures and mineral associations, as well as the absence of evidence of boiling in fluid inclusions, all suggest that the silica–carbonate vein system formed deeper than typically shallow Au and Ag-bearing boiling solutions. A 485 (±25) Ma lamprophyre dike crosscuts some of these veins locally producing metasomatic reactions and skarn formation, which constrains the age of the hydrothermal system to the Cambrian-Early Ordovician time span.     

Paleohydrogeological events recorded by stable isotopes,fluid inclusions and trace elements in fracture minerals in crystalline rock,Simpevarp area,SE Sweden

Fracture minerals calcite, pyrite, gypsum, barite and quartz, formed during several events have been analysed for δ¹³C, δ¹⁸O, δ³⁴S, ⁸⁷Sr/⁸⁶Sr, trace element chemistry and fluid inclusions in order to gain knowledge of the paleohydrogeological evolution of the Simpevarp area, south-eastern Sweden. This area is dominated by Proterozoic crystalline rocks and is currently being investigated by the Swedish Nuclear Fuel and Waste Management Co. (SKB) in order to find a suitable location for a deep-seated repository for spent nuclear fuel. Knowledge of the paleohydrogeological evolution is essential to understand the stability or evolution of the groundwater system over a time scale relevant to the performance assessment for a spent nuclear fuel repository. The ages of the minerals analysed range from the Proterozoic to possibly the Quaternary. The Proterozoic calcite and pyrite show inorganic and hydrothermal-magmatic stable isotope signatures and were probably formed during a long time period as indicated by the large span in temperatures (c. 200–360 °C) and salinities (0–24 wt.% eq. CaCl₂), obtained from fluid inclusion analyses. The Paleozoic minerals were formed from organically influenced brine-type fluids at temperatures of 80–145 °C. The isotopic results indicate that low temperature calcite and pyrite may have formed during different events ranging in time possibly from the end of the Paleozoic until the Quaternary. Formation conditions ranging from fresh to brackish and saline waters have been distinguished based on calcite crystal morphologies. The combination of δ¹⁸O and crystal morphologies show that the fresh–saline water interface has changed considerably over time, and water similar to the present meteoric water and brackish seawater at the site, have most probably earlier been residing in the bedrock. Organic influence and closed system in situ microbial activity causing disequilibrium are indicated by extremely low δ¹³C (down to −99.7‰), extreme variation in δ³⁴S (−42.5‰ to +60.8‰) and trace element compositions. The frequency of calcite low in δ¹³C and high in Mn, as well as pyrite with biogenically modified δ³⁴S decreases with depth. Strontium isotopes have been useful to separate the different generations and the Sr isotope ratios in the groundwaters have been determined mainly by in situ water–rock interaction processes. The difficulty of separating late Paleozoic calcite from possibly recent calcite, and the fact that these calcites are usually found in the same fracture systems indicate that water conducting structures have been intermittently conductive from the Paleozoic and onwards. The methodology used has been successful in separating the different generations and characterising their formation conditions.     

A stable isotope and fluid inclusion study of the Qaleh-ZariCu–Au–Ag deposit, Khorasan Province, Iran

The Qaleh-Zari copper deposit, located in South Khorasan in the Central Lut region of Iran, is a polymetallic vein deposit with major amounts of Cu, Au, Ag and minor amounts of Pb, Zn and Bi. Mineralization occurs in a series of NW–SE trending fault planes and breccia zones in Paleogene andesitic to basaltic volcanic rocks. Argillization, sericitization and propylitization characterize alteration halos bordering mineral veins. The main ore minerals are chalcopyrite, pyrite, galena and sphalerite, with quartz, calcite and minor chlorite as the main gangue phases. Microthermometric measurements of fluid inclusions in cogenetic quartz indicate homogenization temperatures between 160 and 300 °C and salinities from 1 to 4 wt% NaCl equiv. Boiling occurred in the mineralising fluids at 160–1000 m below the paleo-water table at pressures of approximately 15−80 bar at various stages in the formation of the ore body. The wide range of pressures and temperatures reflects the multi-stage nature of the mineralization at Qaleh-Zari. The δ¹⁸O values in quartz (relative to SMOW) and δ³⁴S values in chalcopyrite and galena (relative to CDT) range from 6.5 to 7.5‰ and 0.0–1.5‰ (mean: 7.0‰), respectively. At 300 °C, calculated fluid δ¹⁸O values are close to 0‰. These data suggest a magmatic origin for sulfur and a surficial origin for the mineralizing fluid. Mineralization at Qaleh-Zari is interpreted as epithermal and low-sulfidation in style and was probably related to a deep-seated magmatic system. Ore deposition was the result of boiling, cooling and pressure reduction.     

Geology, mineralogy and stable isotope geochemistry of the Kabwe carbonate-hosted Pb–Zn deposit, Central Zambia

The carbonate-hosted Kabwe Pb–Zn deposit, Central Zambia, has produced at least 2.6 Mt of Zn and Pb metal as well as minor amounts of V, Cd, Ag and Cu. The deposit consists of four main epigenetic, pipe-like orebodies, structurally controlled along NE–SW faults. Sphalerite, galena, pyrite, minor chalcopyrite, and accessory Ge-sulphides of briartite and renierite constitute the primary ore mineral assemblage. Cores of massive sulphide orebodies are surrounded by oxide zones of silicate ore (willemite) and mineralized jasperoid that consists largely of quartz, willemite, cerussite, smithsonite, goethite and hematite, as well as numerous other secondary minerals, including vanadates, phosphates and carbonates of Zn, Pb, V and Cu.Galena, sphalerite and pyrite from the Pb–Zn rich massive orebodies have homogeneous, negative sulphur isotope ratios with mean δ³⁴S_CDT permil (‰) values of − 17.75 ± 0.28 (1σ), − 16.54 ± 0.0.27 and − 15.82 ± 0.25, respectively. The Zn-rich and Pb-poor No. 2 orebody shows slightly heavier ratios of − 11.70 ± 0.5‰ δ³⁴S for sphalerite and of − 11.91 ± 0.71‰ δ³⁴S for pyrite. The negative sulphur isotope ratios are considered to be typical of sedimentary sulphides produced through bacterial reduction of seawater sulphate and suggest a sedimentary source for the sulphur.Carbon and oxygen isotope ratios of the host dolomite have mean δ¹³C_PDB and δ¹⁸O_SMOW values of 2.89‰ and 27.68‰, respectively, which are typical of marine carbonates. The oxygen isotope ratios of dolomite correlate negatively to the SiO₂ content introduced during silicification of the host dolomite. The depletion in ¹⁸O in dolomite indicates high temperature fluid/rock interaction, involving a silica- and ¹⁸O-rich hydrothermal solution.Two types of secondary fluid inclusions in dolomite, both of which are thought to be related to ore deposition, indicate temperatures of ore deposition in the range of 257 to 385 and 98 to 178 °C, respectively. The high temperature fluid inclusions contain liquid + vapour + solid phases and have salinities of 15 to 31 eq. wt.% NaCl, whereas the low temperature inclusions consist of liquid + vapour with a salinity of 11.5 eq. wt.% NaCl.Fluid transport may have been caused by tectonic movements associated with the early stages of the Pan-African Lufilian orogeny, whereas ore deposition within favourable structures occurred due to changes in pressure, temperature and pH in the ore solution during metasomatic replacement of the host dolomite. The termination of the Kabwe orebodies at the Mine Club fault zone and observed deformation textures of the ore sulphides as well as analysis of joint structures in the host dolomite, indicate that ore emplacement occurred prior to the latest deformation phase of the Neoproterozoic Lufilian orogeny.     

Oxygen isotopic fractionation during inorganic calcite precipitation ― Effects of temperature, precipitation rate and pH

Stable oxygen isotopic fractionation during inorganic calcite precipitation was experimentally studied by spontaneous precipitation at various pH (8.3 < pH < 10.5), precipitation rates (1.8 < log R < 4.4 μmol m^− 2 h^− 1) and temperatures (5, 25, and 40 °C) using the CO₂ diffusion technique.The results show that the apparent stable oxygen isotopic fractionation factor between calcite and water (α_{calcite–water}) is affected by temperature, the pH of the solution, and the precipitation rate of calcite. Isotopic equilibrium is not maintained during spontaneous precipitation from the solution. Under isotopic non-equilibrium conditions, at a constant temperature and precipitation rate, apparent 1000lnα_{calcite–water} decreases with increasing pH of the solution. If the temperature and pH are held constant, apparent 1000lnα_{calcite–water} values decrease with elevated precipitation rates of calcite. At pH = 8.3, oxygen isotopic fractionation between inorganically precipitated calcite and water as a function of the precipitation rate (R) can be described by the expressions

at 5, 25, and 40 °C, respectively.The impact of precipitation rate on 1000lnα_{calcite–water} value in our experiments clearly indicates a kinetic effect on oxygen isotopic fractionation during calcite precipitation from aqueous solution, even if calcite precipitated slowly from aqueous solution at the given temperature range. Our results support Coplen's work [Coplen T. B. (2007) Calibration of the calcite–water oxygen isotope geothermometer at Devils Hole, Nevada, a natural laboratory. Geochim. Cosmochim. Acta 71, 3948–3957], which indicates that the equilibrium oxygen isotopic fractionation factor might be greater than the commonly accepted value.     

Fluid inclusion and stable isotope study of the Cobre–Babilonia polymetallic epithermal vein system, Taxco district, Guerrero, Mexico

The Cobre–Babilonia vein system formed during a single major hydrothermal stage and is part of the Taxco district in Guerrero, southern Mexico. Homogenization and ice melting temperatures range from 160 to 290 °C and from − 11.6 to − 0.5 °C, respectively. We determined an approximate thermal gradient of 17 to 20 °C per 100 m using fluid inclusions. A thermal peak marked by the 290 °C isotherm is interpreted as a major feeder channel to the veins. The highest content of Zn + Pb in ore coincides with the 220 and 240 °C isotherms. Salinities of mineralizing fluids range from 0.8 to 15.6 wt.% NaCl equiv, and are distributed in two populations that can be related with barren or ore-bearing vein sections, with 0.8 to 6 wt.% NaCl equiv and 7 to 15.6 wt.% NaCl equiv, respectively. δ¹³C and δ¹⁸O water values from calcite from the Cobre–Babilonia vein system and the Esperanza Vieja and Guadalupe mantos range − 5.4‰ to − 10.4‰ and 9.9‰ to 13.4‰, respectively. δ³⁴S values range from 0‰ to 3.2‰ and − 0.7‰ to − 4.3‰ in sphalerite, − 4‰ to 0.9‰ in pyrite, and − 1.4‰ to − 5.5‰ in galena. Both fluid inclusion and stable isotope data are compatible with magmatic and meteoric sources for mineralizing fluids. Also, sulfur isotope compositions suggest both magmatic and sedimentary sources for sulfur.     

Iron isotopes in acid mine waters and iron-rich solids from the Tinto–Odiel Basin (Iberian Pyrite Belt, Southwest Spain)

The isotopic composition of Fe was determined in water, Fe-oxides and sulfides from the Tinto and Odiel Basins (South West Spain). As a consequence of sulfide oxidation in mine tailings both rivers are acidic (1.45 < pH < 3.85) and display high concentrations of dissolved Fe (up to 420 mmol l^− 1) and sulphates (up to 1190 mmol l^− 1).The δ⁵⁶Fe of pyrite-rich samples from the Rio Tinto and from the Tharsis mine ranged from − 0.56 ± 0.08‰ to + 0.25 ± 0.1‰. δ⁵⁶Fe values for Fe-oxides precipitates that currently form in the riverbed varied from − 1.98 ± 0.10‰ to 1.57 ± 0.08‰. Comparatively narrower ranges of values (− 0.18 ± 0.08‰ and + 0.21 ± 0.14‰) were observed in their fossil analogues from the Pliocene–Pleistocene and in samples from the Gossan (the oxidized layer that formed through exposure to oxygen of the massive sulfide deposits) (− 0.36 ± 0.12‰ to 0.82 ± 0.07‰). In water, δ⁵⁶Fe values ranged from − 1.76 ± 0.10‰ to + 0.43 ± 0.05‰.At the source of the Tinto River, fractionation between aqueous Fe(III) and pyrite from the tailings was less than would be expected from a simple pyrite oxidation process. Similarly, the isotopic composition of Gossan oxides and that of pyrite was different from what would be expected from pyrite oxidation. In rivers, the precipitation of Fe-oxides (mainly jarosite and schwertmannite and lesser amounts of goethite) from water containing mainly (more than 99%) Fe(III) with concentrations up to 372 mmol l^− 1 causes variable fractionation between the solid and the aqueous phase (− 0.98‰ < Δ⁵⁶Fe_{solid–water} < 2.25‰). The significant magnitude of the positive fractionation factor observed in several Fe(III) dominated water may be related to the precipitation of Fe(III) sulphates containing phases.     

Geochemical constraints on the modes of carbonate precipitation in peridotites from the Logatchev Hydrothermal Vent Field and Gakkel Ridge

The ultramafic-hosted Logatchev Hydrothermal Field (LHF) at 15°N on the Mid-Atlantic Ridge and the Arctic Gakkel Ridge (GR) feature carbonate precipitates (aragonite, calcite, and dolomite) in voids and fractures within different types of host rocks. We present chemical and Sr isotopic compositions of these different carbonates to examine the conditions that led to their formation. Our data reveal that different processes have led to the precipitation of carbonates in the various settings. Seawater-like ⁸⁷Sr/⁸⁶Sr ratios for aragonite in serpentinites (0.70909 to 0.70917) from the LHF are similar to those of aragonite from the GR (0.70912 to 0.70917) and indicate aragonite precipitation from seawater at ambient conditions at both sites. Aragonite veins in sulfide breccias from LHF also have seawater-like Sr isotope compositions (0.70909 to 0.70915), however, their rare earth element (REE) patterns show a clear positive europium (Eu) anomaly indicative of a small (< 1%) hydrothermal contribution. In contrast to aragonite, dolomite from the LHF has precipitated at much higher temperatures (~ 100 °C), and yet its ⁸⁷Sr/⁸⁶Sr ratios (0.70896 to 0.70907) are only slightly lower than those of aragonite. Even higher temperatures are calculated for the precipitation of deformed calcite veins in serpentine–talc fault schists form north of the LHF. These calcites show unradiogenic ⁸⁷Sr/⁸⁶Sr ratios (0.70460 to 0.70499) indicative of precipitation from evolved hydrothermal fluids. A simple mixing model based on Sr mass balance and enthalpy conservation indicates strongly variable conditions of fluid mixing and heat transfers involved in carbonate formation. Dolomite precipitated from a mixture of 97% seawater and 3% hydrothermal fluid that should have had a temperature of approximately 14 °C assuming that no heat was transferred. The much higher apparent precipitation temperatures based on oxygen isotopes (~ 100 °C) may be indicative of conductive heating, probably of seawater prior to mixing. The hydrothermal calcite in the fault schist has precipitated from a mixture of 67% hydrothermal fluid and 33% seawater, which should have had an isenthalpic mixing temperature of ~ 250 °C. The significantly lower temperatures calculated from oxygen isotopes are likely due to conductive cooling of hydrothermal fluid discharging along faults. Rare earth element patterns corroborate the results of the mixing model, since the hydrothermal calcite, which formed from waters with the greatest hydrothermal contribution, has REE patterns that closely resemble those of vent fluids from the LHF. Our results demonstrate, for the first time, that (1) precipitation from pure seawater, (2) conductive heating of seawater, and (3) conductive cooling of hydrothermal fluids in the sub-seafloor all can lead to carbonate precipitation within a single ultramafic-hosted hydrothermal system.     

Fluid flow record from fracture-fill calcite in the Eocene limestones from the South-Pyrenean Basin (NE Spain) and its relationship to oil shows

The presence of oil shows associated with fractures provides a significant opportunity to a) unravel the type, origin and evolution of fluids involved in fracture-fills, and b) examine how they relate to oil migration. Two stages of calcite cement (C1 and C2) were distinguished in the fractures of the Eocene Armàncies platform carbonates; C1 is characterised by fence-like crystals, exhibits dull red luminescence and contains abundant twin planes, inclusions and δ¹⁸O values that range from − 6.2‰ to − 4.8‰ VPDB. C2 consists of blocky clean crystals, is characterized by dark brown-red luminescence that alternates with yellow bands, and contains hydrocarbon fluid inclusions with homogenisation temperatures of approximately 120 °C. δ¹⁸O values range from − 9.6‰ to − 8.9‰ VPDB. The remaining porosity after C2 precipitation is filled with liquid oil that reached 115 °C. This would seem to indicate that free oil and fluid inclusions oil probably come from the same migration pulse. Oil migration timing was coeval with C2 and continued after calcite cementation was completed.     

Diagenetic mineralization in Pennsylvanian coals from Indiana, USA: C/C and O/O implications for cleat origin and coalbed methane generation

Cleats and fractures in southwestern Indiana coal seams are often filled with authigenic kaolinite and/or calcite. Carbon- and oxygen-stable isotope ratios of kaolinite, calcite, and coalbed CO₂ were evaluated in combination with measured values and published estimates of δ¹⁸O of coalbed paleowaters that had been present at the time of mineralization. δ¹⁸O_mineral and δ¹⁸O_water values jointly constrain the paleotemperature of mineralization. The isotopic evidence and the thermal and tectonic history of this part of the Illinois Basin led to the conclusion that maximum burial and heat-sterilization of coal seams approximately 272 Ma ago was followed by advective heat redistribution and concurrent precipitation of kaolinite in cleats at a burial depth of < 1600 m at  78 ± 5 °C. Post-Paleozoic uplift, the development of a second generation of cleats, and subsequent precipitation of calcite occurred at shallower burial depth between  500 to  1300 m at a lower temperature of 43 ± 6 °C. The available paleowater in coalbeds was likely ocean water and/or tropical meteoric water with a δ¹⁸O_water  − 1.25‰ versus VSMOW. Inoculation of coalbeds with methanogenic CO₂-reducing microbes occurred at an even later time, because modern microbially influenced ¹³C-enriched coalbed CO₂ (i.e., the isotopically fractionated residue of microbial CO₂ reduction) is out of isotopic equilibrium with ¹³C-depleted calcite in cleats.     

Gas accumulation from oil cracking in the eastern Tarim Basin: A case study of the YN2 gas field

Oil and gas exploration in eastern Tarim Basin, NW China has been successful in recent years, with several commercial gas accumulations being discovered in a thermally mature to over-mature region. The Yingnan2 (YN2) gas field, situated in the Yingnan structure of the Yingjisu Depression, produces gases that are relatively enriched in nitrogen and C₂₊ alkanes. The δ¹³C₁ (−38.6‰ to −36.2‰) and δ¹³C₂ values (−30.9‰ to −34.7‰) of these gases are characteristic of marine sourced gases with relatively high maturity levels. The distributions of biomarkers in the associated condensates suggest close affinities with the Cambrian–Lower Ordovician source rocks which, in the Yingjisu Sag, are currently over-mature (with 3–4%Ro). Burial and thermal maturity modeling results indicate that paleo-temperatures of the Cambrian–Lower Ordovician source rocks had increased from 90 to 210 °C during the late Caledonian orogeny (458–438 Ma), due to rapid subsidence and sediment loading. By the end of Ordovician, hydrocarbon potential in these source rocks had been largely exhausted. The homogenization temperatures of hydrocarbon fluid inclusions identified from the Jurassic reservoirs of the YN2 gas field suggest a hydrocarbon emplacement time as recent as about 10 Ma, when the maturity levels of Middle–Lower Jurassic source rocks in the study area were too low (<0.7%Ro) to form a large quantity of oil and gas. The presence of abundant diamondoid hydrocarbons in the associated condensates and the relatively heavy isotopic values of the oils indicate that the gases were derived from thermal cracking of early-formed oils. Estimation from the stable carbon isotope ratios of gaseous alkanes suggests that the gases may have been formed at temperatures well above 190 °C. Thus, the oil and gas accumulation history in the study area can be reconstructed as follows: (1) during the late Caledonian orogeny, the Cambrian–Lower Ordovician marine source rocks had gone through the peak oil, wet gas and dry gas generation stages, with the generated oil and gas migrating upwards along faults and fractures to form early oil and gas accumulations in the Middle–Upper Ordovician and Silurian sandstone reservoirs; (2) since the late Yanshanian orogeny, the early oil accumulations have been buried deeper and oil has undergone thermal cracking to form gas; (3) during the late Himalayan orogeny, the seals for the deep reservoirs were breached; and the gas and condensates migrated upward and eventually accumulating in the relatively shallow Jurassic reservoirs.     

Emarat carbonate-hosted Zn–Pb deposit, Markazi Province, Iran: A geological, mineralogical and isotopic (S, Pb) study

The Emarat deposit, with a total proved reserve of 10 Mt ore grading 6% Zn and 2.26% Pb, is one of the largest Zn–Pb deposits in the Malayer–Esfahan belt. The mineralization is stratabound and restricted to Early Cretaceous limestones and dolomites. The ore consists mainly of sphalerite and galena with small amounts of pyrite, chalcopyrite, calcite, quartz, and dolomite. Textural evidence shows that the ore has replaced the host rocks and thus is epigenetic.Sulfur isotopes indicate that the sulfur in sphalerite and galena has been derived from Cretaceous seawater through thermochemical sulfate reduction. Sulfur isotope compositions of four apparently coprecipitated sphalerite–galena pairs suggest their precipitation was under equilibrium conditions. The sulfur isotopic fractionation observed for the sphalerite–galena pairs corresponds to formation temperatures between 77 °C and 168 °C, which agree with homogenization temperatures of fluid inclusions.Lead-isotope studies indicate that the lead in galena has been derived from heterogeneous sources including orogenic and crustal reservoirs with high ²³⁸U/²⁰⁴Pb and ²³²Th/²⁰⁴Pb ratios. Ages derived from the Pb-isotope model give meaningless ages, ranging from Early Carboniferous to future. It is probable that the Pb-isotope model ages that point to an earlier origin than the Early Cretaceous host rocks are derived from older reservoirs in the underlying Carboniferous or Jurassic units, either from the host rocks or from earlier-formed ore deposits within these units.This research and other available data show that the Emarat Zn–Pb deposit has many important features of Mississippi Valley-type (MVT) lead–zinc deposits and thus we argue that it is an MVT-type ore deposit.     

Assessing the past thermal and chemical history of fluids in crystalline rock by combining fluid inclusion and isotopic investigations of fracture calcite

Fluid inclusion studies combined with the isotope geochemistry of several generations of fracture calcite from the Olkiluoto research site, Finland, has been used to better understand the past thermal and fluid history in the crystalline rock environment. Typically, fracture mineral investigations use O and C isotopes from calcite and an estimate of the isotopic composition of the water that precipitated the calcite to perform δ¹⁸O geothermometry calculations to estimate past temperature conditions. By combining fluid inclusion information with calcite isotopes, one can directly measure the temperature at which the calcite formed and can better determine past fluid compositions. Isotopic, petrologic and fluid inclusion studies at the Olkiluoto research site in Finland were undertaken as part of an investigation within the Finnish nuclear waste disposal program. The study revealed that four fluids were recorded by fracture calcites. From petrologic evidence, the first fluid precipitated crystalline calcite at 151–225°C with a δ¹³C signature of −21 to −13.9‰ PDB and a δ¹⁸O signature of 12.3–13.0‰ SMOW. These closed fracture fillings were found at depths greater than 500 m and were formed from a high temperature, low salinity, Na–Cl fluid of possible meteoric water altered by exchange with wallrock or dilute basinal origin. The next fluid precipitated crystalline calcite with clay at 92–210°C with a δ¹³C signature of −2.6 to +3.8‰ PDB and a δ¹⁸O signature of 19.4–20.7‰ SMOW. These closed fracture fillings were found at depths less than 500 m and were formed from a moderate to high temperature, low to moderate salinity, Na–Cl fluid, likely of magmatic origin. The last group of calcites to form, record the presence of two distinct fluid types. The platy (a) calcite formed at 95–238°C with a δ¹³C signature of −12.2 to −3.8‰ PDB and a δ¹⁸O signature of 14.9–19.6‰ SMOW, from a high temperature, low salinity, Na–Cl fluid of possible magmatic origin. The platy (b) calcite formed at 67–98°C with a δ¹³C signature of −13.0 to −6.2‰ PDB and a δ¹⁸O signature of 15.1–20.1‰ SMOW, from a low temperature, high salinity, Ca–Na–Cl fluid of possible basinal brine origin. The two calcites are related through a mixing between the two end members. The source of the fluids for the platy grey (a) calcites could be the olivine diabase dykes and sills that cut through the site. The source of fluids for the platy (b) calcites could be the Jotnian arkosic sandstone formations in the northern part of the site. At the Olkiluoto site, δ¹⁸O geothermometry does not agree with fluid inclusion data. The original source of the water that forms the calcite has the largest effect on the isotopic signature of the calcites formed. Large isotopic shifts are seen in any water by mineral precipitation during cooling under rock–water equilibrium fractionation conditions. Different calcite isotopic signatures are produced depending on whether cooling occurred in an open or closed system. Water–rock interaction, at varying W/R ratios, between a water and a host rock can explain the isotopic shifts in many of the calcites observed. In some cases it is possible to shift the δ¹⁸O of the water by +11.5‰ (SMOW) using a realistic water–rock ratio. This process still does not explain some of the very positive δ¹⁸O values calculated using fluid inclusion data. Several other processes, such as low temperature recrystallization, boiling, kinetic effects and dissolution of calcite from fluid inclusion walls can affect isotopic signatures to varying degrees. The discrepancy between fluid inclusion data and δ¹⁸O geothermometry at the Olkiluoto site was most likely due to poor constraint on the original source of the water.     

Petrology, structure and tectonic significance of the Tuclame banded schists in the Sierras Pampeanas of Córdoba and its relationship with the metamorphic basement of northwestern Argentina

In the northwest of the Sierras Pampeanas of Córdoba (Central Argentina), in the Tuclame area, rocks called ‘banded schists’ are recognized. They are known since 120 years ago and are one of the most important lithologies of the metamorphic complex in this region. The compositional banding is the most conspicuous structural mesoscopic feature, composed of quartz-rich and mica-rich layers. It is a tectonic banding produced by pressure solution during a compressive event. P–T conditions of 557 ± 25 °C and 3.9 ± 1 kb were obtained for the main metamorphic event. A detailed field checking allowed recognition of the banded schists as decimetric or centimetric xenoliths isolated within the regional migmatites and the anatectic granitoids and as kilometric-scale belts within Sierras de Córdoba and San Luis. The authors have also identified banded schists in the Sierras de Aconquija, Ambato, Ancasti and Guasayán. Other workers recognized them in the Puna, Cumbres Calchaquíes, Sierras de Quilmes and Fiambalá, among the most well known outcrops. The banded schists have systematic petrological features and a distinctive mesoscopic structure that allow their identification and correlation with the other outcrops, which are arranged as a huge belt 2000 km long and 150 km wide, between 64°00′–66°30′W and 25°00′–41°34′S. In this work, all these rocks are proposed to be integrated into the Puncoviscana Basin, since field evidence indicated that the banded schists transitionally pass by transposition to phyllitic rocks typical of this metamorphosed basin, which would cover a region of about 300,000 km². At present, there is no accurate geochronology available for the metamorphic and deformation events proposed in this work for the Tuclame banded schists. However, considering the regional geological evidence, the great spread of the petrostructural process forming these rocks, the transition between the Puncoviscana Formation and the banded schists, and the earlier idea that the Puncoviscana Formation is the shallowest equivalent of deeper structural levels in the Sierras Pampeanas, we favor for the moment the hypothesis that the banded schists could be part of the oldest evolution of the Pampean orogeny (early Pampean stage) and could represent different structural levels of the same orogen, probably a late Precambrian–early Palaeozoic orogen. The events of migmatization and emplacement of anatectic granitoids could represent a late Pampean stage of early Palaeozoic age. Thus, the Pampean orogeny could have lasted around 30–40 Ma (570–530 Ma).     

Stable carbon and oxygen isotope investigation in historical lime mortar and plaster – Results from field and experimental study

Lime mortar and plaster were sampled from Roman, medieval and early modern buildings in Styria. The historical lime mortar and plaster consist of calcite formed in the matrix during setting and various aggregates. The stable C and O isotopic composition of the calcite matrix was analyzed to get knowledge about the environmental conditions during calcite formation. The δ¹³C_matrix and δ¹⁸O_matrix values range from −31 to 0‰ and −26 to −3‰(VPDB), respectively. Obviously, such a range of isotope values does not represent the local natural limestone assumed to be used for producing the mortar and plaster. In an ideal case, the calcite matrix in lime mortar and plaster is isotopically lighter in the exterior vs. the interior mortar layer according to the relationship δ¹⁸O_matrix = 0.61 · δ¹³C_matrix − 3.3 (VPDB). Calcite precipitation by uptake of gaseous CO₂ into alkaline Ca(OH)₂ solutions shows a similar relationship, δ¹⁸O_calcite = 0.67 · δ¹³C_calcite − 6.4 (VPDB). Both relationships indicate that the ¹³C/¹²C and ¹⁸O/¹⁶O values of the calcite reflect the setting behaviour of the lime mortar and plaster. Initially, CO₂ from the atmosphere is fixed as calcite, which is accompanied by kinetic isotope fractionation mostly due to the hydroxylation of CO₂ (δ¹³C_matrix ≈  −25‰ and δ¹⁸O_matrix ≈ −20‰). As calcite formation continued the remaining gaseous CO₂ is subsequently enriched in ¹³C and ¹⁸O causing later formed calcite to be isotopically heavier along the setting path in the matrix. Deviations from such an ideal isotopic behaviour may be due to the evolution of H₂O, e.g. evaporation, the source of CO₂, e.g. from biogenic origin, relicts of the natural limestone, and secondary effects, such as recrystallization of calcite. The results of the field and experimental study suggest that isotope values can be used as overall proxies to decipher the origin of carbonate and the formation conditions of calcite in the matrix of ancient and recent lime mortar and plaster. Moreover, these proxies can be used to select calcite matrix from historical lime mortar and plaster for ¹⁴C dating.     

Nucleation and crystallization of otavite, witherite, calcite, strontianite, hydrozincite, and hydrocerussite by CO2 membrane diffusion technique

Otavite, witherite, calcite, strontianite, hydrozincite and hydrocerussite nucleation was induced by CO₂ diffusion through a polyethylene membrane into a metal bearing solution. Nucleation and ongoing precipitation was followed at 25 ± 1 °C by the chemical evolution of the solution and the consumption of sodium hydroxide (pH-stat conditions). X-ray diffraction patterns as well as FT-infrared and Raman spectra confirmed the formation of well crystallized solids, except for less crystalline hydrozincite. In several experiments simonkolleite and laurionite precipitated concurrently with hydrozincite and hydrocerussite. The carbonate end-member minerals, smithsonite and cerussite, however were not formed. Carbonate minerals crystallized as spherical aggregates of thin layered otavite, spherical orientated witherite needles, rhombohedral calcite, pseudo-hexagonal strontianite laths, fibrous lumps of hydrozincite and planar hexagonal hydrocerussite crystals. Crystal and aggregate sizes range between 1 and 100 μm. Nucleation occurred at well defined reaction times and distinct critical supersaturation indices (SI_crit). The time for nucleation at constant pH decreased as the initial metal concentration increased for a given solid. The SI_crit values decreased in the order of hydrocerussite (3.2), otavite (2.5), strontianite (1.6), witherite (0.9) and calcite (0.7).     

Post-collisional lamprophyric event in Sierra Norte, Córdoba, Argentina: Mineralogical, geochemical and isotopic characteristics

Over 20 lamprophyre dykes, varying in width between a few centimeters and several meters, have been identified in central Sierra Norte – Eastern Pampean Ranges, Córdoba, Argentina. Their mineralogy and chemistry indicate that they are part of the calc-alkaline lamprophyres clan (CAL). They contain phenocrysts of magnesiohornblende ± augite set in a groundmass of magnesiohornblende, calcic-plagioclase, alkali feldspar, and opaque minerals, which designate them as spessartite-type lamprophyres. Alteration products include chlorite, calcite and iron oxides after mafic phenocrysts, though some are partially replaced by actinolite. Feldspars are replaced by carbonate and clay minerals.The dykes are relatively primitive, and show restricted major element variation (SiO₂ 51.1–55.3 wt.%, Al₂O₃ 12–16.6 wt.%, total alkalies 1.5–4.7 wt.%), high Mg# (55–77), high Cr contents (27–988 ppm) and moderate to high Ni contents (60–190 ppm). Lamprophyre LILE (e.g. Rb averages 110 ppm, Sr 211–387 ppm, Ba 203–452 ppm) are high relative to HFSE (e.g., Ta 0.2–1.6 ppm, Nb 4–11 ppm, Y 17–21 ppm), and are enriched in LREE (30–70 times chondrite). They are characterized by relatively high ²⁰⁸Pb/²⁰⁴Pb (38.8–39.9), ²⁰⁷Pb/²⁰⁴Pb (15.7), and ²⁰⁶Pb/²⁰⁴Pb (18.7–20.1), combined with low (epsilon)ε_Nd (−4.69 to −1.52) and a relative moderately high (⁸⁷Sr/⁸⁶Sr)_i of 0.7055–0.7074. The Rb–Sr whole rock isochron indicates an Early Ordovician age of 485 ± 25 Ma. The calculated T_DM (1.7 Ga) suggests that these rocks appear to have originated from a reservoir that was created during a mantle metasomatism event related to the Pampean orogeny.The Sierra Norte lamprophyres show affinities with a subduction-related magma in an active continental margin. Their geochemical and isotopic features suggest a multicomponent source, composed of enriched mantle material variably contaminated by crustal components. The lamprophyric suite emplacement occurred at the dawning stage of the Pampean orogeny, in a regional post-collisional extensional setting developed in the Sierra Norte-Ambargasta batholith (SNAB) in Early Ordovician times.     

Geology,geochronology and fluid characteristics of the Pingqiu gold deposit,Southeastern Guizhou Province,China

The junction of the southeastern Guizhou, the southwestern Hunan, and the northern Guangxi regions is located within the southwestern Jiangnan orogen and forms a NE-trending ∼250 km gold belt containing more than 100 gold deposits and occurrences. The Pingqiu gold deposit is one of the numerous lode gold deposits in the southeastern Guizhou district. Gold mineralization is hosted in Neoproterozoic lower greenschist facies metamorphic rocks and controlled by fold-related structures. Vein types present at Pingqiu include bedding-parallel and discordant types, with saddle-reefs and their down limb extensions dominating but with lesser discordant types. The major sulfide minerals are arsenopyrite and pyrite, with minor sphalerite, galena, chalcopyrite, and rare pyrrhotite, marcasite, and tetrahedrite. Much of the gold is μm- to mm-sized grains, and occurs as fracture-controlled isolated grains or filaments in quartz, galena, sphalerite, pyrite, and wallrock.Three types of fluid inclusions are distinguished in hydrothermal minerals. Type 1 aqueous inclusions have homogenization temperatures of 171–396 °C and salinities of 1.4–9.8 wt% NaCl equiv. Type 2 aqueous-carbonic inclusions yield final homogenization temperatures of 187–350 °C, with salinities of 0.2–7.7 wt% NaCl equiv. Type 3 inclusions are carbonic inclusions with variable relative content of CO₂ and CH₄, and minor amounts of N₂ and H₂O. The close association of CO₂-rich inclusions and H₂O-rich inclusions in groups and along the same trail suggests the presence of fluid immiscibility. The calculated δ¹⁸O_H2O values range from 4.3‰ to 8.3‰ and δD_H2O values of fluid inclusions vary from −55.8‰ to −46.9‰. A metamorphic origin is preferred on the basis of geological background and analogies with other similar deposit types.Two ore-related sericite samples yield well-defined ⁴⁰Ar/³⁹Ar plateau ages of 425.7 ± 1.7 Ma and 425.2 ± 1.3 Ma, respectively. These data overlap the duration of the Caledonian gold mineralization along the Jiangnan orogen, and suggest that gold mineralization was post-peak regional metamorphism and occurred during the later stages of the Caledonian orogeny.Overall, the Pingqiu gold deposit displays many of the principal characteristics of the Bendigo gold mines in the western Lachlan Orogen (SE Australia) and the Dufferin gold deposit in the Meguma Terrane (Nova Scotia, Canada) but also some important differences, which may lead to the disparity in gold endowment. However, the structural make-up at deposit scale, and the shallow mining depth at present indicate that the Pingqiu gold deposit may have considerable gold potential at depth.     

Stable isotope evidence for multiple fluid regimes during carbonate cementation of the Upper Tertiary Hazeva Formation, Dead Sea Graben, southern Israel

Stable carbon- and oxygen-isotope compositions of calcite and dolomite cements have been used to understand porewater evolution in the Upper Tertiary Hazeva Formation within the Dead Sea Graben, southern Israel. Sandstone samples were obtained from four boreholes in three tectonic blocks of the graben over depths of 253–6448 m, a variation that largely reflects differential subsidence of individual fault-bounded blocks. Early carbonate cements dominate diagenesis. Calcite occurs at <1600 m, but was replaced by dolomite at greater depths. Dolomite at 1600–2700 m is Fe-poor (<0.8 mol% FeCO₃), and at 4700–6200 m, Fe-rich (0.5–7.2 mol% FeCO₃). Magnesite, anhydrite and halite are the final diagenetic phases. Calcite has positively correlated δ¹⁸O (+21‰ to +25‰) and δ¹³C (−6‰ to −2‰) values that generally decrease with depth. Dolomite has a wider variation in δ¹⁸O (+18‰ to +30‰) and δ¹³C (−8‰ to −1‰) values, which also generally are lower with increasing depth. However, the δ¹³C and δ¹⁸O values of dolomite from the uppermost 400 m of the Hazeva Formation in the Sedom Deep-1 borehole are anomalous in spanning the entire range of stable carbon and oxygen isotopic compositions over this relatively small interval.The decreasing dolomite δ¹³C values likely indicate an increased contribution of carbon from organic sources with increasing depth. Except for the uppermost 400 m, Hazeva Formation dolomite in the Sedom Deep-1 borehole has stable carbon-isotope compositions that imply initial dolomitization at much shallower levels, prior to the preferential subsidence of this tectonic block. The oxygen isotopic compositions of the calcite cement are best explained by equilibration at present burial temperatures (≤55 °C) with porewater of meteoric origin. Its δ¹⁸O values increased from −5‰ at the shallowest depths to 0‰ at 1600 m. The dolomite oxygen isotopic compositions also reflect equilibration at present burial temperatures with porewaters ranging from 0‰ at 1600 m to +7‰ at 3600 m (100 °C). In the deepest fault block (Sedom Deep-1 borehole), however, increasingly Fe-rich dolomite has (re)equilibrated with porewater whose δ¹⁸O values decreased from +9‰ at 4750 m (120 °C) to +1‰ to +2‰ by 6200 m (150 °C).Much of the dolomite likely formed at relatively shallow depths from saline brines derived from precursors to the Dead Sea. These infiltrated the Hazeva Formation, mixing with and largely displacing meteoric water, and dolomitizing calcite. Rock–water ratios tended to be high during these processes. However, the upper 400 m of the Hazeva Formation in the deepest fault block were likely deposited during its rapid tectonic subsidence, and largely escaped the initial style of dolomitization pervasive elsewhere in the study area. These sediments were also capped by evaporites. This relatively thin interval likely became a preferential conduit for brines that escaped underlying and overlying strata, including the Fe-rich, lower ¹⁸O fluids (evolved seawater?) present in the deepest part of the graben. These rocks present the most promising target for the passage and accumulation of hydrocarbons in the study area.