Pyrophyllite formation in the thermal aureole of a hydrothermal system in the Lower Saxony Basin,Germany

A combined clay mineralogical, fluid inclusion, and K‐Ar study of Upper Jurassic metasediments at the Gehn (Lower Saxony Basin, Germany) provides evidence for a transient hydrothermal event during Upper Cretaceous basin inversion centered on a prominent gravimetric anomaly. Kaolinite and smectite in Oxfordian pelitic parent rocks that cap a deltaic sandstone unit were locally transformed into pyrophyllite, 2M₁ illite, R3 illite–smectite, chlorite, and berthierine at the Ueffeln quarry. The pyrophyllite‐bearing metapelites lack bedding‐parallel preferred orientation of sheet silicates and experienced peak temperatures of about 260–270°C consistent with microthermometric data on quartz veins in the underlying silicified sandstones. The presence of expandable layers in illite–smectite and high Kübler Index values indicate that the thermal event was rather short‐lived. K‐Ar dating of the <0.2 μm fraction of the pyrophyllite‐bearing Ueffeln metapelite yields a maximum illitization age of 117 ± 2 Ma. Lower trapping temperatures of aqueous fluid inclusions in quartz veins and the absence of pyrophyllite in metapelites of the Frettberg quarry in a distance of about 2.5 km from the Ueffeln quarry infer maximum paleotemperatures of only 220°C. The highly localized thermal anomaly at Ueffeln suggests fault‐controlled fluid migration and heat transfer that provided a thermal aureole for pyrophyllite formation in the metapelites rather than metamorphism due to deep burial. A pH neutral hydrothermal fluid that formed by devolatilization reactions or less likely by mixing of meteoric and marine waters that interacted at depth with shales is indicated by the low salinity (3–5 wt. % NaCl equiv.) of aqueous inclusions, their coexistence with methane–carbon dioxide‐dominated gas inclusions as well as carbon, hydrogen, and oxygen isotope data. The upwelling zone of hydrothermal fluids and the thermal maximum is centered on a gravimetric anomaly interpreted as an igneous intrusion (‘Bramsche Massif’) providing the heat source for the intrabasinal hydrothermal system.     

Fracture mineralization and fluid flow evolution: an example from Ordovician–Devonian carbonates,southwestern Ontario,Canada

Petrography, geochemistry (stable and radiogenic isotopes), and fluid inclusion microthermometry of matrix dolomite, fracture‐filling calcite, and saddle dolomite in Ordovician to Devonian carbonates from southwestern Ontario, Canada, provide useful insights into fluid flow evolution during diagenesis. The calculated δ¹⁸O_fluid, ΣREE, and REE_SN patterns of matrix and saddle dolomite suggest diverse fluids were involved in dolomitization and/or recrystallization of dolomite. The ⁸⁷Sr/⁸⁶Sr ratios of dolomite of each succession vary from values in the range of coeval seawater to values more radiogenic than corresponding seawater, which indicate diagenetic fluids were influenced by significant water/rock interaction. High salinities (22.4–26.3 wt. % NaCl + CaCl₂) of Silurian and Ordovician dolomite–hosted fluid inclusions indicate involvement of saline waters from dissolution of Silurian evaporites. High fluid inclusion homogenization temperatures (>100°C) in all samples from Devonian to Ordovician show temperatures higher than maximum burial (60–90°C) of their host strata and suggest involvement of hydrothermal fluids in precipitation and/or recrystallization of dolomite. A thermal anomaly over the mid‐continent rift during Devonian to Mississippian time likely was the source of excess heat in the basin. Thermal buoyancy resulting from this anomaly was the driving force for migration of hydrothermal fluids through regional aquifers from the center of the Michigan Basin toward its margin. The decreasing trend of homogenization temperatures from the basin center toward its margin further supports the interpreted migration of hydrothermal fluids from the basin center toward its margin. Hydrocarbon‐bearing fluid inclusions in late‐stage Devonian to Ordovician calcite cements with high homogenization temperatures (>80°C) and their ¹³C‐depleted values (approaching ?32‰ PDB) indicate the close relationship between hydrothermal fluids and hydrocarbon migration.     

Linked thermal convection of the basement and basinal fluids in formation of the unconformity‐related uranium deposits in the Athabasca Basin,Saskatchewan, Canada

World‐class unconformity‐related U deposits in the Athabasca Basin (Saskatchewan, Canada) are generally located within or near fault zones that intersect the unconformity between the Athabasca Group sedimentary basin rocks and underlying metamorphic basement rocks. Two distinct subtypes of unconformity‐related uranium deposits have been identified: those hosted primarily in the Athabasca Group sandstones (sediment‐hosted) and those hosted primarily in the underlying basement rocks (basement‐hosted). Although significant research on these deposits has been carried out, certain aspects of their formation are still under discussion, one of the main issues being the fluid flow mechanisms responsible for uranium mineralization. The intriguing feature of this problem is that sediment‐hosted and basement‐hosted deposits are characterized by oppositely directed vectors of fluid flow via associated fault zones. Sediment‐hosted deposits formed via upward flow of basement fluids, basement‐hosted deposits via downward flow of basinal fluids. We have hypothesized that such flow patterns are indicative of the fluid flow self‐organization in fault‐bounded thermal convection (Transport in Porous Media, 110, 2015, 25). To explore this hypothesis, we constructed a simplified hydrogeologic model with fault‐bounded thermal convection of fluids in the faulted basement linked with fluid circulation in the overlying fault‐free sandstone horizon. Based on this model, a series of numerical experiments was carried out to simulate the hypothesized fluid flow patterns. The results obtained are in reasonable agreement with the concept of fault‐bounded convection cells as an explanation of focused upflow and downflow across the basement/sandstone unconformity. We then discuss application of the model to another debated problem, the uranium source for the ore‐forming basinal brines.     

Downward hydrocarbon migration predicted from numerical modeling of fluid overpressure in the Paleozoic Anticosti Basin,eastern Canada

The Anticosti Basin is a large Paleozoic basin in eastern Canada where potential source and reservoir rocks have been identified but no economic hydrocarbon reservoirs have been found. Potential source rocks of the Upper Ordovician Macasty Formation overlie carbonates of the Middle Ordovician Mingan Formation, which are underlain by dolostones of the Lower Ordovician Romaine Formation. These carbonates have been subjected to dissolution and dolomitization and are potential hydrocarbon reservoirs. Numerical simulations of fluid‐overpressure development related to sediment compaction and hydrocarbon generation were carried out to investigate whether hydrocarbons generated in the Macasty Formation could migrate downward into the underlying Mingan and Romaine formations. The modeling results indicate that, in the central part of the basin, maximum fluid overpressures developed above the Macasty Formation due to rapid sedimentation. This overpressured core dissipated gradually with time, but the overpressure pattern (i.e. maximum overpressure above source rock) was maintained during the generation of oil and gas. The downward impelling force associated with fluid‐overpressure gradients in the central part of the basin was stronger than the buoyancy force for oil, whereas the buoyancy force for gas and for oil generated in the later stage of the basin is stronger than the overpressure‐related force. Based on these results, it is proposed that oil generated from the Macasty Formation in the central part of the basin first moved downward into the Mingan and Romaine formations, and then migrated laterally up‐dip toward the basin margin, whereas gas throughout the basin and oil generated in the northern part of the basin generally moved upward. Consequently, gas reservoirs are predicted to occur in the upper part of the basin, whereas oil reservoirs are more likely to be found in the strata below the source rocks. Geofluids (2010) 10 , 334–350     

Basin‐scale fluid movement patterns revealed by veins: Wessex Basin,UK

Calcite veins at outcrop in the Mesozoic, oil‐bearing Wessex Basin, UK, have been studied using field characterization, petrography, fluid inclusions and stable isotopes to help address the extent, timing and spatial and stratigraphic variability of basin‐scale fluid flow. The absence of quartz shows that veins formed at low temperature without an influence of hydrothermal fluids. Carbon isotopes suggest that the majority of vein calcite was derived locally from the host rock but up to one quarter of the carbon in the vein calcite came from CO₂ from petroleum source rocks. Veins become progressively enriched in source‐rock‐derived CO₂ from the outer margin towards the middle, indicating a growing influence of external CO₂. The carbon isotope data suggest large‐scale migration of substantial amounts of CO₂ around the whole basin. Fluid inclusion salinity data and interpreted water‐δ¹⁸O data show that meteoric water penetrated deep into the western part of the basin after interacting with halite‐rich evaporites in the Triassic section before entering fractured Lower and Middle Jurassic rocks. This large‐scale meteoric invasion of the basin probably happened during early Cenozoic uplift. A similar approach was used to reveal that, in the eastern part of the basin close to the area that underwent most uplift, uppermost Jurassic and Cretaceous rocks underwent vein formation in the presence of marine connate water suggesting a closed system. Stratigraphically underlying Upper Jurassic mudstone and Lower Cretaceous sandstone, in the most uplifted part of the basin, contain veins that resulted from intermediate behaviour with input from saline meteoric water and marine connate waters. Thus, while source‐rock‐derived CO₂ seems to have permeated the entire section, water movement has been more restricted. Oil‐filled inclusions in vein calcite have been found within dominant E‐W trending normal faults, suggesting that these may have facilitated oil migration.     

Thermal waters of ‘tectonic origin’: the alkaline,Na‐HCO3 waters of the Rio Valdez geothermal area (Isla Grande de Tierra del Fuego,Argentina)

The geothermal area of Rio Valdez is located in the central portion of the Isla Grande de Tierra del Fuego (South Argentina), ten kilometers south of the southeastern sector of the Fagnano Lake. It consists of a series of thermal springs with low discharge rates (≤1 L/s) and temperatures in the range of 20–33°C distributed in an area of <1 km². The thermal springs are characterized by alkaline, Na‐HCO₃ waters with low salinity (0.53÷0.58 g/L), but relatively high fluoride contents (up to 19.4 mg/L). Their composition is the result of a slow circulation at depth, possibly through deep tectonic discontinuities connected with the Magallanes‐Fagnano Fault (MFF) system. According to geothermometric calculations, thermal waters reach temperatures in the range of 100–150°C and an almost complete chemical equilibrium with the alkali‐feldspars in the metavolcanic country rocks. The relatively high fluorine contents can be explained by the slow ascent and cooling of deep groundwaters followed by a progressive re‐equilibration with F‐bearing, hydrated Mg‐silicates, such as chlorite, which has been recognized as an abundant mineral in the metavolcanics of the Lemaire Formation and metapelites and metagraywackes of the Yahgán Formation. Finally, the isotopic composition of the investigated samples is consistent with the infiltration from local snow melting at altitudes in the range of 610–770 m asl. The comparison of our data with those collected in 1991 seems to suggest a possible progressive decline of the bulk thermal output in the near future. This possibility should be seriously considered before planning a potentially onerous exploitation of the resource. Presently, the only ways to exploit this geothermal resource by the population scattered in the area are the direct use of thermal waters and/or spa structures.     

Episodic fluid flow within continental rift basins: some insights from field data and mathematical models of the Rhinegraben

Vitrinite reflectance data from a petroleum exploration well in the northern Upper Rhinegraben show an unusual vertical maturity trend. Above and below a 500 m thick marl layer the vitrinite reflectance levels are consistent with modern, conductive, geothermal gradients. Between about 1000 and 1500 m depth, however, vitrinite reflectance levels are significantly elevated (about 0.6%Ro). This anomaly cannot be explained with one‐dimensional conductive or conductive–convective heat transfer models, and thermal effects of sedimentation or igneous intrusion seem implausible for this geological setting. The thermal anomaly that formed this maturation anomaly must have been hydrothermal in origin, two‐dimensional in nature, and persisted long enough to elevate the vitrinite reflectance values within this marl unit, yet it must have dissipated before the thermal perturbation would have altered the organic matter below and above the unit. In this study, we propose that the vitrinite reflectance anomalies were caused by a transient thermal inversion induced by episodic, lateral flow of hot (130–160°C) groundwater along conductive fractures and bedding planes. Heat flow constraints suggest that fluids must have moved rapidly up a vertical feeder fault from a depth of at least 3.6 km before migrating laterally. To test this hypothesis, we present a suite of simple, idealized mathematical models of groundwater flow, heat transfer, thermal degradation of kerogen and vitrinite systematics to explore the episodic flow that could have produced the observed thermal anomaly. In these simulations, a single, horizontal aquifer is sandwiched between two less permeable units: the total dimensions of the vertical section model are 4 km thick by 10 km long. The top of the aquifer coincides with the position of the observed thermal maturity anomaly in the Rhinegraben. Boundary conditions along the left edge of this aquifer were varied through time to allow for the migration of hot fluids out into the basin. Inflow temperature, horizontal velocity, duration and frequency of flow and thickness of the aquifer were varied. We found that a thermal maturity anomaly could only be produced by a rather restrictive set of hydrothermal conditions. It was possible to produce the observed vitrinite reflectance anomaly by a single hydrothermal flow event of 130°C fluid migrating laterally into the aquifer at a rate of 1 m a^?1 for about 10 000 years. The anomaly is spatially confined to near the left edge of the basin, near the feeder fault. If the flow event lasted longer than 100 000 years, then the maturation anomaly disappeared as the lower confining unit approached steady‐state thermal conditions. It is possible that such an event occurred about 5 million years ago in response to increases in fault permeability associated with far field Alpine tectonism.     

Modeling thermal convection in supradetachment basins: example from western Norway

The juxtaposition of fault‐bounded sedimentary basins, above crustal‐scale detachments, with warmer exhumed footwalls can lead to thermal convection of the fluids in the sediments. The Devonian basins of western Norway are examples of supradetachment basins that formed in the hanging wall of the Nordfjord‐Sogn Detachment Zone. In the central part of the Hornelen and Kvamshesten basins, the basin‐fill is chiefly represented by fluvial sandstones and minor lacustrine siltstones, whereas the fault margins are dominated by fanglomerates along the detachment contact. Prominent alteration and low‐greenschist facies metamorphic conditions are associated with the peak temperature estimates of the sediments close to the detachment shear zone. Fluid circulation may have been active during the burial of the sediments, and we quantify the potential role played by thermal convection in redistributing heat within the basins. Different models are tested with homogeneous and layered basin‐fill and with material transport properties corresponding to sandstones and siltstones. We found that thermally driven fluid flow is expected in supradetachment basins as a transient process during the exhumation of warmer footwalls. We demonstrate that the fluid flow may have significantly affected the temperature distribution in the upper five kilometers of the Devonian basins of western Norway. The temperature anomaly induced by the flow may locally reach about 80°C. The sedimentary layering formed by sand‐ and siltstones strata does not inhibit fluid circulation at the scale of the basin. The presence of fluid pathways along the detachment has an important impact on the flow and allows an efficient drainage of the basin by channelizing fluids upward along the detachment.     

The hydrogeochemistry of subsurface brines in and west of the Jordan–Dead Sea Transform fault

This study is based on 113 analyses of brines with Cl > 0.57 mol l^?1 (modern seawater), which were collected and analysed mostly during several decades of exploration for gas and oil in Israel. Based on critical evaluation of correlations of elements and ionic ratios and on spider patterns, six different brine events or source brines were identified in the Phanerozoic: the Triassic, Lower Cretaceous and the Mio/Pliocene brine families which were identified in boreholes Sdom‐1, Sdom Deep‐1 and Ha'on, and the Holocene Dead Sea brines. The Triassic brines are nowadays also encountered in under‐ and overlying rock units such as the Paleozoic Negev‐Yam Suf and the Jurassic Arad Groups, respectively. The southern Jordan–Dead Sea Transform (also known as the Rift) hosts the Mio‐Pliocene Sdom Deep and Sdom brine families. Brine bodies not sufficiently isolated by impervious sedimentary layers were flushed out during the Pliocene when the southern Valley drained north‐ and westwards through the Yizre'el Valley to the Mediterranean Sea. In the northern Rift Miocene to Pliocene seawater evaporated and infiltrated into the Rift sediments and into adjacent rocks. Further diluted by freshwater, it emerges as the Ha'on brine. Together with its derivatives, they form the Ha'on family. The derivatives of the Holocene Dead Sea brine family occur along the shoreline of the recent Dead Sea. Apart of all these evaporation brines, brines deriving from dissolution of evaporites locally occur in the area. The time‐bound chemical composition of paleoseawater is considered when discussing the ionic ratios of brines generated during different geological periods. Spider patterns of each brine family are compared and, where necessary, the relationship of brines to distinct families of brines is supported by inverse modelling.     

Barite–pyrite mineralization of the Wiesbaden thermal spring system, Germany: a 500-kyr record of geochemical evolution

Barite–(pyrite) mineralizations from the thermal springs of Wiesbaden, Rhenish Massif, Germany, have been studied to place constraints on the geochemical evolution of the hydrothermal system in space and time. The thermal springs, characterized by high total dissolved solids (TDS) contents and predominance of NaCl, ascend from aquifers at 3–4 km depth and discharge at a temperature of 65–70°C. The barite–(pyrite) mineralization is found in upflow and discharge zones of the present‐day thermal springs as well as at elevations up to 50 m above the current water table. Hence, this mineralization style constitutes a continuous record of the hydrothermal activity, linking the past evolution with the present state of this geothermal system. The sulphur isotope signatures of the mineralization indicate a continuous decrease of the δ³⁴S of sulphate from +16.9‰ in the oldest barite to +10.1‰ in the present‐day thermal water. The δ³⁴S values of barite closely resemble various recently active thermal springs along the southern margin of the Rhenish Massif and contrast strongly with different regional ground and mineral waters. The mineralogical and isotopic signatures, combined with calculations based on uplift rates and the regional geological history, indicate a minimum activity of the thermal spring system at Wiesbaden of about 500 000 years. This timeframe is considerably larger than conservative models, which estimate the duration of thermal spring systems in continental intraplate settings to last for several 10 000 years. The calculated equilibrium sulphur isotope temperatures of coexisting barite and pyrite range between 65 and 80°C, close to the discharge temperature of the springs, which would indicate apparent equilibrium precipitation. Kinetic modelling of the re‐equilibration of the sulphate–sulphide pair during water ascent shows that this process would require 220 Myr. Therefore, we conclude that pyrite is formed from precursor Fe monosulphide phases, which rapidly precipitate in the near‐surface environment, preserving the isotope fractionation between dissolved sulphate and sulphide established in the deep aquifer. Equilibrium modelling of water–mineral reactions shows slight supersaturation of barite at the discharge temperature. Pyrite is already strongly supersaturated at the temperatures estimated for the aquifer (110°C) and processes in the near‐surface environment are most probably related to contact of the thermal water with atmospheric oxygen, resulting in formation of oxidized intermediate sulphur species and precipitation of Fe monosulphide phases, which subsequently recrystallize to pyrite.     

Role of compressive tectonics on gas charging into the Ordovician sandstone reservoirs in the Sbaa Basin,Algeria: constrained by fluid inclusions and mineralogical data

Structure‐ and tectonic‐related gas migration into Ordovician sandstone reservoirs and its impact on diagenesis history were reconstructed in two gas fields in the Sbaa Basin, in SW Algeria. This was accomplished by petrographical observations, fluid inclusion microthermometry and stable isotope geochemistry on quartz, dickite and carbonate cements and veins. Two successive phases of quartz cementation (CQ1 and CQ2) occurred in the reservoirs. Two phase aqueous inclusions show an increase in temperatures and salinities from the first CQ1 diagenetic phase toward CQ2 in both fields. Microthermometric data on gas inclusions in quartz veins reveal the presence of an average of 92 ± 5 mole% of CH₄ considering a CH₄‐CO₂ system, which is similar to the present‐day gas composition in the reservoirs. The presence of primary methane inclusions in early quartz overgrowths and in quartz and calcite veins suggests that hydrocarbon migration into the reservoir occurred synchronically with early quartz cementation in the sandstones located near the contact with the Silurian gas source rock at 100–140°C during the Late Carboniferous period and the late Hercynian episode fracturing at temperatures between 117 and 185°C, which increased in the NW‐direction of the basin. During the fracture filling, three main types of fluids were identified with different salinities and formation temperatures. A supplementary phase of higher fluid temperature (up to 226°C) recorded in late quartz, and calcite veins is related to a Jurassic thermal event. The occurrence of dickite cements close to the Silurian base near the main fault areas in both fields is mainly correlated with the sandstones where the early gas was charged. It implies that dickite precipitation is related to acidic influx. Late carbonate cements and veins (calcite – siderite – ankerite and strontianite) occurred at the same depths resulting from the same groundwater precipitation. The absence of methane inclusions in calcite cements result from methane flushing by saline waters.     

Sources and composition of fluids associated with fluorite deposits of Asturias (N Spain)

The fluorite deposits of Asturias (northern Iberian Peninsula) are hosted by rocks of Permo‐Triassic and Palaeozoic age. Fluid inclusions in ore and gangue minerals show homogenization temperatures from 80 to 170°C and the presence of two types of fluids: an H₂O–NaCl low‐salinity fluid (<8 eq. wt% NaCl) and an H₂O–NaCl–CaCl₂ fluid (7–13 wt% NaCl and 11–14 wt% CaCl₂). The low salinity and the Cl/Br and Na/Br ratios (Cl/Br_molar 100–700 and Na/Br_molar 20–700) are consistent with an evaporated sea water origin of this fluid. The other end‐member of the mixture was highly saline brine with high Cl/Br and Na/Br ratios (Cl/Br_molar 700–13 000 and Na/Br_molar 700–11 000) generated after dissolution of Triassic age evaporites. LA‐ICP‐MS analyses of fluid inclusions in fluorite reveal higher Zn, Pb and Ba contents in the high‐salinity fluids (160–500, 90–170, 320–480 p.p.m. respectively) than in the low‐salinity fluid (75–230, 25–150 and 100–300 p.p.m. respectively). The metal content of the fluids appears to decrease from E to W, from Berbes to La Collada and to Villabona. The source of F is probably related to leaching of volcanic rocks of Permian age. Brines circulated along faults into the Palaeozoic basement. Evaporated sea water was present in permeable rocks and faults along or above the unconformity between the Permo‐Triassic sediments and the Palaeozoic basement. Mineralization formed when the deep brines mixed with the surficial fluids in carbonates, breccias and fractures resulting in the formation of veins and stratabound bodies of fluorite, barite, calcite, dolomite and quartz and minor amounts of sulphides. Fluid movement and mineralization occurred between Late Triassic and Late Jurassic times, probably associated with rifting events related to the opening of the Atlantic Ocean. This model is also consistent with the geodynamic setting of other fluorite‐rich districts in Europe.     

Infiltration of basinal fluids into high-grade basement, South Norway: sources and behaviour of waters and brines

Quartz veins hosted by the high‐grade crystalline rocks of the Modum complex, Southern Norway, formed when basinal fluids from an overlying Palaeozoic foreland basin infiltrated the basement at temperatures of c. 220°C (higher in the southernmost part of the area). This infiltration resulted in the formation of veins containing both two‐phase and halite‐bearing aqueous fluid inclusions, sometimes with bitumen and hydrocarbon inclusions. Microthermometric results demonstrate a very wide range of salinities of aqueous fluids preserved in these veins, ranging from c. 0 to 40 wt% NaCl equivalent. The range in homogenization temperatures is also very large (99–322°C for the entire dataset) and shows little or no correlation with salinity. A combination of aqueous fluid microthermometry, halogen geochemistry and oxygen isotope studies suggest that fluids from a range of separate aquifers were responsible for the quartz growth, but all have chemistries comparable to sedimentary formation waters. The bulk of the quartz grew from relatively low δ¹⁸O fluids derived directly from the basin or equilibrated in the upper part of the basement (T < 200°C). Nevertheless, some fluids acquired higher salinities due to deep wall‐rock hydration reactions leading to salt saturation at high temperatures (>300°C). The range in fluid inclusion homogenization temperatures and densities, combined with estimates of the ambient temperature of the basement rocks suggests that at different times veins acted as conduits for influx of both hotter and colder fluids, as well as experiencing fluctuations in fluid pressure. This is interpreted to reflect episodic flow linked to seismicity, with hotter dry basement rocks acting as a sink for cooler fluids from the overlying basin, while detailed flow paths reflected local effects of opening and closing of individual fractures as well as reaction with wall rocks. Thermal considerations suggest that the duration of some flow events was very short, possibly in the order of days. As a result of the complex pattern of fracturing and flow in the Modum basement, it was possible for shallow fluids to penetrate basement rocks at significantly higher temperatures, and this demonstrates the potential for hydrolytic weakening of continental crust by sedimentary fluids.     

Secular variations in seawater chemistry as a control on the chemistry of basinal brines: test of the hypothesis

The hypothesis that basinal brines inherited their major ion chemistries and elevated salinities from evaporated paleoseawaters is tested by comparing the compositions of basinal brines in Silurian (Michigan basin, Illinois basin, Appalachian basin in eastern Ohio) and Jurassic/Cretaceous (Central Mississippi Salt Dome basin, Arkansas shelf, and south‐central Texas) host rocks, when the world oceans were ‘CaCl₂ seas’, with those from Permian and Pennsylvanian rocks (Palo Duro basin, Central Basin Platform, and Delaware basin, Texas and New Mexico) when the world oceans were ‘MgSO₄ seas’. Basinal brines examined are assumed to have originally formed from evaporation of the same seawaters that produced major evaporites. Sulfate, Mg and K levels in basinal brines are below the concentrations expected from evaporation of seawater of any type, which emphasizes the importance of diagenetic mineral–brine interactions in controlling basinal brine chemistry. There are no major differences in SO₄, Mg and K concentrations between basinal brines hosted by rocks originally formed during ages when the world oceans were MgSO₄ seas versus CaCl₂ seas. Basinal brines in Pennsylvanian–Permian rocks are compositionally distinct (relatively high Na and low Ca) from basinal brines in Silurian, Jurassic and Cretaceous host rocks, which may reflect original differences in seawater chemistry. Basinal brines enriched in Ca and depleted in Na relative to evaporated seawater of any type have traditionally been interpreted to form by albitization of plagioclase feldspar. A new explanation for Ca enrichment and Na depletion of basinal brines is the mixing of evaporated CaCl₂‐type seawater with more dilute water. Some basinal brines are similar in major ion composition to evaporated seawater of a particular age, for example basinal brines in the Cretaceous Edwards Group carbonates, Texas, where dolomitization is the only reaction required to convert evaporated Mesozoic CaCl₂ seawater into Edwards Group brine.     

Measurements of gas permeability and diffusivity of tight reservoir rocks: different approaches and their applications

Permeability and diffusivity are critical parameters of tight reservoir rocks that determine their viability for commercial development. Current methods for measuring permeability and/or diffusivity may lead to erroneous results when applied to very tight rocks including gas shales, coal, and tight gas sands, as well as rocks considered as seals for nuclear waste repositories and strata for geological sequestration of CO₂. The use of He as routinely applied to measure porosity, permeability, and diffusivity may result in non-systematic errors because of the molecular sieving effect of the fine pore structure to larger molecules such as reservoir gases. Utilizing gases with larger adsorption potentials than He, such as N₂, and including all reservoir gases to measure porosity or permeability of rocks with high surface area is a viable alternative, but requires correcting for adsorption in the analyses. This study expands several approaches to measure permeability and diffusivity with considerations for gas adsorption, which has not been explicitly considered in previous studies. We present new models that explicitly correct for adsorption during pulse-decay measurements of core under reservoir conditions, as well as on crushed samples used to approximate permeability or diffusivity. We also present a method to determine permeability or diffusivity from on-site drill-core desorption test data as carried out to determine gas in place in coals or gas shales. Our new approach utilizes late-time data from experimental pressure-decay tests, which we show to be more reliable and theoretically (and practically) accurate than the early-time approach commonly used to estimate gas-transport properties.     

Regional groundwater flow and interactions with deep fluids in western Apennine: the case of Narni‐Amelia chain (Central Italy)

The elemental fluxes and heat flow associated with large aquifer systems can be significant both at local and at regional scales. In fact, large amounts of heat transported by regional groundwater flow can affect the subsurface thermal regime, and the amount of matter discharged towards the surface by large spring systems can be significant relative to the elemental fluxes of surface waters. The Narni‐Amelia regional aquifer system (Central Italy) discharges more than 13 m³ sec^?1 of groundwater characterised by a slight thermal anomaly, high salinity and high pCO₂. During circulation in the regional aquifer, groundwater reacts with the host rocks (dolostones, limestones and evaporites) and mixes with deep CO₂‐rich fluids of mantle origin. These processes transfer large amounts of dissolved substances, in particular carbon dioxide, and a considerable amount of heat towards the surface. Because practically all the water circulating in the Narni‐Amelia system is discharged by few large springs (Stifone‐Montoro), the mass and energy balance of these springs can give a good estimation of the mass and heat transported from the entire system towards the surface. By means of a detailed mass and balance of the aquifer and considering the soil CO₂ fluxes measured from the main gas emission of the region, we computed a total CO₂ discharge of about 7.8 × 10⁹ mol a^?1 for the whole Narni‐Amelia system. Finally, considering the enthalpy difference between infiltrating water and water discharged by the springs, we computed an advective heat transfer related to groundwater flow of 410 ± 50 MW.     

Quantitative estimation of overpressure caused by gas generation and application to the Baiyun Depression in the Pearl River Mouth Basin,South China Sea

Hydrocarbon generation can yield high fluid pressures in sedimentary basins as the conversion of solid kerogen to hydrocarbons can result in an increase in fluid volume. To quantify the relationship between gas generation and overpressure in source rocks, a set of equations for computing the pressure change due to gas generation has been derived. Those equations can be used to quantitatively estimate overpressure generated by type III kerogen in source rocks by considering gas generation and leakage, gas dissolution in formation water and residual oil, thermal cracking of oil to gas, and hydrocarbon episodic expulsion from source rocks. The equations also take consideration of other factors including source rock porosity, transformation ratio, total organic carbon (TOC), hydrogen index, and compressibility of kerogen, oil, and water. As both oil and gas are taken into account in the equations, they can also be used to estimate the evolution of overpressure caused by hydrocarbon generation of type I and type II kerogen source rocks. Sensitivity analyses on the type III kerogen source rock indicate that hydrogen index is the most influential parameter for overpressure generation, while TOC and residual gas coefficient (β: ratio of residual gas over the total gas generated) have a moderate effect. Overpressure can be generated even if the gas leakage/loss in the source rock is up to 80% of the total gas generated. This suggests that the internal pressure seal of the source rock is not a critical factor on the pressure change as long as the source rocks are capable of sealing liquid oil. The equations were applied to evaluate the overpressure in the Eocene–Oligocene Enping Formation source rocks due to hydrocarbon generation in the Baiyun Depression, the Pearl River Mouth Basin by considering the source rock properties, hydrocarbon generation history, and hydrocarbon expulsion timing. Two episodes of overpressure development due to gas generation and release were modeled to have occurred in the Enping Formation source rock since 16 Ma. The overpressure release at 10.2–5.3 Ma via hydrocarbon expulsion was apparently related to the Dongsha phase of tectonic deformation, whereas the pressure release at 2–0 Ma was due to pressure generation that was exceeded the fracture‐sealing pressure in the source rocks.     

Dissolved gases in brackish thermal waters: an improved analytical method

An improved method based on equilibrium partitioning between water samples and an inert host gas, introduced after sampling, is proposed for determining multiple species of dissolved gases in brackish water. The method itself, and the most convenient equations for describing gas solubilities in brackish waters, is described in detail. The method allows the rapid characterization of several sites and represents a useful tool for geochemical surveys. A comparison between replicate samples analyzed using different procedures demonstrates the efficiency of the method and indicates that the abundances of the main dissolved gases can be obtained, which can then be used to determine underlying geochemical processes. A Microsoft Excel worksheet is provided to easily calculate the concentration of dissolved gas species.     

Re‐equilibration of fluid inclusions in diagenetic‐anchizonal rocks of the Ciñera‐Matallana coal basin (NW Spain)

Thermally re‐equilibrated fluid inclusions are reported in natural fissure quartz (qtz1) from polymineralic veins in the diagenetic‐anchizonal clastic sedimentary rocks of the Ciñera‐Matallana coal basin (Variscan, NW Spain). Euhedral quartz formed during early fissure opening from an immiscible fluid mixture composed of a low salinity aqueous solution and a CH₄‐rich vapour phase, at temperatures of about 110–120°C and pressures ranging from 15 to 56 MPa. Five textural types of re‐equilibration are recognised in progressive order of inclusion modification: scalloped, hairy, annular‐ring shaped, haloes and decrepitation clusters. These textures resulted from a combination of brittle fracturing and dissolution and re‐precipitation of quartz, with preferential loss of water. The thermal peak was short‐lived, but was high enough to induce extensive decrepitation of fluid inclusions in vein quartz throughout the entire basin. Enhanced temperatures can be related to the intrusion of diorites in the basin. Careful analysis of textural features in fluid inclusions from diagenetic and very low‐grade metamorphism environments constitutes a useful tool for recording basin thermal history.     

Real‐time mud gas logging and sampling during drilling

Continuous mud gas loggings during drilling as well as offline mud gas sampling are standard procedures in oil and gas operations, where they are used to test reservoir rocks for hydrocarbons while drilling. Our research group has developed real‐time mud gas monitoring techniques for scientific drilling in non‐hydrocarbon formations mainly to sample and study the composition of crustal gases. We describe in detail this technique and provide examples for the evaluation of the continuous gas logs, which are not always easy to interpret. Hydrocarbons, helium, radon and with limitations carbon dioxide and hydrogen are the most suitable gases for the detection of fluid‐bearing horizons, shear zones, open fractures, sections of enhanced permeability and permafrost methane hydrate occurrences. Off‐site isotope studies on mud gas samples helped reveal the origin and evolution of deep‐seated crustal fluids.