Spatial variations in the salinity of pore waters in northern deep water Gulf of Mexico sediments: implications for pathways and mechanisms of solute transport

Spatial variations in the salinity of pore waters in sedimentary basins can provide important insight into basin-scale hydrogeologic processes. Although there have been numerous studies of brine seeps in the deep water Gulf of Mexico, much less is known about porewater salinities in the vast areas between seeps. A study has been made of spatial variation in pore water salinities in sediments in an approximately 500 km by 200 km area of the northern deep water (water depth >500 m) Gulf of Mexico sedimentary basin (GOM) to provide insight into pathways and mechanisms of solute transport in this portion of the basin. A second objective was to document salinities in the upper 500 m of the sedimentary section, the approximate depth to which methane hydrates, a potential future energy resource, may be stable. Elevated salinities would reduce the P – T stability range of hydrates. Salinities were calculated from borehole logs using a dual electrical conductivity model. Even though much of the northern GOM is underlain by allochthonous salt most of the undisturbed shallow sedimentary section has not been permeated by hypersaline waters. These waters are limited to areas near brine seeps. Hypersaline waters having salinities in excess of 100 g l⁻¹ become more common at subseafloor depths of 2 km and greater. A field study at Green Canyon 65 and published numerical simulations of fluid flow above tabular salt bodies suggest that brines produced by salt dissolution migrate laterally and pond above salt and/or within minibasins and that the dominant mechanism of vertical solute transport is a combination of compaction-driven advection and diffusion, not large-scale thermohaline overturn. Superimposed on this diffuse upward flux of dissolved salt is the more focused and localized expulsion of saline fluids up faults.     

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.     

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.     

Abnormally pressured beds as barriers to diffusive solute transport in sedimentary basins

Diffusion can drive significant solute transport over millions of years, but ancient brines and large salinity gradients are still observed in deep sedimentary basins. Fluid flow within abnormally pressured beds may prevent diffusive transfer over geologically significant periods, if the abnormally pressured bed is surrounded by normally pressured beds. Analytic solutions based on sediment loading and unloading demonstrate that this effect should be considered in beds with a compressibility exceeding 10^?8 Pa^?1, with a thickness of 100 m or more, or a sedimentation rate exceeding 10^?5 m year^?1. Conditions favourable for our model of abnormally pressured beds appear common in sedimentary basins. Large salinity gradients associated with clay beds have previously been attributed to membrane effects, but flow patterns associated with abnormally pressured beds appear more robust in the presence of heterogeneity and discontinuities than membrane effects. Calculations suggest that thick underpressured shales in the Alberta basin may have allowed ancient evaporatively concentrated brines to be preserved beneath a vigorous topography‐driven flow system over the last 60 My. In the Illinois basin, drained overpressured beds may have limited solute transport across the New Albany shale until approximately 250 Ma. It is unlikely, however, that overpressures could have persisted long enough to explain concentration gradients observed in the modern basin. These gradients may instead reflect relatively recent halite dissolution above the New Albany shale.     

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.     

Groundwater age,brine migration,and large‐scale solute transport in the Alberta Basin,Canada

There is a great contrast in geochemical and hydrogeologic estimates of the residence times of pore fluids in sedimentary basins. This contrast is particularly evident in the Alberta Basin, Canada, which has served as the study area for important studies of long‐term fluid flow and transport. To address these differences, we developed two‐dimensional simulations of groundwater age, constrained by both hydrogeologic and geochemical observations, to estimate the residence time of fluids and the amount and timing of flushing by meteoric waters in the Alberta Basin. Results suggest that old, residual brines have been retained in the deepest parts of the basin since their formation ca. 400 Ma, but significant dilution by younger waters has reduced the age of these pore waters to no more than approximately 200 My. Shallower formations have been flushed extensively by fresh, young waters. Loss of brines and dilution of older pore waters occurred primarily after the uplift of the Rockies with the introduction of the gravity‐driven flow regime. Despite these large changes in flow regime, solute exchange between deep saline aquifers and the overlying vigorous freshwater flow system was found to be consistent with long‐term dispersive mixing across subhorizontal concentration gradients rather than by direct flushing. Sensitivity studies using an analytic solution supported the use of 100 m for transverse dispersivity in large‐scale numerical models. These simulations confirm that the age and origin of brines are in many cases poor indicators of long‐term solute transport rates in sedimentary basins, but the geochemical indicators that are used to determine the origin of brines can provide useful constraints for calculating groundwater age and are far more commonly available than isotopic groundwater age tracers.     

Geophysical and geochemical evidence of large scale fluid flow within shallow sediments in the eastern Gulf of Mexico,offshore Louisiana

We analyse the fluid flow regime within sediments on the Eastern levee of the modern Mississippi Canyon using 3D seismic data and downhole logging data acquired at Sites U1322 and U1324 during the 2005 Integrated Ocean Drilling Program (IODP) Expedition 308 in the Gulf of Mexico. Sulphate and methane concentrations in pore water show that sulphate–methane transition zone, at 74 and 94 m below seafloor, are amongst the deepest ever found in a sedimentary basin. This is in part due to a basinward fluid flow in a buried turbiditic channel (Blue Unit, 1000 mbsf), which separates sedimentary compartments located below and above this unit, preventing normal upward methane flux to the seafloor. Overpressure in the lower compartment leads to episodic and focused fluid migration through deep conduits that bypass the upper compartment, forming mud volcanoes at the seabed. This may also favour seawater circulation and we interpret the deep sulphate–methane transition zones as a result of high downward sulphate fluxes coming from seawater that are about 5–10 times above those measured in other basins. The results show that geochemical reactions within shallow sediments are dominated by seawater downwelling in the Mars‐Ursa basin, compared to other basins in which the upward fluid flux is controlling methane‐related reactions. This has implications for the occurrence of gas hydrates in the subsurface and is evidence of the active connection between buried sediments and the water column.     

Polyphasic hydrothermal and meteoric fluid regimes during the growth of a segmented fault involving crystalline and carbonate rocks (Barcelona Plain,NE Spain)

A polyphasic tectonic‐fluid system of a fault that involves crystalline and carbonate rocks (Hospital fault, Barcelona Plain) has been inferred from regional to thin section scale observations combined with geochemical analyses. Cathodoluminescence, microprobe analyses and stable isotopy in fracture‐related cements record the circulation of successive alternations of hydrothermal and low‐temperature meteoric fluids linked with three main regional tectonic events. The first event corresponds to the Mesozoic extension, which had two rifting stages, and it is characterized by the independent tectonic activity of two fault segments, namely southern and northern Hospital fault segments. During the Late Permian‐Middle Jurassic rifting, these segments controlled the thickness and distribution of the Triassic sediments. Also, dolomitization was produced in an early stage by Triassic seawater at shallow conditions. During increasing burial, formation of fractures and their dolomite‐related cements took place. Fault activity during the Middle Jurassic–Late Cretaceous rifting was localized in the southern segment, and it was characterized by hydrothermal brines, with temperatures over 180°C, which ascended through this fault segment precipitating quartz, chlorite, and calcite. The second event corresponds to the Paleogene compression (Chattian), which produced exhumation, folding and erosion, favouring the percolation of low‐temperature meteoric fluids which produced the calcitization of the dolostones and of the dolomite cements. The third event is linked with the Neogene extension, where three stages have been identified. During the syn‐rift stage, the southern segment of the Hospital fault grew by tip propagation. In the relay zone, hydrothermal brines with temperature around 140°C upflowed. During the late postrift, the Hospital fault acted as a unique segment and deformation occurred at shallow conditions and under a low‐temperature meteoric regime. Finally, and possibly during the Messinian compression, NW‐SE strike‐slip faults offset the Hospital fault to its current configuration.     

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.     

Reactive transport and thermo‐hydro‐mechanical coupling in deep sedimentary basins affected by glaciation cycles: model development,verification, and illustrative example

Deep sedimentary basins are complex systems that over long time scales may be affected by numerous interacting processes including groundwater flow, heat and mass transport, water–rock interactions, and mechanical loads induced by ice sheets. Understanding the interactions among these processes is important for the evaluation of the hydrodynamic and geochemical stability of geological CO₂ disposal sites and is equally relevant to the safety evaluation of deep geologic repositories for nuclear waste. We present a reactive transport formulation coupled to thermo‐hydrodynamic and simplified mechanical processes. The formulation determines solution density and ion activities for ionic strengths ranging from freshwater to dense brines based on solution composition and simultaneously accounts for the hydro‐mechanical effects caused by long‐term surface loading during a glaciation cycle. The formulation was implemented into the existing MIN3P reactive transport code (MIN3P‐THCm) and was used to illustrate the processes occurring in a two‐dimensional cross section of a sedimentary basin subjected to a simplified glaciation scenario consisting of a single cycle of ice‐sheet advance and retreat over a time period of 32 500 years. Although the sedimentary basin simulation is illustrative in nature, it captures the key geological features of deep Paleozoic sedimentary basins in North America, including interbedded sandstones, shales, evaporites, and carbonates in the presence of dense brines. Simulated fluid pressures are shown to increase in low hydraulic conductivity units during ice‐sheet advance due to hydro‐mechanical coupling. During the period of deglaciation, Darcy velocities increase in the shallow aquifers and to a lesser extent in deeper high‐hydraulic conductivity units (e.g., sandstones) as a result of the infiltration of glacial meltwater below the warm‐based ice sheet. Dedolomitization is predicted to be the most widespread geochemical process, focused near the freshwater/brine interface. For the illustrative sedimentary basin, the results suggest a high degree of hydrodynamic and geochemical stability.     

Fluid inclusion constraints on the origin of the brines responsible for Pb–Zn mineralization at Pine Point and coarse non‐saddle and saddle dolomite formation in southern Northwest Territories

The Pine Point region is a classic metallogenic mining camp that produced over 58 million short tons of Zn–Pb ore from approximately 40 base‐metal mineralized deposits hosted by Middle Devonian carbonates. The ore deposits are localized in paleokarstic features found in the epigenetic ‘Presqu'ile’ dolomite that preferentially replaced some of the upper barrier limestones. The main ore‐stage sulfides include galena, sphalerite, marcasite, and pyrite. A bulk fluid inclusion chemistry study was carried out on sulfide, coarse non‐saddle and saddle dolomite and calcite samples from the Pine Point and Great Slave Reef deposits, and unmineralized coarse non‐saddle and saddle dolomite samples from Hay West, Windy Point and Qito areas. Molar Cl/Br ratio data from Pine Point indicate the presence of four fluids at different stages of the paragenesis. The fluids trapped in sulfides and ore‐stage dolomites predominately consist of a Br‐rich fluid with a composition similar to that of evaporated seawater (fluid A), and a very Br‐enriched fluid of unknown origin (fluid B). Both these fluids are CaCl₂–NaCl (Na to Ca ratios of 1:10)‐rich brines and have compositions unlike the modern formation waters in the Devonian aquifers in the basin today. A third, relatively Cl‐rich (or Br‐poor), fluid (fluid C) was identified in two samples and may have acquired some chlorinity by dissolving halide minerals. Mixing between the Br‐rich fluid A and a dilute fluid also occurred in the later stages of the paragenesis, resulting in the formation of calcite and native sulfur. Saddle and coarse dolomites not associated with significant sulfide mineralization have a narrow range of halogen compositions similar to fluid A. There is no evidence of fluid B or C in the unmineralized samples. Relative to a modern‐day seawater compositions all the fluids have had some modification of their cation compositions. There is some weak evidence for interactions with clastic units or crystalline basement rocks. It is also possible however, that the evaporative brines could have formed from a relatively CaCl₂‐rich, NaCl‐depleted Devonian seawater, unlike the composition of modern‐day seawater.     

Impacts of Pleistocene glaciation on large‐scale groundwater flow and salinity in the Michigan Basin

Pleistocene melting of kilometer‐thick continental ice sheets significantly impacted regional‐scale groundwater flow in the low‐lying stable interiors of the North American and Eurasian cratons. Glacial meltwaters penetrated hundreds of meters into the underlying sedimentary basins and fractured crystalline bedrock, disrupting relatively stagnant saline fluids and creating a strong disequilibrium pattern in fluid salinity. To constrain the impact of continental glaciation on variable density fluid flow, heat and solute transport in the Michigan Basin, we constructed a transient two‐dimensional finite‐element model of the northern half of the basin and imposed modern versus Pleistocene recharge conditions. The sag‐type basin contains up to approximately 5 km of Paleozoic strata (carbonates, siliciclastics, and bedded evaporites) overlain by a thick veneer (up to 300 m) of glacial deposits. Formation water salinity increases exponentially from <0.5 g l^?1 total dissolved solids (TDS) near the surface to >350 g l^?1 TDS at over 800 m depth. Model simulations show that modern groundwater flow is primarily restricted to shallow glacial drift aquifers with discharge to the Great Lakes. During the Pleistocene, however, high hydraulic heads from melting of the Laurentide Ice Sheet reversed regional flow patterns and focused recharge into Paleozoic carbonate and siliciclastic aquifers. Dilute waters (<20 g l^?1 TDS) migrated approximately 110 km laterally into the Devonian carbonate aquifers, significantly depressing the freshwater‐saline water mixing zones. These results are consistent with ¹⁴C ages and oxygen isotope values of confined groundwaters in Devonian carbonates along the basin margin, which reflect past recharge beneath the Laurentide Ice Sheet (14–50 ka). Constraining the paleohydrology of glaciated sedimentary basins, such as the Michigan Basin, is important for determining the source and residence times of groundwater resources, in addition to resolving geologic forces responsible for basinal‐scale fluid and solute migration.     

Indications of formation water flow and compartmentalization on the flank of a salt structure derived from salinity and seismic data

Vertical and lateral variations in lithology, salinity, temperature, and pressure determined from wireline LAS logs, produced water samples, and seismic data on the south flank of a salt structure on the continental shelf, offshore Louisiana indicate three hydrogeologic zones in the study area: a shallow region from 0 to 1.1 km depth with hydrostatically pressured, shale‐dominated Pleistocene age sediments containing pore waters with sea water (35 g l^?1) or slightly above sea water salinity; a middle region from 1.1 to 3.2 km depth with near hydrostatically pressured, sand‐dominated Pliocene age sediments that contain pore waters that range from seawater salinity to up to 5 times sea water salinity (180 g l^?1); and a deep section below 3.2 km depth with geopressured, shale‐dominated Miocene age sediments containing pore waters that range from sea water salinity to 125 g l^?1. Salt dissolution has generated dense, saline waters that appear to be migrating down dip preferentially through the thick Pliocene sandy section. Sand layers that come in contact with salt contain pore waters with high salinity. Isolated sands have near sea water salinity. Salinity information in conjunction with seismic data is used to infer fluid compartmentalization. Both vertical and lateral lithologic barriers to fluid flow at tens to hundreds of meters scale are observed. Fluid compartmentalization is also evident across a supradomal normal fault. Offset of salinity contours are consistent with the throw of the fault, which suggests that saline fluids migrated before fault formation.     

Relationship of brines in the Kinnarot Basin,Jordan‐Dead Sea Rift Valley

Element ratios and water stable isotopes reveal the presence of only two independent deep brines in the Kinnarot Basin, Israel: the evaporite dissolution brine of Zemah‐1 and the inferred Ha’on mother brine (HMB) with low and high Br/Cl ratios, respectively. HMB is considered to be a representative of the Late Pliocene evaporated Sedom Sea. The freshwater‐diluted evaporation brine emerges as Ha’on brine on the eastern shore of Lake Tiberias and is also identified in the pore water of lake sediments. HMB is converted into Tiberias mother brine (TMB) by dolomitization of limestones and alteration of abundant volcanic rocks occurring along the western side of the lake. The Ha’on and Tiberias brines, both characterized by high δD and δ¹⁸O values, are similar in Na/Cl and Br/Cl ratios but are dissimilar in Br/K ratios because these brines were subjected to different degrees of interactions with rocks and sediments. Excepting the brine from KIN 8, all brines from the Tabigha area including the nearby off‐shore Barbutim brine are related to the TMB. The brine KIN 8 and all brines from the Fuliya and Hammat Gader areas are related to the HMB. The brine encountered in wildcat borehole Zemah‐1 is generated by halite‐anhydrite/gypsum dissolution and is independent from the HMB system.     

Fluids and halogens at the diagenetic–metamorphic boundary: evidence from veins in continental basins, western Norway

Seven vein types are recognized in three continental Devonian molasse basins (the Hornelen, Kvamshesten and Solund basins) in western Norway. These include calcite‐, quartz‐ and epidote‐dominated veins. The salinities of fluid inclusions from quartz‐dominated veins in the Hornelen and Kvamshesten basins are close to or slightly higher than those for modern seawater, whereas the fluids from quartz‐ and calcite‐dominated veins in the Solund basin range from seawater values to 20 wt % NaCl equivalent. Minerals such as biotite, amphibole, titanite, chlorite and epidote are abundant in the latter veins, and are important constituents of the authigenic mineral assemblages. A combination of fluid inclusion and petrological data suggest that at least some of the veins formed at depths around 12–14 km. The Cl/Br ratios and the salinity of the fluid inclusions can be explained by interactions with evaporites, implying that the sedimentary environment forming the basin fill had the strongest influence upon low‐grade metamorphic fluid Cl and Br contents. Differences in the Cl/I and Na/Br ratios between the Solund basin and the Hornelen and Kvamshesten basins are best explained by local mass transfer between pore fluids and the surrounding rock matrix during burial and increasing temperatures.     

Salt tectonics and shallow subseafloor fluid convection: models of coupled fluid‐heat‐salt transport

Thermohaline convection associated with salt domes has the potential to drive significant fluid flow and mass and heat transport in continental margins, but previous studies of fluid flow associated with salt structures have focused on continental settings or deep flow systems of importance to petroleum exploration. Motivated by recent geophysical and geochemical observations that suggest a convective pattern to near‐seafloor pore fluid flow in the northern Gulf of Mexico (GoMex), we devise numerical models that fully couple thermal and chemical processes to quantify the effects of salt geometry and seafloor relief on fluid flow beneath the seafloor. Steady‐state models that ignore halite dissolution demonstrate that seafloor relief plays an important role in the evolution of shallow geothermal convection cells and that salt at depth can contribute a thermal component to this convection. The inclusion of faults causes significant, but highly localized, increases in flow rates at seafloor discharge zones. Transient models that include halite dissolution show the evolution of flow during brine formation from early salt‐driven convection to later geothermal convection, characteristics of which are controlled by the interplay of seafloor relief and salt geometry. Predicted flow rates are on the order of a few millimeters per year or less for homogeneous sediments with a permeability of 10^?15 m², comparable to compaction‐driven flow rates. Sediment permeabilities likely fall below 10^?15 m² at depth in the GoMex basin, but such thermohaline convection can drive pervasive mass transport across the seafloor, affecting sediment diagenesis in shallow sediments. In more permeable settings, such flow could affect methane hydrate stability, seafloor chemosynthetic communities, and the longevity of fluid seeps.     

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.     

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.     

Temperature‐dependent Li isotope ratios in Appalachian Plateau and Gulf Coast Sedimentary Basin saline water

Lithium (Li) concentrations of produced water from unconventional (horizontally drilled and hydraulically fractured shale) and conventional gas wells in Devonian reservoirs in the Appalachian Plateau region of western Pennsylvania range from 0.6 to 17 mmol kg^?1, and Li isotope ratios, expressed as in δ⁷Li, range from +8.2 to +15‰. Li concentrations are as high as 40 mmol kg^?1 in produced waters from Plio‐Pleistocene through Jurassic‐aged reservoirs in the Gulf Coast Sedimentary Basin analyzed for this study, and δ⁷Li values range from about +4.2 to +16.6‰. Because of charge‐balance constraints and rock buffering, Li concentrations in saline waters from sedimentary basins throughout the world (including this study) are generally positively correlated with chloride (Cl), the dominant anion in these fluids. Li concentrations also vary with depth, although the extent of depth dependence differs among sedimentary basins. In general, Li concentrations are higher than expected from seawater or evaporation of seawater and therefore require water–mineral reactions that remove lithium from the minerals. Li isotope ratios in these produced waters vary inversely with temperature. However, calculations of temperature‐dependent fractionation of δ⁷Li between average shale δ⁷Li (?0.7‰) and water result in δ⁷Li_water that is more positive than that of most produced waters. This suggests that aqueous δ⁷Li may reflect transport of water from depth and/or reaction with rocks having δ⁷Li lighter than average shale.     

Long‐term chemical evolution and modification of continental basement brines – a field study from the Schwarzwald,SW Germany

Highly saline, deep‐seated basement brines are of major importance for ore‐forming processes, but their genesis is controversial. Based on studies of fluid inclusions from hydrothermal veins of various ages, we reconstruct the temporal evolution of continental basement fluids from the Variscan Schwarzwald (Germany). During the Carboniferous (vein type i), quartz–tourmaline veins precipitated from low‐salinity (<4.5wt% NaCl + CaCl₂), high‐temperature (≤390°C) H₂O‐NaCl‐(CO₂‐CH₄) fluids with Cl/Br mass ratios = 50–146. In the Permian (vein type ii), cooling of H₂O‐NaCl‐(KCl‐CaCl₂) metamorphic fluids (T ≤ 310°C, 2–4.5wt% NaCl + CaCl₂, Cl/Br mass ratios = 90) leads to the precipitation of quartz‐Sb‐Au veins. Around the Triassic–Jurassic boundary (vein type iii), quartz–haematite veins formed from two distinct fluids: a low‐salinity fluid (similar to (ii)) and a high‐salinity fluid (T = 100–320°C, >20wt% NaCl + CaCl₂, Cl/Br mass ratios = 60–110). Both fluids types were present during vein formation but did not mix with each other (because of hydrogeological reasons). Jurassic–Cretaceous veins (vein type iv) record fluid mixing between an older bittern brine (Cl/Br mass ratios ~80) and a younger halite dissolution brine (Cl/Br mass ratios >1000) of similar salinity, resulting in a mixed H₂O‐NaCl‐CaCl₂ brine (50–140°C, 23–26wt% NaCl + CaCl₂, Cl/Br mass ratios = 80–520). During post‐Cretaceous times (vein type v), the opening of the Upper Rhine Graben and the concomitant juxtaposition of various aquifers, which enabled mixing of high‐ and low‐salinity fluids and resulted in vein formation (multicomponent fluid H₂O‐NaCl‐CaCl₂‐(SO₄‐HCO₃), 70–190°C, 5–25wt% NaCl‐CaCl₂ and Cl/Br mass ratios = 2–140). The first occurrence of highly saline brines is recorded in veins that formed shortly after deposition of halite in the Muschelkalk Ocean above the basement, suggesting an external source of the brine's salinity. Hence, today's brines in the European basement probably developed from inherited evaporitic bittern brines. These were afterwards extensively modified by fluid–rock interaction on their migration paths through the crystalline basement and later by mixing with younger meteoric fluids and halite dissolution brines.