Equations of state for basin geofluids: algorithm review and intercomparison for brines

Physical properties of formation waters in sedimentary basins can vary by more than 25% for density and by one order of magnitude for viscosity. Density differences may enhance or retard flow driven by other mechanisms and can initiate buoyancy‐driven flow. For a given driving force, the flow rate and injectivity depend on viscosity and permeability. Thus, variations in the density and viscosity of formation waters may have or had a significant effect on the flow pattern in a sedimentary basin, with consequences for various basin processes. Therefore, it is critical to correctly estimate water properties at formation conditions for proper representation and interpretation of present flow systems, and for numerical simulations of basin evolution, hydrocarbon migration, ore genesis, and fate of injected fluids in sedimentary basins. Algorithms published over the years to calculate water density and viscosity as a function of temperature, pressure and salinity are based on empirical fitting of laboratory‐measured properties of predominantly NaCl solutions, but also field brines. A review and comparison of various algorithms are presented here, both in terms of applicability range and estimates of density and viscosity. The paucity of measured formation‐water properties at in situ conditions hinders a definitive conclusion regarding the validity of any of these algorithms. However, the comparison indicates the versatility of the various algorithms in various ranges of conditions found in sedimentary basins. The applicability of these algorithms to the density of formation waters in the Alberta Basin is also examined using a high‐quality database of 4854 water analyses. Consideration is also given to the percentage of cations that are heavier than Na in the waters.     

Topography‐driven flow versus buoyancy‐driven flow in the U.S. midcontinent: implications for the residence time of brines

Topography‐driven flow is normally considered to be the dominant groundwater flow system in uplifted sedimentary basins. In the U.S. midcontinent region east of the Rocky Mountains, the presence of brines derived from dissolution of halite suggests that significant topography‐driven flushing has occurred to remove older brines that presumably formed concurrently with Permian evaporites in the basin. However, the presence of evaporites and brines in the modern basin suggests that buoyancy‐driven flow could limit topography‐driven flushing significantly. Here we used numerical models of variable‐density fluid flow, halite dissolution, solute transport, and heat transport to quantify flow patterns and brine migration. Results indicate the coexistence of large‐scale topography‐ and buoyancy‐driven flow. Buoyancy‐driven flow and low permeability evaporites act to isolate brines, and the residence time of the brines was found to be quite long, at least 50 Myr. The modern distribution of salinity appears to reflect near‐steady‐state conditions. Results suggest that flushing of original evaporatively‐concentrated brines occurred tens of millions of years ago, possibly concurrent with maximum uplift ca. 60 Ma. Simulations also suggest that buoyancy‐driven convection could drive chemical exchange with crystalline basement rocks, which could supply significant Ca²⁺, Sr²⁺, and metals to brines.     

Diverse origins and timing of formation of basinal brines in the Gulf of Mexico sedimentary basin

A review of five different field areas in the Gulf of Mexico sedimentary basin (GOM) illustrates some of the potentially diverse chemical and physical processes which have produced basinal brines. The elevated salinities of most of the formation waters in the GOM are ultimately related to the presence of the Middle Jurassic Louann Salt. Some of these brines likely inherited their salinity from evaporated Mesozoic seawater, while other saline fluids have been produced by subsequent dissolution of salt, some of which is occurring today. The timing of the generation of brines has thus not been restricted to the Middle Jurassic. The mechanisms of solute transport that have introduced brines throughout much of the sedimentary section of the GOM are not entirely understood. Free convection driven by spatial variations in formation water temperature and salinity is undoubtedly occurring around some salt structures. However, the driving mechanisms for the broad, diffusive upward solute transport in the northern Gulf rim of Arkansas and northern Louisiana are not known. In the Lower Cretaceous of Texas, fluid flow was much more highly focused, and perhaps episodic. It is clear that many areas of the Gulf basin are hydrologically connected and that large‐scale fluid flow, solute transport, and dispersion have occurred. The Na‐Mg‐Ca‐Cl compositions of brines in the areas of the Gulf Coast sedimentary basin reviewed in this article are products of diagenesis and do not reflect the composition of the evaporated marine waters present at the time of sediment deposition. Large differences in Na, Ca, and Mg trends for waters hosted by Mesozoic versus Cenozoic sediments may reflect differences in: (i) the sources of salinity (evaporated seawater for some of the Mesozoic sediments, dissolution of salt for some of the Cenozoic sediments); (ii) sediment lithology (dominantly carbonates for much of the Mesozoic sediments, and dominantly siliciclastics for the Cenozoic sediments); or (iii) residence times of brines associated with these sediments (tens of millions of years versus perhaps days).     

Quantitative basin modeling: present state and future developments towards predictability

A critique review of the state of quantitative basin modeling is presented. Over the last 15 years, a number of models are proposed to advance our understanding of basin evolution. However, as of present, most basin models are two dimensional (2‐D) and subject to significant simplifications such as depth‐ or effective stress‐dependent porosity, no stress calculations, isotropic fracture permeability, etc. In this paper, promising areas for future development are identified. The use of extensive data sets to calibrate basin models requires a comprehensive reaction, transport, mechanical (RTM) model in order to generate the synthetic response. An automated approach to integrate comprehensive basin modeling and seismic, well‐log and other type of data is suggested. The approach takes advantage of comprehensive RTM basin modeling to complete an algorithm based on information theory that places basin modeling on a rigorous foundation. Incompleteness in a model can self‐consistently be compensated for by an increase in the amount of observed data used. The method can be used to calibrate the transport, mechanical, or other laws underlying the model. As the procedure is fully automated, the predictions can be continuously updated as new observed data become available. Finally, the procedure makes it possible to augment the model itself as new processes are added in a way that is dictated by the available data. In summary, the automated data/model integration places basin simulation in a novel context of informatics that allows for data to be used to minimize and assess risk in the prediction of reservoir location and characteristics.     

A vector of high‐temperature paleo‐fluid flow deduced from mass transfer across permeability barriers (quartz veins)

Quartz veins acted as impermeable barriers to regional fluid flow and not as fluid‐flow conduits in Mesoproterozoic rocks of the Mt Painter Block, South Australia. Systematically distributed asymmetric alteration selvedges consisting of a muscovite‐rich zone paired with a biotite‐rich zone are centered on quartz veins in quartz–muscovite–biotite schist. Geometric analysis of the orientation and facing of 126 veins at Nooldoonooldoona Waterhole reveals a single direction along which a maximum of all veins have a muscovite‐rich side, irrespective of their specific individual orientation. This direction represents a Mesoproterozoic fluid‐flow vector and the veins represent permeability barriers to the flow. The pale muscovite‐rich zones formed on the downstream side of the vein and the dark biotite‐rich zones mark the upstream side. The alteration couplets formed from mica schist at constant Zr, Ga, Sc, and involved increases in Si, Na, Al and decreases in K, Fe, Mg for pale alteration zones, and inverse alteration within dark zones. The asymmetry of the alteration couplets is best explained by the pressure dependence of mineral–fluid equilibria. These equilibria, in combination with a Darcian flow model for coupled advection and diffusion, and with permeability barriers imposed by the quartz veins, simulate the pattern of both fluid flow and differential, asymmetric metasomatism. The determined vector of fluid flow lies along the regional foliation and is consistent with the known distribution of regional alteration products. The presence of asymmetric alteration zones in rock containing abundant pre‐alteration veins suggests that vein‐rich material may have generally retarded regional fluid flow.     

Hydrothermal dolomitization,mixing corrosion and deep burial porosity formation: numerical results from 1‐D reactive transport models

Major corrosion has been found at depth in carbonate hydrocarbon reservoirs from different geologic provinces. Fluid inclusion microthermometry and stable isotopic compositions of carbonate cements, predating major corrosion, constrain the interpretation of the evolution of parental fluids during progressive burial and prior to the major corrosion event. Post‐major corrosion mineral paragenesis includes pyrite (‐marcasite), anhydrite, kaolinite (dickite) and fluorite. Although the post‐corrosion mineral paragenesis represents minor volumes of rock, it may provide valuable insights into the post‐corrosion brine chemistry. Using reactive transport numerical models, the roles of cooling and/or mixing of brines on corrosion have been evaluated as controls for dolomitization, deep burial corrosion and precipitation of the post‐corrosion mineral paragenesis. Modelling results show that cooling of deep‐seated fluids moving upward along a fracture may cause minor calcite dissolution and porosity generation. Significant dolomitization along a fracture zone and nearby host‐rock only occurs when deep‐seated fluids have high salinities (4 mol Cl kg^?1 of solution) and Darcian flow rates are relatively high (1 m³ m^?2 year^?1). Only minor volumes of quartz and fluorite precipitate in the newly formed porosity. Moreover, modelling results cannot reproduce the authigenic precipitation of kaolinite (dickite at high temperatures) by cooling. As an alternative to cooling as a cause of corrosion, mixing between two brines of different compositions and salinities is represented by two main cases. One case consists of the flow up along a fracture of deep‐seated fluids with higher salinities than the fluid in the wall rock. Dolomite does not precipitate at a fracture zone. Nevertheless, minor volumes of dolomite are formed away from the fracture. The post‐corrosion mineral paragenesis can be partly reproduced, and the results are comparable to those obtained from cooling calculations. Minor volumes of quartz and fluorite are formed, and kaolinite‐dickite does not precipitate. The major outputs of this scenario are calcite dissolution and slight net increase in porosity. A second case corresponds to the mixing of low salinity deep‐seated fluids, flowing up along fractures, with high salinity brines within the wall rock. Calculations predict major dissolution of calcite and precipitation of dolomite. The post‐corrosion mineral paragenesis can be reproduced. High volumes of quartz, fluorite and kaolinite‐dickite precipitate and may even completely occlude newly formed porosity.     

Salinity structure of the central North Slope foreland basin, Alaska, USA: implications for pathways of past and present topographically driven regional fluid flow

Previous studies of the areal variation in heat flow in the National Petroleum Reserve Alaska (NPRA) support the existence of an active topographically driven regional fluid flow regime in this central part of the North Slope foreland basin. Drilling records and wireline logs for over 30 wells drilled in the NPRA provide additional field information, which can be used to further constrain interpretation of the pattern of regional flow of basinal waters within the NPRA. Hydraulic heads estimated from drilling mud weights show that ground water flow occurs generally from south to north, but with divergence to the north‐east and north‐west away from the central part of the NPRA towards coastal areas of elevated shallow heat flow. Salinities calculated from SP logs range from less than 1 g L^?1, to marine values of 35 g L^?1, to hypersaline values of over 150 g L^?1. The entire upper sedimentary section to a depth of 2 km or more in the eastern part of the NPRA has been preferentially flushed with meteoric water through an area corresponding to the sandiest portion of the Nanushuk group. Deeper areas of low salinity occur within the Sadlerochit and Lisburne sections. The pattern of regional flow in the east is complicated, however, by the presence of a large mass of hypersaline water at depth. It is not known whether these brines are being displaced laterally and upward towards the discharge end of the basin or whether fresher waters are simply riding up over the top. Deep, hypersaline waters also occur in fault slices in the Brooks Range and have survived meteoric flushing. The brines were probably formed at the time of deposition of the Lisburne carbonates. The fluid flow regime to the west is different. Low‐salinity waters may be flowing northward underneath this section through the Ellesmerian section and discharging upward nearer the coast. However, sparse well log control severely limits what can be deduced about the details of flow paths in the central and western parts of the NPRA.     

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.     

The upper continental crust, an aquifer and its fluid: hydaulic and chemical data from 4 km depth in fractured crystalline basement rocks at the KTB test site

Detailed information on the hydrogeologic and hydraulic properties of the deeper parts of the upper continental crust is scarce. The pilot hole of the deep research drillhole (KTB) in crystalline basement of central Germany provided access to the crust for an exceptional pumping experiment of 1‐year duration. The hydraulic properties of fractured crystalline rocks at 4 km depth were derived from the well test and a total of 23100 m³ of saline fluid was pumped from the crustal reservoir. The experiment shows that the water‐saturated fracture pore space of the brittle upper crust is highly connected, hence, the continental upper crust is an aquifer. The pressure–time data from the well tests showed three distinct flow periods: the first period relates to wellbore storage and skin effects, the second flow period shows the typical characteristics of the homogeneous isotropic basement rock aquifer and the third flow period relates to the influence of a distant hydraulic border, probably an effect of the Franconian lineament, a steep dipping major thrust fault known from surface geology. The data analysis provided a transmissivity of the pumped aquifer T = 6.1 × 10^?6 m² sec^?1, the corresponding hydraulic conductivity (permeability) is K = 4.07 × 10^?8 m sec^?1 and the computed storage coefficient (storativity) of the aquifer of about S = 5 × 10^?6. This unexpected high permeability of the continental upper crust is well within the conditions of possible advective flow. The average flow porosity of the fractured basement aquifer is 0.6–0.7% and this range can be taken as a representative and characteristic values for the continental upper crust in general. The chemical composition of the pumped fluid was nearly constant during the 1‐year test. The total of dissolved solids amounts to 62 g l^?1 and comprise mainly a mixture of CaCl₂ and NaCl; all other dissolved components amount to about 2 g l^?1. The cation proportions of the fluid (X_Ca approximately 0.6) reflects the mineralogical composition of the reservoir rock and the high salinity results from desiccation (H₂O‐loss) due to the formation of abundant hydrate minerals during water–rock interaction. The constant fluid composition suggests that the fluid has been pumped from a rather homogeneous reservoir lithology dominated by metagabbros and amphibolites containing abundant Ca‐rich plagioclase.     

Computing geochemical mass transfer and water/rock ratios in submarine hydrothermal systems: implications for estimating the vigour of convection

A method of calculating chemical water/rock ratios is presented that enables the estimation of fluid velocities in open, flow‐through hydrologic systems. The approach is based on relating the gain/loss of a chemical species per kilogram of solid phase to the loss/gain of that species in the fluid phase, integrated across a specified length of the flowpath. After examining the underlying approximations of the approach using a one‐dimensional model of seawater moving through a basalt under nonisothermal conditions, the method is applied to representative zones within a two‐dimensional hydrothermal convective system. The method requires that regions within the flow system can be identified in which the direction of flow is steady for an extended period of time. Estimates of fluid velocity are spatial and temporal averages for the length of the flowpath used in the calculation. The location within the flow system and the nature of the alteration reactions determine which species can provide reliable values of the chemical water/rock ratio and useful estimates of fluid velocities. Over the length of the flowpath considered, the calculation of water/rock ratios works best when a species is controlled by a single reaction. Accurate estimates are favoured if the concentration profile of a species along the flowpath increases or decreases monotonically. If the length of the flowpath extends over more than one reaction zone, then erroneous estimates of the water/rock ratio and fluid velocity are more likely. Model calculations suggest that the quartz/silica system should provide reliable estimates for fluid velocity under a wide range of temperature and flow conditions, in particular in those regions of a system at or near quartz equilibrium, so that the aqueous silica concentration is buffered by quartz and correlated with the temperature distribution.     

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     

The stress regime of the Western Canadian Sedimentary Basin

All available information relevant to in situ stress orientations and magnitudes in the Western Canadian Sedimentary Basin (WCSB) were examined to provide a better understanding of how regional stress fields may affect geothermal development. The smallest principal stress is horizontal over most of the Western Canadian Sedimentary Basin, and it varies in magnitude across the region. Horizontal stress trajectories show that S_Hmax axes are generally aligned SW–NE. A total of 1643 measurements of microfracture and minifracture closure pressures, leak‐off pressures and fracture breakdown pressures have been harnessed to map S_Hmin gradients across the basin at depths of 156–500, 500–1000, 1000–4185 and 2000–4185 m. Vertical stress magnitudes, calculated in 91 wells, showed that at constant depth, S_V increases towards the Canadian Rocky Mountains. Resultant regional stress maps show consistent trends in orientation of stress axes. As a result, predictions can be made that propagation axes of subsurface hydraulic fractures will be dominantly SW–NE, except over the Peace River Arch area, where they will trend more towards SSW–NNE. Engineered geothermal systems in the WCSB can be optimised by drilling horizontal wells parallel to S_Hmin.     

Hydrogeochemical modelling of CO2 equilibria and mass transfer induced by organic–inorganic interactions in siliciclastic petroleum reservoirs

Different feldspar types control complex hydrogeochemical processes in hydrocarbon‐bearing siliciclastic reservoirs, which have undergone different degrees of degradation. To test such processes generically, carbon dioxide equilibria and mass transfers induced by organic–inorganic interactions have been modelled for different hydrogeochemical scenarios. The approach is based on and compared with data from the Norwegian continental shelf ( Smith & Ehrenberg 1989 ) and assumes local thermodynamic equilibrium among solids and fluids. Equilibrating mineral assemblages (different feldspar types, quartz, kaolinite, calcite) are based on the primary reservoir composition. Equilibration and coupled mass transfer were triggered by the addition and reaction of different amounts of CO₂, CH₄ and H₂ (plus acetic acid) at temperatures between 50 and 95°C (323 and 368 K). These components occur in oil fields as products of anaerobic bacterial degradation, hydrolytic disproportionation of hydrocarbons and/or thermal maturation of kerogen. We apply two different computer codes and two different thermodynamic data bases to calculate the results. Reaction of 0.32–0.6 mol CO₂, 0.16–0.3 mol CH₄ and 0.8–1.5 mol H₂ with K‐feldspar, quartz, kaolinite and calcite in 1 l of pore water results in modelled values of 0.3–2.3 mol% CO₂ in a multicomponent gas phase that resembles measured data (0.2–1.5 mol%). Similar CO₂ contents result from acetic acid addition (CO₂, CH₄, H₂ + 0.016 mol CH₃COOH). Equilibration with albite or anorthite reduces the release of CO₂ into the multicomponent gas phase dramatically, by 1 or 4 orders of magnitude compared with the equilibration with K‐feldspar. Minor differences in the modelled CO₂ content (0.1–0.2 mol%) result from calculations with different computer codes if the same thermodynamic data base is applied. Relevant differences (up to 1.9 mol% CO₂) result from calculations using different thermodynamic data bases.