Br/Cl ratios and O, H, C, and B isotopic constraints on the origin of saline waters from eastern Canada

Saline groundwaters were recovered from undisturbed (Restigouche deposit) and active (Brunswick #12 mine) Zn-Pb volcanogenic massive sulfide deposits in the Bathurst Mining Camp (BMC), northern New Brunswick, Canada. These groundwaters, along with fresh to brackish meteoric ground and surface waters from the BMC, have been analyzed to determine their major, trace element and stable isotopic (O, H, C, and B) compositions. Saline groundwaters (total dissolved solids = 22-45 g/L) are characterized by relatively high Na/Ca ratios compared to brines from the Canadian Shield and low Na/Cl_molar and δ¹¹B isotopic compositions (−2.5‰ to 11.1‰) compared to seawater. Although saline waters from the Canadian Shield commonly have oxygen and hydrogen isotopic compositions that plot to the left of the global meteoric water line, those from the BMC fall close to the water line. Fracture and vein carbonate minerals at the Restigouche deposit have restricted carbon isotopic compositions of around −5‰ to −6‰. The carbon isotopic compositions of the saline waters at the Restigouche deposit (+12‰ δ¹³C_DIC) are the result of fractionation of dissolved inorganic carbon by methanogenesis. We suggest that, unlike previous models for shield brines, the composition of saline waters in the BMC is best explained by prolonged water-rock reaction, with no requirement of precursor seawater. We suggest that elevated Br/Cl ratios of saline waters compared to seawater may be explained by differential uptake of Br and Cl during groundwater evolution through water-rock reaction.     

Comparison of the Sr isotopic signatures in brines of the Canadian and Fennoscandian shields

A synthesis of Sr isotope data from shallow and deep groundwaters, and brines from the Fennoscandian and Canadian Shields is presented. A salinity gradient is evident in the water with concentrations varying from approximately 1–75 g L⁻¹ below 1500 m depth in the Fennoscandian Shield and from 10 up to 300 g L⁻¹ below 650 m depth in the Canadian Shield. Strontium isotope ratios were measured to assess the origin of the salinity and evaluate the degree of water–rock interaction in the systems. In both shields, the Sr concentrations are enriched relative to Cl, defining a positive trend parallel to the seawater dilution line and indicative of Sr addition through weathering processes. The depth distribution for Sr concentration increases strongly with increasing depth in both shields although the variation in Sr-isotope composition does not mirror that of Sr concentrations. Strontium-isotope compositions are presented for surface waters, and groundwaters in several sites in the Fennoscandian and Canadian Shields. Numerous mixing lines can be drawn reflecting water–rock interaction. A series of calculated lines links the surface end-members (surface water and shallow groundwater) and the deep brines; these mixing lines define a range of ⁸⁷Sr/⁸⁶Sr ratios for the deep brines in different selected sites. All sites show a specific ⁸⁷Sr/⁸⁶Sr signature and the occurrence of large ⁸⁷Sr/⁸⁶Sr variations is site specific in both shields. In Canadian Shield brines, the Sr isotope ratios clearly highlight large water rock interaction that increases the ⁸⁷Sr/⁸⁶Sr ratio from water that could have been of marine origin. In contrast to the Canadian Shield, groundwater does not occur in closed pockets in the Fennoscandian, and the well-constrained ⁸⁷Sr/⁸⁶Sr signatures in deep brines should correspond to a large, well-mixed and homogeneous water reservoir, whose Sr isotope signature results from water–rock interaction.     

Geochemistry of the formation waters in the Po plain (Northern Italy): an overview.

The Po Valley brines represent the base level of the Quaternary aquifer located in a thick clay-sands sedimentary sequence. Geochemistry indicates that these are marine waters, evaporated to the stage of gypsum precipitation and trapped at the bottom of the basin in the late Messinian. Most of the groundwater samples collected from different springs and wells in the plain result from a mixture of these Na–Cl brines and shallow groundwaters laterally recharged by the Alpine and Apennine chains.Natural outflows of brackish waters are associated with major tectonic features. Mud volcanoes, located in the eastern sector of the Po plain, are constantly monitored as sudden chemical changes are significant precursors of seismic activity. In the western sector, calcite-filled veins isotopically record different degrees of water-rock interaction. These are outcropping fossil conduits, where mixing between shallow groundwaters and deep seated brines has occurred. The temporal continuity of the hydrological circuits allows the reconstruction of past and present groundwater circulation patterns.This paper summarises and integrates the geochemical data produced over many years in order to obtain a regional picture of brine origins and the natural mechanisms of groundwater flow.     

Isotopic composition (H,O, Cl,Sr) of ground brines of the Siberian Platform

New data on the geochemistry and isotopic composition of chloride brines of the Siberian Platform are presented. The distribution of stable isotopes (²H, ¹⁸O, and ³⁷Cl) in brines of the Tunguska, Angara-Lena, western part of the Yakutian and Olenek artesian basins and ⁸⁷Sr/⁸⁶Sr in brines of the western part of the Olenek artesian basin was studied in the context of the problem of genesis of highly mineralized groundwaters. Results of the study and comparative analysis of the geochemical and isotopic peculiarities of the Siberian Platform brines conform to the theory of brine formation through the interaction of connate waters with enclosing rocks.     

Geochemistry and origin of saline groundwaters in the Fennoscandian Shield

Chemical and isotopic analyses of water from drill holes and mines throughout the Fennoscandian Shield show that distinct layers of groundwater are present. An upper layer of fresh groundwater is underlain by several sharply differentiated saline layers, which may differ in salinity, relative abundance of solutes, and O, H, Sr and S isotope signature. Saline groundwater can be classified into four major groups based on geochemistry and presumed origin. Brackish and saline waters from 50–200 m depth in coastal areas around the Baltic Sea exhibit distinct marine chemical and isotopic fingerprints, modified by reactions with host rocks. These waters represent relict Holocene seawater. Inland, three types of saline groundwater are observed: an uppermost layer of brackish and saline water from 300–900 m depth; saline water and brines from 1000–2000 m depth; and superdeep brines which have been observed to a depth of at least 11 km in the drill hole on the Kola Peninsula, U.S.S.R. Electrical and seismic studies in shield areas suggest that such brines are commonly present at even greater depths. The salinity of all inland groundwaters is attributed predominantly to water-rock interaction. The main solutes are Cl, Ca, Na and Mg in varying proportions, depending on the host rock lithology. The abundance of dissolved gases increases with depth but varies from site to site. The main gas components are N₂, CH₄ (up to 87 vol.%) and locally H₂. The δ¹³C value for methane is highly variable (−25 to −46%), and it is suggested that hydrothermal or metamorphic gases trapped within the surrounding rocks are the most obvious source of CH₄. The uppermost saline water has meteoric oxygen-hydrogen isotopic compositions, whereas values from deeper water plot above the meteoric water line, indicating considerably longer mean residence time and effective low temperature equilibration with host rocks. Geochemical and isotopic results from some localities demonstrate that the upper saline water cannot have been formed through simple mixing between fresh water and deep brines but rather is of independent origin. The source of water itself has not been satisfactorily verified although superdeep brines at least may contain a significant proportion of relict Precambrian hydrothermal or metamorphic fluids.     

The Hydrogeochemistry Of Fractured Plutonic Rocks In The Canadian Shield

The composition of groundwater has been determined in selected granitic, gabbroic and gneissic plutons in the Canadian Shield as part of the Canadian Nuclear Fuel Waste Management Program. A similar geochemical evolution of the groundwater is seen with increasing depth or with flow along the hydraulic gradient, irrespective of rock type. This pattern is comparable to that seen in mine groundwaters from throughout the Canadian Shield. Near-surface groundwaters are typically dilute, slightly alkaline and Ca-(Na)-HCO₃ in composition. They evolve to higher pH, Na-(Ca)-HCO₃ compositions along the flow path because of interaction with plagioclase, calcite precipitation and ion exchange on clay minerals. At greater depths (>≈200 m), groundwater salinity increases as a result of the dissolution of Cl-rich salts in the rock matrix and, in certain areas, mixing with Na-Cl brines from seawater or basinal formation water. Stable and radioactive isotopic data for the groundwaters help to interpret these characteristics and indicate high residence times for the deeper, saline groundwater.

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3 évoluent du fait des interactions avec les plagioclases, de la précipitation de la calcite et des échanges d'ions avec les argiles. Aux plus grandes profondeurs (>≈200 m), l'accroissement de la salinité de l'eau souterraine est provoqué par la dissolution de chlorures de la matrice et, en certains endroits, par le mélange avec des saumures à Na et Cl d'eau de mer ou d'eau de formation de bassin. Les données des isotopes stables et radioactifs des eaux souterraines aident à interpréter leurs caractéristiques; elles indiquent des temps de séjour longs pour les eaux souterraines salées, les plus profondes.

     

Hydrogeochemistry,groundwater ages and sources of salts in a granitic batholith on the Canadian Shield,southeastern Manitoba

The hydrogeochemistry of the Lac du Bonnet granitic batholith has been determined for the region of the Whiteshell Research Area (WRA) in southeastern Manitoba, Canada. This work forms part of the geosciences studies performed for the Canadian Nuclear Fuel Waste Management Program over the period 1980–1995 by Atomic Energy of Canada Limited (AECL). Knowledge of the variation of groundwater chemistry and its causes is useful in assessing the performance and safety of a nuclear fuel waste vault located at depths of up to 1000 m in a crystalline rock formation of the Canadian Shield. Groundwaters and matrix pore fluids have been obtained by standard sampling methods from shallow piezometers in clay-rich overburden, from packer-isolated borehole zones intersecting fractures or fault zones in the bedrock, and from boreholes in unfractured rock in AECL's Underground Research Laboratory (URL). Eighty-six individual fracture groundwaters have been sampled and analysed from permeable zones in 53 boreholes drilled to depths of up to 1000 m in the Lac du Bonnet batholith. In addition, 28 groundwaters from piezometers in a large wetland area near the URL have been sampled and analysed to determine the influence of clay-rich overburden on the bedrock hydrogeochemistry. Analyses have been made for major and minor ions, pH, Eh, trace metals, and stable and radioactive isotopes, to characterise these groundwaters and relate them to their hydrogeologic regimes. Shallow groundwaters in the fractured bedrock are generally dilute (TDS <0.3 g/l), Ca–Na–HCO₃ waters and show little indication of mixing with Ca–Mg–HCO₃–SO₄ groundwater from overburden sediments. The near-modern levels of ³H and ¹⁴C, and a warm-climate ²H/¹⁸O signature in these groundwaters, indicates that the upper ∼200 m of fractured bedrock contains an active groundwater circulation system with a residence time of tens to hundreds of years. Deeper fracture groundwaters (200–400 m depth) in recharge areas, are more alkaline, Na–Ca–HCO₃ waters and evolve to Na–Ca–HCO₃–Cl–SO₄ waters with increasing distance along the flow path. Isotopic data indicate the presence of a glacial melt-water component suggesting that the residence times of these waters are 10³–10⁵ a. These waters form a transition zone between the upper, advective flow regime and a deeper regime in sparsely fractured rock where groundwater in fractures and fracture zones is largely stagnant. At these depths (> 500 m), Na–Ca–Cl–SO₄ waters of increasing salinity (up to 50 g/l) with depth are found and in some fractures the waters have evolved to a Ca–Na–Cl composition. Isotopic data indicate that these waters are warm-climate and pre-glacial in origin, with residence times of over 1 Ma. Pore fluids observed to drain from the unfractured rock matrix in the URL facility are almost pure Ca–Cl in composition, ∼90 g/l salinity, and have a ²H/¹⁸O composition displaced well to the left of the global meteoric water line, about which all other WRA groundwaters lie. This information indicates that these pore fluids have undergone prolonged water-rock interaction and have residence times of 10¹–10³ Ma. Most of the deeper fracture groundwaters and pore fluids have low Br/Cl ratios and moderate to high δ³⁴S values of dissolved SO₄ which indicates that their salinity could be derived from a marine source such as the basinal sedimentary brines and evaporites to the west of the batholith. These fluids may have entered the batholith during early Paleozoic times when sedimentary rocks were deposited over the granite and were driven by a hydraulic gradient resulting from higher ground in western Canada. The hydrogeochemical data and interpretations show that below ∼500 m in the WRA, fracture-hosted groundwaters are very saline, reducing and old, and are, therefore, indicative of stagnant conditions over the period of concern for nuclear waste disposal (1 Ma). The intact rock matrix at these depths is extremely impermeable as indicated by the presence of pore fluids with unusual geochemical and isotopic characteristics. The pore fluids may represent basinal brines that have evolved geochemically and isotopically to their current composition over periods as long as 10³ Ma.     

The geochemistry of formation waters in the molasse basin of upper Austria

The geochemistry of formation waters in the Molasse basin of Upper Austria has been investigated to ascertain the extent of meteoric water replacement of the connate interstitial fluids in these sediments. The chemistry, isotopic composition, and dissolved gas contents of the groundwaters and of oil and gas associated brines have been determined. The most superficial sediments of the basin, the Innviertel (Miocene), have been completely flushed by meteoric waters within the last 200 ka. The underlying Hall and Puchkirchen formations (Miocene/Oligocene) form gas reservoirs for biogenic methane, and the associated formation waters are chemically and isotopically modified connate brines of the original marine deposition. In the northeastern part of the basin, the connate brines of the deeper sediments (Cretaceous/Jurassic) have been partially or completely replaced by meteoric waters, whereas in the south of the basin these sediments contain high salinity fluids which are substantially of connate origin. These conclusions are supported by the stable isotope composition of the various brines. Oil-associated brines from the Eocene sediments contain large amounts of dissolved radiogenic⁴⁰Ar, which suggests that the oils have migrated from high-temperature environments. This is in contrast with the Puchkirchen, for which the observed absence of radiogenic⁴⁰Ar suggests that the biogenic methane has been formed in situ. The⁴He contents of these brines and of the Cretaceous/Jurassic groundwaters are, however, less than those in the overlying Puchkirchen formation and suggest that He has been removed from the deeper sediments as a result of flushing by meteoric water. The ratios of dissolved methane and nitrogen to argon increase with increasing ammonium content of the formation waters. All of these parameters may be used as indices for the maturation of the system. The heavy noble gases, Kr and Xe, are abnormally abundant in the dissolved gases, and this is attributed to geochemical concentration of these gases by adsorption onto shales in the sediment sequence. The overall geochemical situation confirms the existence of separate hydraulic systems with little interconnection in the several overlying geological horizons.     

Salinization of groundwater in the North German Basin: results from conjoint investigation of major, trace element and multi-isotope distribution

Conjoint consideration of distribution of major, rare earth elements (REE) and Y (combined to REY) and of H, O, C, S, Sr isotopes reveals that four types of groundwater are distinguishable by their chemical composition presented by spider patterns. REY patterns indicate thermo-saline deep water and two types of shallow saline groundwaters. Presence of connate waters is not detectable. Sr isotope ratios distinguish three sources of Sr: fast and slow weathering of biotite and K-feldspar in Pleistocene sediments, respectively, and dissolution of limestones. δ¹³C(DIC) indicate dissolution of limestone under closed and open system conditions. Numerous samples show δ¹³C(DIC) > 13‰ which is probably caused by incongruent dissolution of calcite and dolomite. The brines from below 1,000 m represent mixtures of pre-Pleistocene seawater or its evaporation brines and infiltrated post-Pleistocene precipitation. The shallow waters represent mixtures of Pleistocene and Recent precipitation salinized by dissolution of evaporites or by mixing with ascending brines. The distribution of water types is independent on geologic units and lithologies. Even the Tertiary Rupelian aquiclude does not prevent salinization of the upper aquifer.     

Origin of salinity in produced waters from the Palm Valley gas field,Northern Territory,Australia

The chemical composition and evolution of produced waters associated with gas production in the Palm Valley gas field, Northern Territory, has important implications for issues such as gas reserve calculations, reservoir management and saline water disposal. The occurrence of saline formation water in the Palm Valley field has been the subject of considerable debate. There were no occurrences of mobile water early in the development of the field and only after gas production had reduced the reservoir pressure, was saline formation water produced. Initially this was in small quantities but has increased dramatically with time, particularly after the initiation of compression in November 1996.The produced waters range from highly saline (up to 300,000 mg/L TDS), with unusual enrichments in Ca, Ba and Sr, to low salinity fluids that may represent condensate waters. The Sr isotopic compositions of the waters (⁸⁷Sr/⁸⁶Sr = 0.7041–0.7172) are also variable but do not correlate closely with major and trace element abundances. Although the extreme salinity suggests possible involvement of evaporite deposits lower in the stratigraphic sequence, the Sr isotopic composition of the high salinity waters suggests a more complex evolutionary history.The formation waters are chemically and isotopically heterogeneous and are not well mixed. The high salinity brines have Sr isotopic compositions and other geochemical characteristics more consistent with long-term residence within the reservoir rocks than with present-day derivation from a more distal pool of brines associated with evaporites. If the high salinity brines entered the reservoir during the Devonian uplift and were displaced by the reservoir gas into a stagnant pool, which has remained near the reservoir for the last 300–400 Ma, then the size of the brine pool is limited. At a minimum, it might be equivalent to the volume displaced by the reservoired gas.     

Chemical and isotopic compositions of groundwater and stream water in a heavy agricultural basin of Korea

The chemical and isotopic compositions of groundwater and stream water in the Haean basin, Korea, which have been intensively used for agricultural irrigation, were examined. The field parameters and chemical compositions were typical of relatively uncontaminated waters, except for the agricultural impact. The low EC levels indicated that the waters had not experienced any significant geochemical processes such as water-rock interaction and evaporation. The very similar chemical compositions and ionic ratios were also indicative of fast circulation and good hydraulic connection. The oxygen and hydrogen isotopic compositions of most of the samples in wet and dry seasons showed very similar range which indicated a single source for both waters without any significant geochemical alteration. However, in the wet season, evaporation trends were observed in some groundwaters because of inflow of irrigation return flow from a rice paddy field. The isotopes of both waters were affected by the altitude and amount of precipitation.     

Oxygen and Hydrogen Isotopes of Waters in the Ordos Basin,China: Implications for Recharge of Groundwater in the North of Cretaceous Groundwater Basin

Hundreds of precipitation samples collected from meteorological stations in the Ordos Basin from January 1988 to December 2005 were used to set up a local meteoric water line and to calculate weighted average isotopic compositions of modern precipitation. Oxygen and hydrogen isotopes, with averages of ?7.8‰ and ?53.0‰ for δ18O and δD, respectively, are depleted in winter and rich in spring, and gradually decrease in summer and fall, illustrating that the seasonal effect is considerable. They also show that the isotopic difference between south portion and north portion of the Ordos Basin are not obvious, and the isotope in the middle portion is normally depleted. The isotope compositions of 32 samples collected from shallow groundwater (less than a depth of 150 m) in desert plateau range from ?10.6‰ to ?6.0‰ with an average of ?8.4‰ for δ18O and from ?85‰ to ?46‰ with an average of ?63‰ for δD. Most of them are identical with modern precipitation. The isotope compositions of 22 middle and deep groundwaters (greater than a depth of 275 m) fall in ranges from ?11.6‰ to ?8.8‰ with an average of ?10.2‰ for δ18O and from ?89‰ to ?63‰ with an average of ?76‰ for δD. The average values are significantly less than those of modern precipitation, illustrating that the middle and deep groundwaters were recharged at comparatively lower air temperatures. Primary analysis of 14C shows that the recharge of the middle and deep groundwaters started at late Pleistocene. The isotopes of 13 lake water samples collected from eight lakes define a local evaporation trend, with a relatively flat slope of 3.77, and show that the lake waters were mainly fed by modern precipitation and shallow groundwater.     

Paleowaters in Silurian-Devonian carbonate aquifers: Geochemical evolution of groundwater in the Great Lakes region since the Late Pleistocene

Changes in the climatic conditions during the Late Quaternary and Holocene greatly impacted the hydrology and geochemical evolution of groundwaters in the Great Lakes region. Increased hydraulic gradients from melting of kilometer-thick Pleistocene ice sheets reorganized regional-scale groundwater flow in Paleozoic aquifers in underlying intracratonic basins. Here, we present new elemental and isotopic analyses of 134 groundwaters from Silurian-Devonian carbonate and overlying glacial drift aquifers, along the margins of the Illinois and Michigan basins, to evaluate the paleohydrology, age distribution, and geochemical evolution of confined aquifer systems. This study significantly extends the spatial coverage of previously published groundwaters in carbonate and drift aquifers across the Midcontinent region, and extends into deeper portions of the Illinois and Michigan basins, focused on the freshwater-saline water mixing zones. In addition, the hydrogeochemical data from Silurian-Devonian aquifers were integrated with deeper basinal fluids, and brines in Upper Devonian black shales and underlying Cambrian-Ordovician aquifers to reveal a regionally extensive recharge system of Pleistocene-age waters in glaciated sedimentary basins. Elemental and isotope geochemistry of confined groundwaters in Silurian-Devonian carbonate and glacial drift aquifers show that they have been extensively altered by incongruent dissolution of carbonate minerals, dissolution of halite and anhydrite, cation exchange, microbial processes, and mixing with basinal brines. Carbon isotope values of dissolved inorganic carbon (DIC) range from −10 to −2‰, ⁸⁷Sr/⁸⁶Sr ratios range from 0.7080 to 0.7090, and δ³⁴S-SO₄ values range from +10 to 30‰. A few waters have elevated δ¹³C_DIC values (>15‰) from microbial methanogenesis in adjacent organic-rich Upper Devonian shales. Radiocarbon ages and δ¹⁸O and δD values of confined groundwaters indicate they originated as subglacial recharge beneath the Laurentide Ice Sheet (14-50 ka BP, −15 to −13‰ δ¹⁸O). These paleowaters are isolated from shallow flow systems in overlying glacial drift aquifers by lake-bed clays and/or shales. The presence of isotopically depleted waters in Paleozoic aquifers at relatively shallow depths illustrates the importance of continental glaciation on regional-scale groundwater flow. Modern groundwater flow in the Great Lakes region is primarily restricted to shallow unconfined glacial drift aquifers. Recharge waters in Silurian-Devonian and unconfined drift aquifers have δ¹⁸O values within the range of Holocene precipitation: −11 to −8‰ and −7 to −4.5‰ for northern Michigan and northern Indiana/Ohio, respectively. Carbon and Sr isotope systematics indicate shallow groundwaters evolved through congruent dissolution of carbonate minerals under open and closed system conditions (δ¹³C_DIC = −14.7 to−11.1‰ and ⁸⁷Sr/⁸⁶Sr = 0.7080-0.7103). The distinct elemental and isotope geochemistry of Pleistocene- versus Holocene-age waters further confirms that surficial flow systems are out of contact with the deeper basinal-scale flow systems. These results provide improved understanding of the effects of past climate change on groundwater flow and geochemical processes, which are important for determining the sustainability of present-day water resources and stability of saline fluids in sedimentary basins.     

Microbial hydrocarbon gases in the Witwatersrand Basin, South Africa: Implications for the deep biosphere

In this study, compositions and δ¹³C and δ²H isotopic values of hydrocarbon gases from 5 mines in the Witwatersrand basin, South Africa, support the widespread occurrence of microbially produced methane in millions of years-old fissure waters. The presence of microbial methane is, to a large extent, controlled by the geologic formations in which the gases are found. Samples from the Witwatersand Supergroup have the largest microbial component based on δ¹³C and δ²H signatures and CH₄/C₂+ values. Based on mixing between a microbial CH₄ component and a more ¹³C-enriched and ²H-depleted C₂+-rich end member, conservative estimates of the % contribution of microbial CH₄ to the gas samples range from >90% microbial CH₄ at Beatrix, Masimong, and Merriespruit, to between 5 and 80% microbial CH₄ at Evander, and <18% microbial CH₄ at Kloof. The Witwatersrand basin’s history of thermal alteration of organic-rich ancient sedimentary units suggests a thermogenic origin for this ¹³C-enriched end member. Alternatively, the potential for an abiogenic origin similar to hydrocarbon gases produced by water-rock interaction at other Precambrian Shield mines is discussed. Microbial methane is predominantly found in paleo-meteoric fissure waters with δ¹⁸O and δ²H values that fall on the meteoric waterline, and have temperatures between 30 to 40°C. In contrast, fissure waters with a larger component of nonmicrobial hydrocarbon gases show a trend towards more enriched δ¹⁸O and δ²H values that fall well above the meteoric waterline, and temperatures of 45 to 60°C. The enrichment in ¹⁸O and ²H in these samples, and their high salinity, are similar to the isotopic and compositional characteristics of saline groundwaters and brines produced by water-rock interaction at Precambrian Shield sites elsewhere. The reported 100 Ma ages of fissure waters from the Witwatersrand and Ventersdorp formations suggest that these microbial hydrocarbon gases are the product of in situ methanogenic communities in the deep subsurface of the Witswaterand basin. Small subunit ribosomal RNA genes were amplified using archaeal-specific primer sets from DNA extracts derived from several of these waters. Fissure waters with a high proportion of microbial methane also contained sequences resembling those of known methanogens.     

Genesis and evolution of high-pCO2 groundwaters of the Mukhen spa (Russian Far East)

We present the chemical and isotope compositions of the water and gas phases of the unique Mukhen cold high-pCO₂ spa. Estimated 5¹⁸O, 5D, and 5¹³C_tic values and data on geology and hydrogeology of the studied area indicate that the source of the groundwaters is meteoric waters, whereas carbon dioxide is of deep genesis and numerous regional faults are gas-feeding channels. Calculations of equilibrium reactions in the water-rock system show that the upper-aquifer waters (HCO₃-Ca-Mg) with low TDS are undersaturated with carbonate minerals, montmorillonites, and aluminosilicates but are oversaturated with kaolinite, whereas the lower-aquifer waters (HCO3-Na) with high TDS are oversaturated with calcite, dolomite, and clay minerals but are undersaturated with main aluminosilicates. We propose a new concept of the formation of these groundwaters, demonstrating that long interaction between rocks and groundwaters in the presence of CO₂ and considerable precipitation of secondary minerals are responsible for the high TDS of the lower-aquifer waters (up to 14 g/L) and their geochemical type (HCO₃-Na) and unusual isotope composition (5¹⁸O = -25.2%c, 5D = -69.0%c).     

Saline groundwaters in the hercynian granites (Chardon Mine,France): geochemical evidence for the salinity origin

In this study, the chemical evolution of high Cl⁻ Chardon mine groundwaters is modelled as a mixing between an oxidising recharge and an old marine component on which the water–rock interaction is superimposed. Chemical and isotopic similarities with saline Carnmenellis mine groundwaters are emphasised and a general comparison with other brines is discussed.The cation content of deep granitic groundwaters is indicative of the water–rock interaction. In the case of Chardon and Carnmenellis groundwaters, the high Na/Cl ratio can still be related to the contribution of a brine of sedimentary origin to the water salinity. The differences in the hydrochemistry related to their geological context only appears at the trace metals level. On the contrary, brines in plutonic rocks which exhibit a low Na/Cl ratio represent groundwaters having a residence time in the host rock, long enough to equilibrate with secondary aluminosilicates. In that case, the brine origin is difficult to assess if only based on the water cation content.     

Stable isotope geochemistry of ground and surface waters associated with undisturbed massive sulfide deposits; constraints on origin of waters and water-rock reactions

Stable isotopes (H, O, C) were determined for ground and surface waters collected from two relatively undisturbed massive sulfide deposits (Halfmile Lake and Restigouche) in the Bathurst Mining Camp (BMC), New Brunswick, Canada. Additional waters from active and inactive mines in the BMC were also collected. Oxygen and hydrogen isotopes of surface and shallow groundwaters from both the Halfmile Lake and Restigouche deposits are remarkably uniform (− 13 to − 14‰ and − 85 to − 95‰ for δ¹⁸O_VSMOW and δ²H_VSMOW, respectively). These values are lighter than predicted for northern New Brunswick and, combined with elevated deuterium excess values, suggest that recharge waters are dominated by winter precipitation, recharged during spring melting. Deeper groundwaters from the Restigouche deposit, and from active and inactive mines have heavier δ¹⁸O_VSMOW ratios (up to − 10.8‰) than shallow groundwaters suggesting recharge under warmer climate or mixing with Shield-type brines. Some of the co-variation in Cl concentrations and δ¹⁸O_VSMOW ratios can be explained by mixing between saline and shallow recharge water end-members. Carbon isotopic compositions of dissolved inorganic carbon (DIC) are variable, ranging from − 15 to − 5‰ δ¹³C_VPDB for most ground and surface waters. Much of the variation in the carbon isotopes is consistent with closed system groundwater evolution involving soil zone CO₂ and fracture zone carbonate minerals (calcite, dolomite and siderite; average = − 6.5‰ δ¹³C_VPDB). The DIC of saline Restigouche deposit groundwater is isotopically heavy (∼+ 12‰ δ¹³C_VPDB), indicating carbon isotopic fractionation from methanogenesis via CO₂ reduction, consistent with the lack of dissolved sulfate in these waters and the observation of CH₄-degassing during sampling.     

Hydrologic hydrochemical characterization of texas frio formation used for deep-well injection of chemical wastes

Hydrologic hydrochemical investigations were conducted to determine the long-term fate of hazardous chemical waste disposed in the Texas Gulf Coast Tertiary formations by deep-well injection. The study focused on the hydrostatic section of the Frio Formation because it is the host of a very large volume of injected waste and because large data bases of formation pressures and water chemistry are available.Three hydrologic regimes exist within the Frio Formation: a shallow fresh to moderately saline water section in the upper 3,000–4,000 ft (914–1,219 m); an underlying 4,000- to 5,000-ft-thick (1,219- to 1,524-m) section with moderate to high salinities: and a deeper overpressured section with moderate to high salinities. The upper two sections are normally pressured and reflect either freshwater or brine hydrostatic pressure gradients. Geopressured conditions are encountered as shallow as 6,000 ft (1,829 m). The complexity of the hydrologic environment is enhanced due to extensive depressurization in the 4,000- to 8,000-ft-depth (1,219- to 2,438-m) interval, which presumably results from the estimated production of over 10 billion barrels (208 × 10⁶ m³) of oil equivalent and associated brines from the Frio in the past 50 yr. Because of the higher fluid density and general depressurization in the brine hydrostatic section, upward migration of these brines to shallow fresh groundwaters should not occur. Depressured oil and gas fields, however, may become sinks for the injected chemical wastes.Water samples appear to be in approximate oxygen isotopic equilibrium with the rock matrix, suggesting that active recharge of the Frio by continental waters is not occurring. In the northern Texas Gulf Coast region salt dome dissolution is a prime process controlling water chemistry. In the central and southern Frio Formation, brines from the deeper geopressured section may be leaking into the hydrostatic section. The lack of organic acids and the alteration of Frio oils from samples collected from depths shallower than approximately 7,000 ft (2,133 m) suggest microbial degradation of organic material. This has useful implications for degradation of injected chemical wastes and needs to be investigated further.     

Sedimentology and isotope geochemistry of lacustrine carbonates of the Oligocene Campins Basin, north-east Spain

The non-marine Campins Basin developed in the Oligocene, during a period of early rifting of the Catalan Coastal Ranges. Lacustrine deposits, interbedded between two alluvial units, comprise shallow and deep lacustrine facies. The lower, shallow lacustrine facies are made up of microbialite buildups and thin limestone beds. In the studied area, these facies are overlain by deep lacustrine facies which consist of alternations of several, metre-thick carbonate- and mudstone-dominated intervals. In addition to calcite, which is characteristic of the shallow lacustrine facies, aragonite and abundant dolomite are present in the deep lacustrine facies. This mineralogical change in the sequence reflects an overall increase in the Mg/Ca ratio of the lake waters. The deep lacustrine sequences are interpreted as having formed in a hydrologically closed basin that was subject to changes in the Mg/Ca ratio of the water, probably related to variations in the evaporation/precipitation rate. The sedimentological, mineralogical and isotopic characteristics of the Campins Basin dolomites suggest that, in general, they are primary in origin. The stable isotope data show an approximate covariance between δ¹³C and δ¹⁸O in the lower shallow lacustrine carbonates (calcite) which suggests that they formed during the onset of closure of the lake. The δ¹³C and δ¹⁸O values of the deep lacustrine carbonates display three different clusters that are roughly related to the carbonate mineralogy. Normalisation with respect to calcite of the isotopic compositions of dolomite and aragonite from the deep lacustrine carbonates allows the integration of all these isotope values into one covariant trend. The sequential appearance of different carbonate minerals and the isotopic covariant trend may indicate an overall evaporative concentration of the lake waters. The change in slope of the covariant trend for the isotope values between the shallow and the deep lacustrine carbonates might reflect the change in the waterbody morphology recorded in the basin fill sequence.