Thermochemical and bacterial sulfate reduction in the Cambrian and Lower Ordovician carbonates in the Tazhong Area,Tarim Basin,NW China: evidence from fluid inclusions,C, S,and Sr isotopic data

Petrographic features, C, O, S, and Sr isotopes were determined, and fluid inclusions (FI) were analyzed on various stages of vug‐ and fracture‐fillings from the Cambrian and Lower Ordovician reservoirs in the Tazhong area, Tarim basin, NW China. The aim was to assess the origin of pyrite and anhydrite and the processes affecting sulfur during diagenesis of the carbonates. Pyrite from seven wells has δ³⁴S values from ?22‰ to +31‰. The pyrites with low δ³⁴S values from ?21.8‰ to ?12.3‰ were found close to fracture‐filling calcites with vapor‐liquid double‐phase aqueous fluid inclusions homogenization temperatures (FI‐Th) from 55.7 to 73.2°C, salinities from 1.4wt% to 6.59wt% NaCl equiv and δ¹³C values from ?2.3‰ to ?14.2‰, indicating an origin from bacterial sulfate reduction by organic matter. Other sulfides with heavier δ³⁴S values may have formed by thermochemical sulfate reduction (TSR) during two episodes. The earlier TSR in the Middle and Lower Cambrian resulted in pyrites and H₂S having δ³⁴S values from 30 to 33‰, close to those of bedded anhydrite and oilfield water (approximately 34‰). The later TSR is represented by calcites with δ¹³C values as light as ?17.7‰ and FI‐Th of about 120–145°C, and pyrite and H₂S with δ³⁴S values close to those of the Upper Cambrian burial‐diagenetic anhydrite (between +14.8‰ and +22.6‰). The values of the anhydrite are significantly lighter than contemporary seawater sulfates. This together with ⁸⁷Sr/⁸⁶Sr values of anhydrite and TSR calcites from 0.7091 to 0.7125 suggests a source from the underlying Ediacaran seawater sulfate and detrital Sr contribution.     

Fluid inclusion and stable isotope constraints on the genesis of the Jian copper deposit,Sanandaj–Sirjan metamorphic zone,Iran

The Jian copper deposit, located on the eastern edge of the Sanandaj–Sirjan metamorphic zone, southwest of Iran, is contained within the Surian Permo‐Triassic volcano‐sedimentary complex. Retrograde metamorphism resulted in three stages of mineralization (quartz ± sulfide veins) during exhumation of the Surian metamorphic complex (Middle Jurassic time; 159–167 Ma), and after the peak of the metamorphism (Middle to Late Triassic time; approximately 187 Ma). The early stage of mineralization (stage 1) is related to a homogeneous H₂O–CO₂ (XCO₂ > 0.1) fluid characterized by moderate salinity (<10 wt.% NaCl equivalent) at high temperature and pressure (>370°C, >3 kbar). Early quartz was followed by small amounts of disseminated fine‐grained pyrite and chalcopyrite. Most of the main‐ore‐stage (stage 2) minerals, including chalcopyrite, pyrite and minor sphalerite, pyrrhotite, and galena, precipitated from an aqueous‐carbonic fluid (8–18 wt.% NaCl equivalent) at temperatures ranging between 241 and 388°C during fluid unmixing process (CO₂ effervescence). Fluid unmixing in the primary carbonaceous fluid at pressures of 1.5–3 kbar produced a high XCO₂ (>0.05) and a low XCO₂ (<0.01) aqueous fluid in ore‐bearing quartz veins. Oxygen and hydrogen isotope compositions suggest mineralization by fluids derived from metamorphic dehydration (δ¹⁸O_fluid = +7.6 to +10.7‰ and δD = ?33.1 to ?38.5‰) during stage 2. The late stage (stage 3) is related to a distinct low salinity (1.5–8 wt.% NaCl equivalent) and temperatures of (120–230°C) aqueous fluid at pressures below 1.5 kbar and the deposition of post‐ore barren quartz veins. These fluids probably derived from meteoric waters, which circulated through the metamorphic pile at sufficiently high temperatures and acquire the characteristics of metamorphic fluids (δ¹⁸O_fluid = +4.7 to +5.1‰ and δD = ?52.3 to ?53.9‰) during waning stages of the postearly Cimmerian orogeny in Surian complex. The sulfide‐bearing quartz veins are interpreted as a small‐scale example of redistribution of mineral deposits by metamorphic fluids. This study suggests that mineralization at the Jian deposit is metamorphogenic in style, probably related to a deep‐seated mesothermal system.     

Hydrology of the Western Arkoma basin and Ozark platform during the Ouachita orogeny: implications for Mississippi Valley-type ore formation in the Tri-State Zn–Pb district

Numerical groundwater modeling was used to investigate the role of fluid flow associated with uplift of the Arkoma basin during the closing stages of the Ouachita orogeny in forming the Mississippi Valley‐type Zn–Pb ores of the Tri‐State district. The model hydrostratigraphy was flexurally compensated to account for the restoration of Pennsylvanian–Permian sediments removed since the close of the orogeny in estimating the regional paleotopographic gradient. Estimates of the amount of Pennsylvanian–Permian sediment that has been removed by erosion vary widely. A thick and a thin endmember case were considered, and in both cases topographydriven fluid flow was shown to have been an important mechanism for groundwater motion, with a lesser component contributed during the early stages of uplift by overpressuring created by compaction in the deep portion of the Arkoma basin. The Pennsylvanian–Permian sediments and underlying Western Interior Plains confining system acted as thick capping aquitards that caused slow rates of groundwater flow over much of the profile. As a result, meteoric water infiltration initiated during uplift was slow to flush saline formation waters, allowing MVT ore‐forming salinities to persist at Tri‐State on the order of at least 10⁰ Myr. The slow groundwater flow rates also caused heat transport to occur primarily by conduction rather than advection. Despite this, MVT ore‐forming temperatures were still reached at Tri‐State for both endmember cases of Pennsylvanian–Permian aquitard thickness, though much more readily in the thick aquitard case. Faults within the Tri‐State district served as a regional fluid focusing mechanism and probably played a more important role in localizing mineralization than the window in the Ozark confining unit that occurs in the district. Fluids rising along these faults could have cooled by about 8–10°C and as much as another 0.3°C km^?1 as they flowed laterally northward. This temperature change alone however would not have been sufficient to precipitate the total mass of metal sulfide ore occurring at Tri‐State.     

Experimental study of aqueous fluid infiltration into quartzite: implications for the kinetics of fluid redistribution and grain growth driven by interfacial energy reduction

To investigate the kinetics of interfacial energy‐driven fluid infiltration, experiments were carried out in a quartzite–water system at 621–925°C and 0.8 GPa. Infiltration couples were made by juxtaposing presynthesized dry quartzite cylinders and fluid reservoirs. The infiltration process was confirmed by the presence of pores at the quartzite grain edges. As predicted from theoretical considerations and previous experiments, wetting fluids such as pure water and NaCl aqueous solution infiltrated into quartzite, whereas nonwetting CO₂‐rich fluids did not. Newly precipitated quartz layers at the surfaces of the infiltrated sample proved that infiltration took place by a dissolution–precipitation mechanism. The enhancement of grain growth by fluid infiltration was observed over the entire range of experimental temperatures. The fluid fraction, gauged by the porosity of the run products, increases at the infiltration front and then decreases towards the fluid reservoir to form a high‐porosity zone with a maximum porosity of 2.3–2.9%. As infiltration proceeds, the high‐porosity zone advances like a travelling wave. This porosity wave is probably caused by a grain curvature gradient resulting from preferential grain growth in the infiltrated part of the quartzite, perhaps combined with other factors. The infiltration kinetics were modelled with a steady‐state diffusion model over the high‐porosity zone. The solubility difference between dissolving and precipitating grains was deduced to be 2 × 10^?2?3 × 10^?1 wt %. The experimentally obtained infiltration rate of aqueous fluid in the steady‐state diffusion regime (2 ± 0.5 × 10^?8 m sec^?1 at 823°C) is much faster than the estimated metamorphic fluid flux rates, so that interfacial energy‐driven fluid redistribution in quartz‐rich layers could significantly contribute to the fluid flux in high‐grade metamorphism, at least over a short distance. Cathodoluminescence observations of the run products revealed that the grain growth of quartzite in the presence of fluid proceeds extensively, which would promote the chemical equilibration between fluid and rock more effectively than would volume diffusion in quartz crystals.     

Fluid mixing induced by hydrothermal activity in the ordovician carbonates in Tarim Basin,China

Permian hydrothermal activity in the Tarim Basin may have been responsible for the invasion of hot brines into Ordovician carbonate reservoirs. Studies have been undertaken to explain the origin and geochemical characteristics of the diagenetic fluid present during this hydrothermal event although there is no consensus on it. We present a genetic model resulting from the study of δ¹³C, δ¹⁸O, δ³⁴S, and ⁸⁷Sr/⁸⁶Sr isotope values and fluid inclusions (FIs) from fracture‐ and vug‐filling calcite, saddle dolomite, fluorite, barite, quartz, and anhydrite from Ordovician outcrops in northwest (NW) Tarim Basin and subsurface cores in Central Tarim Basin. The presence of hydrothermal fluid was confirmed by minerals with fluid inclusion homogenization temperatures being >10°C higher than the paleo‐formation burial temperatures both in the NW Tarim and in the Central Tarim areas. The mixing of hot (>200°C), high‐salinity (>24 wt% NaCl), ⁸⁷Sr‐rich (up to 0.7104) hydrothermal fluid with cool (60–100°C), low‐salinity (0 to 3.5 wt% NaCl), also ⁸⁷Sr‐rich (up to 0.7010) meteoric water in the Ordovician unit was supported by the salinity of fluid inclusions, and δ¹³C, δ¹⁸O, and ⁸⁷Sr/⁸⁶Sr isotopic values of the diagenetic minerals. Up‐migrated hydrothermal fluids from the deeper Cambrian strata may have contributed to the hot brine with high sulfate concentrations which promoted thermochemical sulfate reduction (TSR) in the Ordovician, resulting in the formation of ¹²C‐rich (δ¹³C as low as ?13.8‰) calcite and ³⁴S‐rich (δ³⁴S values from 21.4‰ to 29.7‰) H₂S, pyrite, and elemental sulfur. Hydrothermal fluid mixing with fresh water in Ordovician strata in Tarim Basin was facilitated by deep‐seated faults and up‐reaching faults due to the pervasive Permian magmatic activity. Collectively, fluid mixing, hydrothermal dolomitization, TSR, and faulting may have locally dissolved the host carbonates and increased the reservoir porosity and permeability, which has significant implications for hydrocarbon exploration.     

Origin of palaeo‐waters in the Ordovician carbonates in Tahe oilfield,Tarim Basin: constraints from fluid inclusions and Sr,C and O isotopes

Petrographic features, isotopes, and trace elements were determined, and fluid inclusions were analyzed on fracture‐filling, karst‐filling and interparticle calcite cement from the Ordovician carbonates in Tahe oilfield, Tarim basin, NW China. The aim was to assess the origin and evolution of palaeo‐waters in the carbonates. The initial water was seawater diluted by meteoric water, as indicated by bright cathodoluminescence (CL) in low‐temperature calcite. The palaeoseawater was further buried to temperatures from 57 to 110°C, nonluminescent calcite precipitated during the Silurian to middle Devonian. Infiltration of meteoric water of late Devonian age into the carbonate rocks was recorded in the first generation of fracture‐ and karst‐filling dull red CL calcite with temperatures from <50°C to 83°C, low salinities (<9.0 wt%), high Mn contents and high ⁸⁶Sr/⁸⁷Sr ratios from 0.7090 to 0.7099. During the early Permian, ⁸⁷Sr‐rich hydrothermal water may have entered the carbonate rocks, from which precipitated a second generation of fracture‐filling and interparticle calcite and barite cements with salinities greater than 22.4 wt%, and temperatures from 120°C to 180°C. The hydrothermal water may have collected isotopically light CO₂ (possibly of TSR‐origin) during upward migration, resulting in hydrothermal calcite and the present‐day oilfield water having δ¹³C values from ?4.3 to ?13.8‰ and showing negative relationships of ⁸⁷Sr/⁸⁶Sr ratios to δ¹³C and δ¹⁸O values. However, higher temperatures (up to 187°C) and much lower salinities (down to 0.5 wt%) measured from some karst‐filling, giant, nonluminescent calcite crystals may suggest that hydrothermal water was deeply recycled, reduced (Fe‐bearing) meteoric water heated in deeper strata, or water generated from TSR during hydrothermal water activity. Mixing of hydrothermal and local basinal water (or diagenetically altered connate water) with meteoric waters of late Permian age and/or later may have resulted in large variations in salinity of the present oilfield waters with the lowest salinity formation waters in the palaeohighs.     

Retrograde P–T evolution and high temperature–low pressure fluid circulation in relation to late Hercynian intrusions: a mineralogical and fluid inclusion study of the Charroux-Civray plutonic complex (north-western Massif Central, France)

The calc‐alkaline plutonic complex from Charroux‐Civray (north‐western part of the French Massif Central) displays multiphase hydrothermal alteration. Plutonic rocks, as well as early retrograde Ca–Al silicate assemblages, which have crystallized during cooling and uplifting of the plutonic series, are affected by multiphase chlorite–phengite–illite–carbonate alteration linked to intense pervasive fluid circulation through microfractures. The petrographic study of alteration sequences and their associated fluid inclusions in microfissures of the plutonic rocks, as well as in mineral fillings of the veins, yields a reconstruction of the P–T–X evolution of the Hercynian basement after the crystallization of the main calc‐alkaline plutonic bodies. This reconstruction covers the uplift of the basement to its exposure and the subsequent burial by Mesozoic sediments. Cooling of the calc‐alkaline plutonic series started at solidus temperatures (～650°C), at a pressure of about 4 kbar (1 bar = 10⁵ N m^?2), as indicated by magmatic epidote stability, hornblende barometry and fluid inclusion data. Cooling continued under slightly decreasing pressure during uplift down to 2–3 kbar at 200–280°C (prehnite–pumpellyite paragenesis). Then, a hot geothermal circulation of CO₂‐bearing fluids was induced within the calc‐alkaline rocks leading to the formation of greisen‐like mineralizations. During this stage, temperatures around 400–450°C were still high for the inferred depths (～2 kbar). They imply abnormal heat flows and thermal gradients of 60–80°C km^?1. The hypothesis of the existence of one large or a succession of smaller peraluminous plutons at depth, supported by geophysical data, suggests that localized heat flows were linked to concealed leucogranite intrusions. As uplift continued, greisen mineralization was subsequently affected by the chlorite–phengite–dolomite assemblage, correlated with aqueous and nitrogen‐bearing fluid circulations in the temperature range of 400–450°C. In a later stage, a continuous temperature decrease at constant pressure (～0.5 kbar) led to the alteration of the dolomite–illite–chlorite type in the 130–250°C temperature range.     

The role of thermochemical sulfate reduction in the origin of Mississippi Valley‐type deposits. II. Carbonate–sulfide relationships

The two‐dimensional (2D) reactive transport model of Corbella et al. [Min. Deposita 39 (2004) 344] of the classic ‘mixing hypothesis’, in which a solution containing reduced sulfur and a solution containing aqueous Zn are mixed, has been extended to the case where one brine contains sulfate rather than reduced sulfur, and H₂S is produced during the mixing process by thermochemical sulfate reduction (TSR), using a possible rate law and experimentally derived rate constants. It is shown that TSR can provide sufficient reduced sulfur to form an ore body in geologically reasonable times, using rate constants in the upper part of the experimental range, in agreement with the results of a constant stirring tank reactor model ( Thom & Anderson in press ). The results of the 2D model are also compared with the results of titration (zero dimensional) and one‐dimensional models, showing that these models fail to adequately show the amount of carbonate precipitation. Although the 2D model qualitatively shows the distribution and amounts of carbonate precipitation and dissolution, these results are quantitatively inaccurate due to several factors that are intrinsically hard to define.     

A comprehensive review of hydrocarbons and genetic model of the sandstone‐hosted Dongsheng uranium deposit,Ordos Basin,China

The Dongsheng uranium deposit, the largest in situ leach uranium mine in the Ordos Basin, geometrically forms a roll‐front type deposit that is hosted in the Middle Jurassic Zhiluo Formation. The genesis of the mineralization, however, has long been a topic of great debate. Regional faults, epigenetic alterations in surface outcrops, natural oil seeps, and experimental findings support a reducing microenvironment during ore genesis. The bulk of the mineralization is coffinite. Based on thin‐section petrography, some of the coffinite is intimately intergrown with authigenic pyrite (ore‐stage pyrite) and is commonly juxtaposed with some late diagenetic sparry calcite (ore‐stage calcite) in primary pores, suggesting simultaneous precipitation. Measured homogenization temperatures of greater than 100°C from fluid inclusions indicate circulation of low‐temperature hydrothermal fluids in the ore zone. The carbon isotopic compositions of late calcite cement (δ¹³C_VPDB = ?31.0 to ?1.4‰) suggest that they were partly derived from sedimentary organic carbon, possibly from deep‐seated petroleum fluids emanating from nearby faults. Hydrogen and oxygen isotope data from kaolinite cement (δD = ?133 to ?116‰ and δ¹⁸O_SMOW = 12.6–13.8‰) indicate that the mineralizing fluids differed from magmatic and metamorphic fluids and were more depleted in D (²H) than modern regional meteoric waters. Such a strongly negative hydrogen isotopic signature suggests that there has been selective modification of δD by CH₄±H₂S±H₂ fluids. Ore‐stage pyrite lies within a very wide range of δ³⁴S (?39.2 to 26.9‰), suggesting that the pyrite has a complex origin and that bacterially mediated sulfate reduction cannot be precluded. Hydrocarbon migration and its role in uranium reduction and precipitation have here been unequivocally defined. Thus, a unifying model for uranium mineralization can be established: Early coupled bacterial uranium mineralization and hydrocarbon oxidation were followed by later recrystallization of ore phases in association with low‐temperature hydrothermal solutions under hydrocarbon‐induced reducing conditions.     

Molecular transport of methane, ethane and nitrogen and the influence of diffusion on the chemical and isotopic composition of natural gas accumulations

Laboratory experiments have been performed to determine diffusion coefficients of natural gas components (methane, ethane and nitrogen) and isotope fractionation effects under simulated in situ pressure (up to 45 MPa effective stress) and temperature conditions (50–200°C) in water‐saturated pelitic and coarse‐grained rocks. Effective diffusion coefficients of molecular nitrogen (0.39 × 10^?11 to 21.6 × 10^?11 m² sec^?1 at 90°C) are higher than those for methane (0.18 × 10^?11 to 18.2 × 10^?11 m² sec^?1 at 90°C). Diffusive flux rates expressed in mass units are generally higher for N₂ than for CH₄. Both methane and (to a lesser extent) nitrogen diffusion coefficients decrease with increasing total organic carbon (TOC) content of the rock samples because of sorption processes on the organic matter. This effect decreases with increasing temperature. Effective diffusion coefficients increase upon a temperature increase from 50 to 200°C by a factor of four. Effective diffusion coefficients and steady‐state diffusive flux decrease with effective stress. Stationary diffusive fluxes drop by 50–70% for methane and 45–62% for nitrogen while effective diffusion coefficients are reduced by 38% (CH₄) and 32–48% (N₂), respectively. Isotope fractionation coefficients of diffusive transport are higher for methane (?1.56 and ?2.77‰) than for ethane (?0.84 and ?1.62‰). Application of the experimental results to geological systems show that diffusive transport has only a low transport efficiency. Significant depletion of natural gas reservoirs by molecular diffusion is only expected in cases of very poor caprock qualities (in terms of thickness and/or porosity) and over extended periods of geological time. Under these circumstances, the chemical and isotopic composition of a gas reservoir will change and maturity estimates based on these parameters may be deceptive. To account for these potential effects, nomograms have been developed to estimate diffusive losses and apply maturity corrections.     

Geological setting, nature of ore fluids and sulphur isotope geochemistry of the Fu Ning Carlin-type gold deposits, Yunnan Province, China

Carlin‐type gold deposits in southern China are present in Palaeozoic to Mesozoic siliciclastic and carbonate rocks. The border region of Yunnan, Guizhou and Guangxi Provinces contains gold deposits on the south‐western margin of the Pre‐Cambrian South China Craton in south‐eastern Yunnan Province. The Fu Ning gold deposits host epigenetic, micron‐sized disseminated gold in: (i) Middle Devonian (D₁p) black carbonaceous mudstone at the Kuzhubao gold deposit and (ii) fault breccia zones at the contact between Triassic gabbro (β ) and the Devonian mudstone (D₁p) at the Bashishan gold deposit. The deposits are associated with zones of intense deformation with enhanced permeability and porosity that focused hydrothermal fluid flow, especially where low‐angle N‐S striking thrust faults are cut by NW striking strike‐slip and/or NE striking normal faults. Major sulphide ore minerals in the Fu Ning gold deposits are pyrite, arsenopyrite, arsenic‐rich pyrite, stibnite and minor iron‐poor sphalerite. Gangue minerals are quartz, sericite, calcite, ankerite and chlorite. Hypogene ore grades range from 1 to 7 g t^?1 Au and up to 18 g t^?1 Au at the Kuzhubao gold deposit and are generally less than 3 g t^?1 Au at the Bashishan gold deposit. Sub‐microscopic gold mineralization is associated with finely disseminated arsenic‐rich pyrite in the Stage III mineral assemblage. Two types of primary fluid inclusions have been recorded: Type I liquid–vapour inclusions with moderate‐to‐high liquid/vapour ratios, and Type II inclusions containing moderate liquid/vapour ratios with CO₂ as determined from laser Raman analysis. Temperature of homogenization (T_h) data collected from these primary fluid inclusions in gold‐ore Stage III quartz ranged from 180 to 275°C at the Kuzhubao gold deposit and 210 to 330°C at the Bashishan gold deposit. Salinity results indicate that there were possibly two fluids present during gold deposition, including: (i) an early fluid with 0.8–6.5 wt.% NaCl equivalent, similar to salinity in shear‐zone‐hosted gold deposits with metamorphic derived fluids; and (ii) a late fluid with 11.8–13.4 wt.% NaCl equivalent, indicating possible derivation from connate waters and/or brine sources. CO₂ and trace CH₄ were only detected by laser Raman spectrometry in gold‐ore‐stage primary fluid inclusions. Results of sulphur isotope studies showed that δ³⁴S values for pyrite and arsenopyrite associated with gold‐ore mineralization during Stage III at the Kuzhubao and Bashishan gold deposits are isotopically similar and moderately heavy with a range from +9 to +15 per mil, and also fall into the range of δ³⁴S values reported for Carlin‐type gold deposits. Sulphur isotopes suggest that the Fu Ning gold deposits were formed from connate waters and/or basinal brines. Fluid geochemistry data from the Fu Ning gold deposits suggest a Carlin‐type genetic model, involving fluid mixing between: (i) deep CO₂‐rich metamorphic fluids, (ii) moderately saline, reduced connate waters and/or basinal brines; and (iii) evolved meteoric waters.     

Modelling the Lost City hydrothermal field: influence of topography and permeability structure

The Lost City hydrothermal field (LCHF) is hosted in serpentinite at the crest of the Atlantis Massif, an oceanic core complex close to the mid‐Atlantic Ridge. It is remarkable for its longevity and for venting low‐temperature (40–91°C) alkaline fluids rich in hydrogen and methane. IODP Hole U1309D, 5 km north of the LCHF, penetrated 1415 m of gabbroic rocks and contains a near‐conductive thermal gradient close to 100°C km^?1. This is remarkable so close to an active hydrothermal field. We present hydrothermal modelling using a topographic profile through the vent field and IODP site U1309. Long‐lived circulation with vent temperatures similar to the LCHF can be sustained at moderate permeabilities of 10^?14 to 10^?15 m² with a basal heatflow of 0.22 W m^?2. Seafloor topography is an important control, with vents tending to form and remain in higher topography. Models with a uniform permeability throughout the Massif cannot simultaneously maintain circulation at the LCHF and the near‐conductive gradient in the borehole, where permeabilities <10^?16 m² are required. A steeply dipping permeability discontinuity between the LCHF and the drill hole is required to stabilize venting at the summit of the massif by creating a lateral conductive boundary layer. The discontinuity needs to be close to the vent site, supporting previous inferences that high permeability is most likely produced by faulting related to the transform fault. Rapid increases in modelled fluid temperatures with depth beneath the vent agree with previous estimates of reaction temperature based on geochemical modelling.     

Numerical model of pore‐pressure diffusion associated with the initiation of the 2010–2011 Guy–Greenbrier,Arkansas earthquakes

We model pore‐pressure diffusion caused by pressurized waste‐fluid injection at two nearby wells and then compare the buildup of pressure with the observed initiation and migration of earthquakes during the early part of the 2010–2011 Guy–Greenbrier earthquake swarm. Pore‐pressure diffusion is calculated using MODFLOW 2005 that allows the actual injection histories (volume/day) at the two wells to diffuse through a fractured and faulted 3D aquifer system representing the eastern Arkoma basin. The aquifer system is calibrated using the observed water‐level recovery following well shut‐in at three wells. We estimate that the hydraulic conductivities of the Boone Formation and Arbuckle Group are 2.2 × 10^?2 and 2.03 × 10^?3 m day^?1, respectively, with a hydraulic conductivity of 1.92 × 10^?2 m day^?1 in the Hunton Group when considering 1.72 × 10^?3 m day^?1 in the Chattanooga Shale. Based on the simulated pressure field, injection near the relatively conductive Enders and Guy–Greenbrier faults (that hydraulically connect the Arbuckle Group with the underlying basement) permits pressure diffusion into the crystalline basement, but the effective radius of influence is limited in depth by the vertical anisotropy of the hydraulic diffusivity. Comparing spatial/temporal changes in the simulated pore‐pressure field to the observed seismicity suggests that minimum pore‐pressure changes of approximately 0.009 and 0.035 MPa are sufficient to initiate seismic activity within the basement and sedimentary sections of the Guy–Greenbrier fault, respectively. Further, the migration of a second front of seismicity appears to follow the approximately 0.012 MPa and 0.055 MPa pore‐pressure fronts within the basement and sedimentary sections, respectively.     

Precipitation of lead–zinc ores in the Mississippi Valley‐type deposit at Trèves,Cévennes region of southern France

The Trèves zinc–lead deposit is one of several Mississippi Valley‐type (MVT) deposits in the Cévennes region of southern France. Fluid inclusion studies show that the ore was deposited at temperatures between approximately 80 and 150°C from a brine that derived its salinity mainly from the evaporation of seawater past halite saturation. Lead isotope studies suggest that the metals were extracted from local basement rocks. Sulfur isotope data and studies of organic matter indicate that the reduced sulfur in the ores was derived from the reduction of Mesozoic marine sulfate by thermochemical sulfate reduction or bacterially mediated processes at a different time or place from ore deposition. The large range of δ³⁴S values determined for the minerals in the deposit (12.2–19.2‰ for barite, 3.8–13.8‰ for sphalerite and galena, and 8.7 to ?21.2‰ for pyrite), are best explained by the mixing of fluids containing different sources of sulfur. Geochemical reaction path calculations, based on quantitative fluid inclusion data and constrained by field observations, were used to evaluate possible precipitation mechanisms. The most important precipitation mechanism was probably the mixing of fluids containing different metal and reduced sulfur contents. Cooling, dilution, and changes in pH of the ore fluid probably played a minor role in the precipitation of ores. The optimum results that produced the most metal sulfide deposition with the least amount of fluid was the mixing of a fluid containing low amounts of reduced sulfur with a sulfur‐rich, metal poor fluid. In this scenario, large amounts of sphalerite and galena are precipitated, together with smaller quantities of pyrite precipitated and dolomite dissolved. The relative amounts of metal precipitated and dolomite dissolved in this scenario agree with field observations that show only minor dolomite dissolution during ore deposition. The modeling results demonstrate the important control of the reduced sulfur concentration on the Zn and Pb transport capacity of the ore fluid and the volumes of fluid required to form the deposit. The studies of the Trèves ores provide insights into the ore‐forming processes of a typical MVT deposit in the Cévennes region. However, the extent to which these processes can be extrapolated to other MVT deposits in the Cévennes region is problematic. Nevertheless, the evidence for the extensive migration of fluids in the basement and sedimentary cover rocks in the Cévennes region suggests that the ore forming processes for the Trèves deposit must be considered equally viable possibilities for the numerous fault‐controlled and mineralogically similar MVT deposits in the Cévennes region.     

Isotopic and petrological evidence of fluid–rock interaction at a Tethyan ocean–continent transition in the Alps: implications for tectonic processes and carbon transfer during early ocean formation

We report overprinting stable isotope evidence of fluid–rock interaction below two detachment faults along which mantle rocks were exhumed to the seafloor, between the respective landward and seaward limits of oceanic and continental crust, at a Tethyan ocean–continent transition (OCT). This OCT, which is presently exposed in the Tasna nappe (south‐eastern Switzerland) is considered an on‐land analogue of the well‐studied Iberian OCT. We compare our results with the fault architecture (fault core–damage zone–protolith) described by Caine et al. [Geology (1996) Vol. 24, pp. 1025–1028]. We confirm the existence of a sharp boundary between the fault core and damage zone based on isotopic data, but the boundary between the damage zone and protolith is gradational. We identify evidence for: (1) pervasive isotopic modification to 8.4 ± 0.1‰ which accompanied or post‐dated serpentinization of these mantle rocks at an estimated temperature of 67–109°C, (2) either (i) partial isolation of some highly strained regions [fault core(s) and mylonite] from this pervasive isotopic modification, because of permeability reduction (Caine et al.) or (ii) subsequent isotopic modification caused by structurally channelled flow of warm fluids within these highly strained regions, because of permeability enhancement, and (3) isotopic modification, which is associated with extensive calcification at T = 54–100°C, primarily beneath the younger of the two detachment faults and post‐dating initial serpentinization. By comparing the volumetric extent of calcification with an experimentally verified model for calcite precipitation in veins, we conclude that calcification could have occurred in response to seawater infiltration, with a calculated flux rate of 0.1–0.2 m year^?1 and a minimum duration of 0.2–4.0 × 10⁴ years. The associated time‐averaged uptake flux of carbon during this period was 8–120 mol m^?2 year^?1. By comparison with the estimated area of exhumed mantle rocks at the Iberian OCT, we calculate a maximum annual uptake flux for carbon of 2–30 Tg year^?1. This is an order of magnitude greater than that for carbon exchange at the mid‐ocean ridges and 0.1–1.4% of the global oceanic uptake flux for carbon.     

High‐temperature magmatic fluid exsolved from magma at the Duobuza porphyry copper–gold deposit,Northern Tibet

The Duobuza porphyry copper–gold deposit (proven Cu resources of 2.7 Mt, 0.94% Cu and 13 t gold, 0.21 g t^?1 Au) is located at the northern margin of the Bangong‐Nujiang suture zone separating the Qiangtang and Lhasa Terranes. The major ore‐bearing porphyry consists of granodiorite. The alteration zone extends from silicification and potassic alteration close to the porphyry stock to moderate argillic alteration and propylitization further out. Phyllic alteration is not well developed. Sericite‐quartz veins only occur locally. High‐temperature, high‐salinity fluid inclusions were observed in quartz phenocrysts and various quartz veins. These fluid inclusions are characterized by sylvite dissolution between 180 and 360°C and halite dissolution between 240 and 540°C, followed by homogenization through vapor disappearance between 620 and 960°C. Daughter minerals were identified by SEM as chalcopyrite, halite, sylvite, rutile, K–feldspar, and Fe–Mn‐chloride. They indicate that the fluid is rich in ore‐forming elements and of high oxidation state. The fluid belongs to a complex hydrothermal system containing H₂O – NaCl – KCl ± FeCl₂ ± CaCl₂ ± MnCl₂. With decreasing homogenization temperature, the fluid salinity tends to increase from 34 to 82 wt% NaCl equiv., possibly suggesting a pressure or Cl/H₂O increase in the original magma. No coexisting vapor‐rich fluid inclusions with similar homogenization temperatures were found, so the brines are interpreted to have formed by direct exsolution from magma rather than trough boiling off of a low‐salinity vapor. Estimated minimum pressure of 160 MPa imply approximately 7‐km depth. This indicates that the deposit represents an orthomagmatic end member of the porphyry copper deposit continuum. Two key factors are proposed for the fluid evolution responsible for the large size of the gold‐rich porphyry copper deposit of Duobuza: (i) ore‐forming fluids separated early from the magma, and (ii) the hydrothermal fluid system was of magmatic origin and highly oxidized.     

3D numerical modeling of hydrothermal processes during the lifetime of a deep geothermal reservoir

Understanding hydrothermal processes during production is critical to optimal geothermal reservoir management and sustainable utilization. This study addresses the hydrothermal (HT) processes in a geothermal research doublet consisting of the injection well E GrSk3/90 and production well Gt GrSk4/05 at the deep geothermal reservoir of Groß Schönebeck (north of Berlin, Germany) during geothermal power production. The reservoir is located between ?4050 to ?4250 m depth in the Lower Permian of the Northeast German Basin. Operational activities such as hydraulic stimulation, production (T = 150°C; Q = ?75 m³ h^?1; C = 265 g l^?1) and injection (T = 70°C; Q = 75 m³ h^?1; C = 265 g l^?1) change the HT conditions of the geothermal reservoir. The most significant changes affect temperature, mass concentration and pore pressure. These changes influence fluid density and viscosity as well as rock properties such as porosity, permeability, thermal conductivity and heat capacity. In addition, the geometry and hydraulic properties of hydraulically induced fractures vary during the lifetime of the reservoir. A three‐dimensional reservoir model was developed based on a structural geological model to simulate and understand the complex interaction of such processes. This model includes a full HT coupling of various petrophysical parameters. Specifically, temperature‐dependent thermal conductivity and heat capacity as well as the pressure‐, temperature‐ and mass concentration‐dependent fluid density and viscosity are considered. These parameters were determined by laboratory and field experiments. The effective pressure dependence of matrix permeability is less than 2.3% at our reservoir conditions and therefore can be neglected. The results of a three‐dimensional thermohaline finite‐element simulation of the life cycle performance of this geothermal well doublet indicate the beginning of thermal breakthrough after 3.6 years of utilization. This result is crucial for optimizing reservoir management. Geofluids (2010) 10 , 406–421     

Analytical and numerical models of hydrothermal fluid flow at fault intersections

Fault intersections are the locus of hot spring activity and Carlin‐type gold mineralization within the Basin and Range, USA. Analytical and numerical solutions to Stokes equation suggest that peak fluid velocities at fault intersections increase between 20% and 47% when fracture apertures have identical widths but increase by only about 1% and 8% when aperture widths vary by a factor of 2. This suggests that fault zone intersections must have enlarged apertures. Three‐dimensional finite element models that consider intersecting 10‐ to 20‐m wide fault planes resulted in hot spring activity being preferentially located at fault zone intersections when fault zones were assigned identical permeabilities. We found that the onset of convection at the intersections of the fault zones occurred in our hydrothermal model over a narrow permeability range between 5 × 10^?13 and 7 × 10^?13 m². Relatively high vertical fluid velocities (0.3–3 m year^?1) extended away from the fault intersections for about 0.5–1.5 km. For the boundary conditions and fault plane dimensions used, peak discharge temperatures of 112°C at the water table occurred with an intermediate fault zone permeability of 5 × 10^?13 m². When fault plane permeability differed by a factor of 2 or more, the locus of hot spring activity shifted away from the intersections. However, increasing the permeability at the core of the fault plane intersection by 40% shifted the discharge back to the intersections. When aquifer units were assigned a permeability value equal to those of the fault planes, convective rolls developed that extend about 3 km laterally along the fault plane and into the adjacent aquifer.     

The link between fluids and rank variation in the South Wales Coalfield: evidence from fluid inclusions and stable isotopes

Fluid inclusion and stable isotope data from quartz and carbonate minerals in fracture fillings and ‘ironstone’ nodules from the South Wales Coalfield have been used to characterise the fluids generated during basin evolution and associated coalification. Carbonates grew first, probably at relatively shallow depths and low temperatures (<100°C). The carbonates exhibit a trend of increasing C‐isotopic values across the coalfield, ranging from δ¹³C = ?12‰ VPDB in the SE of the coalfield to 0‰ VPDB in the NW, possibly as a result of increasing methanogenesis in the deeper (NW) parts of the coalfield. Quartz formed at a later stage of basin formation, probably at temperatures between 150 and 200°C. Fluid inclusions in these minerals suggest that burial and coalification of the sediments were associated with mixed aqueous–petroleum fluids. Furthermore, the density of these petroleum fluids decreases towards the NW of the coalfield, where the rank of the associated coal increases to anthracite grade. The study confirms that the composition and temperature of these fluids closely correlate with the variations in coal rank, indicating a possible causal link. The data also give general support to models that propose regional fluid flow in the basin. and are consistent with the erosion of approximately 2 km of section which is not preserved today. A geothermal gradient (at maximum burial) of 45°C km^?1 is proposed, and thus no exceptionally anomalous thermal regime is required to explain coal rank variation.     

Hydraulic observations from a 1 year fluid production test in the 4000 m deep KTB pilot borehole

A long‐term pump test was conducted in the KTB pilot borehole (KTB‐VB), located in the Oberpfalz area, Germany. It produced 22 300 m³ of formation fluid. Initially, fluid production rate was 29 l min^?1 for 4 months, but was then raised to an average of 57 l min^?1 for eight more months. The aim of this study was to examine the fluid parameters and hydraulic properties of fractured, crystalline crusts as part of the new KTB programme ‘Energy and Fluid Transport in Continental Fault Systems’. KTB‐VB has an open‐hole section from 3850 to 4000 m depth that is in hydraulic contact with a prominent continental fault system in the area, called SE2. Salinity and temperature of the fluid inside the borehole, and consequently hydrostatic pressure, changed significantly throughout the test. Influence of these quantities on variations in fluid density had to be taken into account for interpretation of the pump test. Modelling of the pressure response related to the pumping was achieved assuming the validity of linear Darcy flow and permeability to be independent of the flow rate. Following the principle ‘minimum in model dimension’, we first examined whether the pressure response can be explained by an equivalent model where rock properties around the borehole are axially symmetric. Calculations show that the observed pressure data in KTB‐VB can in fact be reproduced through such a configuration. For the period of high pumping rate (57 l min^?1) and the following recovery phase, the resulting parameters are 2.4 × 10^?13 m³ in hydraulic transmissivity and 3.7 × 10^?9 m Pa^?1 in storativity for radial distances up to 187 m, and 4.7 × 10^?14 m³ and 6.0 × 10^?9 m Pa^?1, respectively, for radial distances between 187 and 1200 m. The former pair of values mainly reflect the hydraulic properties of the fault zone SE2. For a more realistic hydraulic study on a greater scale, program FEFLOW was used. Parameter values were obtained by matching the calculated induced pressure signal to fluid‐level variations observed in the KTB main hole (KTB‐HB) located at 200 m radial distance from KTB‐VB. KTB‐HB is uncased from 9031 to 9100 m and shows indications of leakage in the casing at depths 5200–5600 m. Analysis of the pressure record and hydraulic modelling suggest the existence of a weak hydraulic communication between the two boreholes, probably at depths around the leakage. Hydraulic modelling of a major slug‐test in KTB‐HB that was run during the pumping in KTB‐VB reveals the effective transmissivity of the connected formation to be 1 to 2 orders of magnitude lower than the one determined for the SE2 fault zone.