An evaporated seawater origin for the ore-forming brines in unconformity-related uranium deposits (Athabasca Basin, Canada): Cl/Br and δCl analysis of fluid inclusions

Analyses of halogen concentration and stable chlorine isotope composition of fluid inclusions from hydrothermal quartz and carbonate veins spatially and temporally associated with giant unconformity-related uranium deposits from the Paleoproterozoic Athabasca Basin (Canada) were performed in order to determine the origin of chloride in the ore-forming brines. Microthermometric analyses show that samples contain variable amounts of a NaCl-rich brine (Cl concentration between 120,000 and 180,000 ppm) and a CaCl₂-rich brine (Cl concentration between 160,000 and 220,000 ppm). Molar Cl/Br ratios of fluid inclusion leachates range from ∼100 to ∼900, with most values between 150 and 350. Cl/Br ratios below 650 (seawater value) indicate that the high salinities were acquired by evaporation of seawater. Most δ³⁷Cl values are between −0.6‰ and 0‰ (seawater value) which is also compatible with a common evaporated seawater origin for both NaCl- and CaCl₂-rich brines.Slight discrepancies between the Cl concentration, Cl/Br, δ³⁷Cl data and seawater evaporation trends, indicate that the evaporated seawater underwent secondary minor modification of its composition by: (i) mixing with a minor amount of halite-dissolution brine or re-equilibration with halite during burial; (ii) dilution in a maximum of 30% of connate and/or formation waters during its migration towards the base of the Athabasca sandstones; (iii) leaching of chloride from biotites within basement rocks and (iv) water loss by hydration reactions in alteration haloes linked to uranium deposition.The chloride in uranium ore-forming brines of the Athabasca Basin has an unambiguous dominantly marine origin and has required large-scale seawater evaporation and evaporite deposition. Although the direct evidence for evaporative environments in the Athabasca Basin are lacking due to the erosion of ∼80% of the sedimentary pile, Cl/Br ratios and δ³⁷Cl values of brines have behaved conservatively at the basin scale and throughout basin history.     

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.     

Salinity mapping model and brine chemistry of Mishrif reservoir in Basrah oilfields,Southern Iraq

Cation and anion concentrations and boron isotopic ratio of brines in the Mishrif Formation (U. Campanian-Tuoronian) from North Rumaila, South Rumaila, Majnoon, Zubair, and West Qurna oilfields southern Iraq were investigated. The aims of this study are to define the type, origin of the oilfield waters, and its flow model in the subsurface oil traps. Mishrif brines are characterized by having higher concentrations of sodium (50,500–84,200 ppm), chlorine (102,100–161,500 ppm), and boron (21.9–31.1 ppm) with lower sulfate contents (187–1350 ppm) relative to the modern seawater. Samples have slightly depleted in δ ¹¹B (35.4‰) relative to seawater fall near the seawater intrusion of the diagram Cl/Br Vs δ ¹¹B and occupied the field of evaporated seawater on the diagrams of Cl vs B and 1/Br vs δ ¹¹B. The brine of Na-chloride type is characteristics of the Mishrif reservoir in all oilfields except WQ which defined by facies of Na-Ca-chloride type. A weak acidic brine of a salinity six-time greater than seawater plays a role in generating the formation pressure and controlling the fluid flow. The reservoir rock-fluid interactions were interpreted using boron isotopes which eventually reveal an ongoing dilution process by the present seawater intrusion and injection water used for the secondary production under conditions of high-temperature digenetic reactions. The ¹¹B in the oilfield water is resulted from uptake of the tetrahedral borate after precipitation of calcium carbonate, while ¹⁰B is sourced from the thermal maturation of organic matters.     

Comparison of stable isotopes,ratios of Cl/Cl and I/I in brine and deep groundwater from the Pacific coastal region and the eastern margin of the Japan Sea

Fifty-three samples, including brines associated with oil and natural gas reservoirs and groundwater samples from deep boreholes, were collected from the Pacific and Japan Sea coastal regions in Japan. The ¹²⁹I/¹²⁷I and ³⁶Cl/Cl ratios, and stable isotopes (δD and δ¹⁸O) are compared to investigate differences related to the geotectonic settings of the two regions. The δD and δ¹⁸O data indicate that brine and groundwater from the Pacific coastal region reflect mixing of meteoric water with connate seawater in the pores of sedimentary rocks. On the other hand, brine and groundwater from the Japan Sea coastal region have been hydrothermally altered. In particular, brines associated with petroleum accumulations at Niigata and Akita showed the same isotopic characteristics as fluids found in the Kuroko deposits of the Green Tuff region in northeastern Japan. There is little difference in the ³⁶Cl/Cl ratios in brine and groundwater from the Pacific and Japan Sea coasts. Most brine and some deep groundwater, except those from the Pleistocene Kazusa Group, have already reached the average secular equilibrium ratio of 9.9 ± 2.7 × 10⁻¹⁵ for their mudstone and sandstone reservoirs. There was no correlation between the ³⁶Cl/Cl ratios and differences in geotectonic setting between the Pacific and the Japan Sea coast. The molar I/Br ratio suggests that the I in all of water samples was of biogenic origin. The average ¹²⁹I/¹²⁷I ratio was 290 ± 130 × 10⁻¹⁵ to 294 ± 105 × 10⁻¹⁵ in both regions, showing no relationship to the different geotectonic settings. The uncontaminated brine and groundwater samples are likely to have retained the original ¹²⁹I/¹²⁷I ratios of marine I released from the old organic matter stored in sedimentary rock.     

Messinian Ca–Cl Brines from Mediterranean Basins: Tracing Diagenetic Effects by Ca/Mg Versus Ca/Sr Diagram

In natural resource exploration, Ca–Cl basinal brines are important for understanding the origin and spatial and temporal distribution of hydrocarbons and sedimentary ore deposits. Little attention has been paid to the possible connection between fossil basinal brines and paleo-seawaters and to the implications for reconstructing paleo-seawater compositions. Secular variations of Ca/Mg and Ca/Sr ratios in seawater have been documented mainly using fluid inclusions in halite, calcareous fossils and mineral analyses. However, brines and other sedimentary records connected to paleo-seawater or its evaporated residues may be chemically affected by burial diagenesis or the effects of continental waters of meteoric origin, thus complicating interpretations of the analytical results. To investigate these effects on fluids and minerals related to the Messinian salinity crisis of the Mediterranean basin, we re-evaluate published data from: (1) brackish-to-brine waters from onshore (Northern Apennine foredeep; Levantine basin) and offshore (porewaters from the Deep Sea Drilling Project); (2) Messinian parental seawater deduced from calcareous fossils, fluid inclusions and sulfate minerals; (3) meteoric waters dissolving evaporites. The compositional trends related to seawater evaporation, diagenesis and mixing that affect the Ca/Mg and Ca/Sr molar ratios of the basinal brines are effectively discriminated on a binary plot depicting the proper fields for seawater and meteoric-derived fluids. Brines showing stronger dolomitization start from Ca/Mg and Ca/Sr molar ratios of Messinian seawater deduced from the published analysis of fluid inclusions and open ocean fossils, that are therefore here validated ex post.     

Halogens and noble gases in sedimentary formation waters and Zn–Pb deposits: A case study from the Lennard Shelf,Australia

Halogen ratios (Br/Cl and I/Cl) and concentrations provide important information about how sedimentary formation waters acquire their salinity, but the possible influence of organic Br derived from sedimentary wall-rocks is rarely quantified. Here, it is demonstrated that Br/Cl versus I/Cl mixing diagrams can be used to deconvolve organic Br contributions; that organic matter has a limited range of Br/I ratios; and that organic Br is a more significant component in Zn–Pb deposit ore fluids than previously recognised. The significance of these findings is illustrated for the Lennard Shelf Zn–Pb deposits of Western Australia.Fluid inclusions related to Lennard Shelf Zn–Pb mineralisation have variable salinity and hydrocarbon contents. The halogen data from these fluid inclusions require mixing of three fluid end-members: (1) an evaporated seawater bittern brine (30 wt.% NaCl equiv.) with greater than seawater Br/Cl ratio; (2) a lower salinity pore fluid (?5 wt.% NaCl equiv.) with moderately elevated Br/Cl and I/Cl; and (3) fluids with Br/Cl ratios of ～5 times seawater and extremely elevated I/Cl ratios of ～11,500 times seawater. The first two fluids have ⁴⁰Ar/³⁶Ar of 300–400 and greater than air saturated water ³⁶Ar concentrations that are typical of fluid inclusions related to Zn–Pb mineralisation. The third ‘organic-rich’ fluid has the highest ⁴⁰Ar/³⁶Ar ratio of up to 1500 and a depleted ³⁶Ar concentration.Mineralisation is interpreted to have resulted from mixing of Zn-rich evaporitic brines and H₂S present in hydrocarbons. It is suggested that aqueous fluids acquired organic Br and I from hydrocarbons, and that hydrocarbons exsolving from the aqueous fluid removed noble gases from solution. Interaction of variably saline brines and hydrocarbons could account for the variable Br/Cl and I/Cl composition, and ³⁶Ar concentrations, recorded by Lennard Shelf fluid inclusions. The distinct ⁴⁰Ar/³⁶Ar signature of the fluid with the highest I/Cl ratio suggests the hydrocarbons and brines were sourced independently from different parts of the sedimentary basin. These data indicate the complementary nature of halogen and noble gas analysis and provide new constraints on important mixing processes during sediment-hosted Zn–Pb mineralisation.     

The use of bromide and chloride mass ratios to differentiate salt-dissolution and formation brines in shallow groundwaters of the Western Canadian Sedimentary Basin

In the Western Canadian Sedimentary Basin, the petroleum industry handles two geochemically distinctive brines that are traceable in the environment: formation brines extracted along with hydrocarbons from the basin, and salt-dissolution brines, produced by dissolving deep halite formations to create caverns for petroleum product storage. The concentrations of the conservative ions chloride (Cl) and bromide (Br) in many formation brines plot closely to the seawater evaporation trajectory of previous studies. These brines contain Cl/Br mass ratios of around 300, while salt-dissolution brines are relatively Br depleted, having Cl/Br mass ratios in excess of 20,000. An oilfield site in central Alberta had experienced nearby releases of both salt-dissolution and formation brines. Geochemical mixing trends were defined by theoretically mixing samples of local salt-dissolution and formation brine sources with background shallow groundwater. Most site monitoring wells and local surface water samples plotted directly on a salt-dissolution brine dilution trend, while results from four monitoring wells, all located directly downgradient of formation brine spills, suggested the mixing of formation brines into shallow groundwater. This work indicates that there is a large-scale salt-dissolution brine plume beneath the site and reinforces the use of Cl and Br concentrations and mass ratios as environmental tracers.     

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.     

Theoretical estimates of equilibrium chlorine-isotope fractionations

Equilibrium chlorine-isotope (³⁷Cl/³⁵Cl) fractionations have been determined by using published vibrational spectra and force-field modeling to calculate reduced partition function ratios for Cl-isotope exchange. Ab initio force fields calculated at the HF/6-31G(d) level are used to estimate unknown vibrational frequencies of ³⁷Cl-bearing molecules, whereas crystalline phases are modeled by published lattice-dynamics models. Calculated fractionations are principally controlled by the oxidation state of Cl and its bond partners. Molecular mass (or the absence of C-H bonds) also appears to play a role in determining relative fractionations among simple Cl-bearing organic species. Molecules and complexes with oxidized Cl (i.e., Cl⁰, Cl⁺, etc.) will concentrate ³⁷Cl relative to chlorides (substances with Cl⁻). At 298 K, ClO₂ (containing Cl⁴⁺) and [ClO₄]⁻ (containing Cl⁷⁺) will concentrate ³⁷Cl relative to chlorides by as much as 27‰ and 73‰, respectively, in rough agreement with earlier calculations. Among chlorides, ³⁷Cl will be concentrated in substances where Cl is bonded to +2 cations (i.e., FeCl₂, MnCl₂, micas, and amphiboles) relative to substances where Cl is bonded to +1 cations (such as NaCl) by ∼2 to 3‰ at 298 K; organic molecules with C-Cl bonds will be even richer in ³⁷Cl (∼5 to 9‰ at 298 K). Precipitation experiments, in combination with our results, provide an estimate for Cl-isotope partitioning in brines and suggest that silicates (to the extent that their Cl atoms are associated with nearest-neighbor +2 cations analogous with FeCl₂ and MnCl₂) will have higher ³⁷Cl/³⁵Cl ratios than coexisting brine (by ∼2 to 3‰ at room temperature). Calculated fractionations between HCl and Cl₂, and between brines and such alteration minerals, are in qualitative agreement with both experimental results and systematics observed in natural samples. Our results suggest that Cl-bearing organic molecules will have markedly higher ³⁷Cl/³⁵Cl ratios (by 5.8‰ to 8.5‰ at 295 K) than coexisting aqueous solutions at equilibrium. Predicted fractionations are consistent with the presence of an isotopically heavy reservoir of HCl that is in exchange equilibrium with Cl⁻_aq in large marine aerosols.     

Behaviour of Li and its isotopes during metasomatism of French Massif Central lherzolites

Li behaviour and distribution in the mantle were investigated by ion microprobe in situ measurements on co-existing olivine (ol), orthopyroxene (opx), clinopyroxene (cpx) and amphibole (amp) in xenoliths from the French Massif Central. The fertile spinel lherzolites of this study record increasing degrees of mantle metasomatism, from unmetasomatised anhydrous samples through cryptically metasomatised samples to highly metasomatised amphibole-rich samples. In anhydrous lherzolites, Li is preferentially incorporated into olivine (1.1-1.4 ppm, average values) compared to pyroxenes (0.2-0.9 ppm). The hydrous samples clearly show enrichment of Li in ol (1.5-5.0 ppm), opx (1.1-2.4 ppm) and cpx (2.4-5.4 ppm), while amphibole incorporates less Li than the co-existing phases (0.8-1.3 ppm). Average δ⁷Li values range from +7.6 to +14.5‰ in ol, from 5.1 to +13.7‰ in opx and from 8.8 to +10.3‰ in cpx from the anhydrous lherzolites. A layered peridotite sample (Sdi) shows higher Li content in all phases, with lighter isotopic composition in opx and cpx (−0.6 and −2‰ average δ⁷Li values, respectively). In the hydrous lherzolites average δ⁷Li values both overlap and extend beyond these ranges in ol (up to 17.5 ‰) and in opx (up to 22.9‰), and vary widely in cpx (−2.7 to +9.7‰). Low δ⁷Li values are observed in some opx (−10.4‰) and cpx (−13‰) from sample Sdi, and in cpx from three hydrous samples (from −9.7 to −5.3‰). The different anhydrous phases from the hydrous samples show large intra-grain variations in Li isotopic ratios (e.g., up to 18‰) compared to the same phases from the anhydrous samples (mostly less than 6‰), excepting sample Sdi which has up to 20.4‰ variation in cpx. Similar to the anhydrous silicates, amphiboles show a wide variation of δ⁷Li values on the intra-grain scale (2-27‰). These variations are interpreted to result from fractionation processes during metasomatism by a silicate melt undergoing compositional changes as it percolates through and reacts with the peridotite phases. Thus Li abundances and isotopic in situ measurements are useful for tracing metasomatic processes but the heterogeneities observed in the samples preclude any identification of a specific mantle source by its Li signature.     

Lithium isotopic composition and concentration of the upper continental crust

The Li isotopic composition of the upper continental crust is estimated from the analyses of well-characterized shales, loess, granites and upper crustal composites (51 samples in total) from North America, China, Europe, Australia and New Zealand. Correlations between Li, δ⁷Li, and chemical weathering (as measured by the Chemical Index of Alteration (CIA)), and δ⁷Li and the clay content of shales (as measured by Al₂O₃/SiO₂), reflect uptake of heavy Li from the hydrosphere by clays. S-type granites from the Lachlan fold belt (-1.1 to -1.4‰) have δ⁷Li indistinguishable from their associated sedimentary rocks (-0.7 to 1.2‰), and show no variation in δ⁷Li throughout the differentiation sequence, suggesting that isotopic fractionation during crustal anatexis and subsequent differentiation is less than analytical uncertainty (±1‰, 2σ). The isotopically light compositions for both I- and S-type granites from the Lachlan fold belt (-2.5 to + 2.7 ‰) and loess from around the world (-3.1 to + 4.5‰) reflect the influence of weathering in their source regions. Collectively, these lithologies possess a limited range of Li isotopic compositions (δ⁷Li of −5‰ to + 5‰), with an average (δ⁷Li of 0 ± 2‰ at 1σ) that is representative of the average upper continental crust. Thus, the Li isotopic composition of the upper continental crust is lighter than the average upper mantle (δ⁷Li of + 4 ± 2‰), reflecting the influence of weathering on the upper crustal composition. The concentration of Li in the upper continental crust is estimated to be 35 ± 11 ppm (2σ), based on the average loess composition and correlations between insoluble elements (Ti, Nb, Ta, Ga and Al₂O₃, Th and HREE) and Li in shales. This value is somewhat higher than previous estimates (∼20 ppm), but is probably indistinguishable when uncertainties in the latter are accounted for.     

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.     

Massive dolomitization of a late Miocene carbonate platform: a case of mixed evaporative brines with meteoric water,Nijar, Spain

Late Miocene platform carbonates from Nijar, Spain, have been extensively dolomitized. Limestones are present in the most landward parts of the platform, in stratigraphically lower units and topographically highest outcrops, suggesting that dolomitizing fluids were derived from the adjacent Nijar Basin. The dolomite crystals range from <10 to ≈100 μm existing as both replacements and cements. Na, Cl and SO₄ concentrations in the dolomites range from 200 to 1700 p.p.m., 250–650 p.p.m., and 600–7000 p.p.m., respectively, comparable with other Tertiary and modern brine dolomite values, and also overlapping values from mixing-zone dolomites. Sr concentrations range between 50 and 300 p.p.m., and the molar Sr/Ca ratios of dolomitizing fluids are estimated to range between 7× seawater brine to freshwater ratios. The δ¹⁸O and δ¹³C of the dolomites range from ?1·0 to +4·2‰ PDB, and ?4·0 to +2·0‰ PDB, respectively. ⁸⁷Sr/⁸⁶Sr values (0·70899–0·70928) of the dolomites range from late Miocene seawater to values greater than modern seawater. Mixtures of freshwater with seawater and evaporative brines probably precipitated the Nijar dolomites. Modelled covariations of molar Sr/Ca vs. δ¹⁸O and Na/Ca vs. δ¹⁸O from these mixtures are consistent with those of the proposed Nijar dolomitizing fluids. Complete or partial dolomite recrystallization is ruled out by well preserved CL zoning, nonstoichiometry and quantitative water–rock interaction modelling of covariations of Na vs. Sr and δ¹⁸O vs. δ¹³C. The possibility of multiple dolomitization events induced by evaporative brines, seawater and freshwater, respectively, is consistent with mineral-mineral mixing modelling. The basin-derived dolomitizing brines probably mixed with freshwater in the Nijar Basin or mixed with fresh groundwater in the platform, and were genetically related either to deposition of the Yesares gypsum or the Feos gypsum. Dolomitization occurred during either the middle Messinian or the early upper Messinian. Nijar dolomitization models may be applicable to dolomitization of other late Miocene platform carbonates of the western Mediterranean. Moreover, the Nijar models may offer an analogue for more ancient evaporite-absent platform carbonates fringing evaporite basins.     

A chlorine isotope study of DSDP/ODP serpentinized ultramafic rocks: Insights into the serpentinization process

Eight DSDP/ODP cores were analyzed for major ion concentrations and δ³⁷Cl values of water-soluble chloride (δ³⁷Cl_WSC) and structurally bound chloride (δ³⁷Cl_SBC) in serpentinized ultramafic rocks. This diverse set of cores spans a wide range in age, temperature of serpentinization, tectonic setting, and geographic location of drilled serpentinized oceanic crust. Three of the cores were sampled at closely spaced intervals to investigate downhole variation in Cl concentration and chlorine isotope composition.The average total Cl content of all 86 samples is 0.26 ± 0.16 wt.% (0.19 ± 0.10 wt.% as water-soluble Cl (X_WSC) and 0.09 ± 0.09 wt.% as structurally bound Cl (X_SBC)). Structurally bound Cl concentration nearly doubles with depth in all cores; there is no consistent trend in water-soluble Cl content among the cores. Chlorine isotope fractionation between the structurally bound Cl⁻ site and the water-soluble Cl⁻ site varies from − 1.08‰ to + 1.16‰, averaging to + 0.21‰. Samples with negative fractionations may be related to reequilibration of the water-soluble chloride with seawater post-serpentinite formation. Six of the cores have positive bulk δ³⁷Cl values (+ 0.05‰ to + 0.36‰); the other two cores (173-1068A (Leg-Hole) and 84-570) have negative bulk δ³⁷Cl values (− 1.26‰ and − 0.54‰). The cores with negative δ³⁷Cl values also have variable Cl⁻ / SO₄² ratios, in contrast to all other cores. The isotopically positive cores (153-920D and 147-895E) show no isotopic variation with depth; the isotopically negative core (173-1068A) decreases by ∼1‰ with depth for both the water-soluble and structurally bound Cl fractions.Non-zero bulk δ³⁷Cl values indicate Cl in serpentinites was incorporated during original hydration and is not an artifact of seawater infiltration during drilling. Cores with positive δ³⁷Cl values are most likely explained by open system fractionation during hydrothermal alteration, with preferential incorporation of ³⁷Cl from seawater into the serpentinite and loss of residual light Cl back to the ocean. Fluid / rock ratios were probably low as evidenced by the presence of water-soluble salts. The two isotopically negative cores are characterized by a thick overlying sedimentary package that was in place prior to serpentinization. We believe the low δ³⁷Cl values of these cores are a result of hydration of ultramafic rock by infiltrating aqueous pore fluids from the overlying sediments. The resulting serpentinites inherit the characteristic negative δ³⁷Cl values of the pore waters. Chlorine stable isotopes can be used to identify the source of the serpentinizing fluid and ultimately discern chemical and tectonic processes involved in serpentinization.     

Origin and evolution of fluids from mud volcanoes in the Barbados accretionary complex

A large collection of fluids (54 interstitial fluids and four expelled fluids) were sampled at the Manon site, at the outer edge of the Barbados accretionary complex. These warm fluids (up to 20°C) are expelled by sub-marine (5000 mbsl) mud volcanoes consisting of diapirs (unchanneled flow) and diatremes (channeled).Chlorine stable isotope ratios of these fluids were measured by IRMS with a reproducibility of ± 0.05‰ (1σ) versus SMOC (Standard Mean Ocean Chloride).A large range of δ³⁷Cl between −5.3‰ and +0.1‰ is observed. Data from each volcanic structure describe a mixing between seawater and a low-δ³⁷Cl fluid. The whole set of data is interpreted as the result of a mixing between two deep components and seawater. The two deep fluids are chemically distinct (e.g., in Ca, Mg, K, Li, Sr and Br contents and Br/Cl ratio). They display low and significantly different ⁸⁷Sr/⁸⁶Sr ratios (0.707790 and 0.707892, respectively) and δ³⁷Cl values (−4.51 and −5.24‰, respectively).Physicochemical processes such as mineralogical transformation, diffusion, compaction or ion filtration are known to fractionate chlorine stable isotopes and can produce fluids with negative δ³⁷Cl values. Ion filtration due to sediment compaction appears to be the more likely process to explain the negative δ³⁷Cl values observed at the Manon site. A model for the generation of these signatures is proposed where a residual negative δ³⁷Cl fluid reservoir is created at the bottom of the prism or the sediment pile. Further compaction/fracturing and/or dewatering of the slab may flush out these fluids and focus them towards the décollement zone. Mixing between the fluids and ultimately with seawater and water released during gas hydrate destabilizations may explain the data set within the individual cores and between the different structures.     

Lithium isotopes in island arc geothermal systems: Guadeloupe, Martinique (French West Indies) and experimental approach

We report lithium (Li) isotopic measurements in seawater-derived waters that were discharged from geothermal wells, thermal springs, and sub-marine springs located in volcanic island arc areas in Guadeloupe (the Bouillante geothermal field) and Martinique (Lamentin plain and the Diamant areas). While Li isotopic signatures of the geothermal fluids collected from deep reservoirs were found to be homogeneous for a given site, the δ⁷Li signatures for each of these reservoirs were significantly different. The first low temperature (25-250 °C) experiments of Li isotope exchange during seawater/basalt interaction confirmed that Li isotopic exchange is strongly temperature dependent, as previously inferred from natural studies. Li isotopic fractionation ranged from +19.4‰ (Δ_{solution-solid}) at 25 °C to +6.7‰ at 250 °C. These experiments demonstrated the importance of Li isotopic fractionation during the formation of Li-bearing secondary minerals and allowed us to determine the following empirical relationship between isotopic fractionation and temperature: Δ_{solution-solid} = 7847/T − 8.093. Application of experimental results and literature data to the Bouillante area suggested that geothermal water was in equilibrium at 250-260 °C. It likely has a deep and large reservoir located in the upper sheeted dike complex of the oceanic crust, just below the transition zone between andesite volcanic flows and the basaltic dikes. The upper dike section, from which Li is extracted by hydrothermal fluids, was characterized by light Li isotopic values in the rocks, indicating retention of ⁶Li by the altered rocks. For the Lamentin and Diamant areas, the geothermal fluids appeared to be in equilibrium with reservoir volcano-sedimentary rocks at 90-120 °C and 180 °C, respectively. Further evidence for this argument is provided by the fact that only the Na/Li thermometric relationship determined for sedimentary basins yielded temperature values in agreement with those measured or estimated for the reservoir fluids. This suggests the importance of a sedimentary signature in these reservoir rocks. Altogether, this study highlights that the use of Li isotopic systematics is a powerful tool for characterizing the origin of geothermal waters as well as the nature of their reservoir rocks.     

Lithium isotope systematics in a forested granitic catchment (Strengbach, Vosges Mountains, France)

Over the last decade it has become apparent that Li isotopes may be a good proxy to trace silicate weathering. However, the exact mechanisms which drive the behaviour of Li isotopes in surface environments are not totally understood and there is a need to better calibrate and characterize this proxy. In this study, we analysed the Li concentrations and isotopic compositions in the various surface reservoirs (soils, rocks, waters and plants) of a small forested granitic catchment located in the Vosges Mountains (Strengbach catchment, France, OHGE http://ohge.u-strasbg.fr). Li fluxes were calculated in both soil profiles and at the basin scale and it was found that even in this forested basin, atmospheric inputs and litter fall represented a minor flux compared to input derived from the weathering of rocks and soil minerals (which together represent a minimum of 70% of dissolved Li). Li isotope ratios in soil pore waters show large depth dependent variations. Average dissolved δ⁷Li decreases from −1.1‰ to −14.4‰ between 0 and −30 cm, but is +30.7‰ at −60 cm. This range of Li isotopic compositions is very large and it encompasses almost the entire range of terrestrial Li isotope compositions that have been previously reported. We interpret these variations to result from both the dissolution and precipitation of secondary phases. Large isotopic variations were also measured in the springs and stream waters, with δ⁷Li varying from +5.3‰ to +19.6‰. δ⁷Li increases from the top to the bottom of the basin and also covaries with discharge at the outlet. These variations are interpreted to reflect isotopic fractionations occurring during secondary phase precipitation along the water pathway through the rocks. We suggest that the dissolved δ⁷Li increases with increasing residence time of waters through the rocks, and so with increasing time of interaction between waters and solids. A dissolution precipitation model was used to fit the dissolved Li isotopic compositions. It was found that the isotopic compositions of springs and stream waters are explicable by an isotopic fractionation of −5‰ to −14‰ (best fit −10.8‰), in agreement with Li incorporation into clay. In soil solutions, it was found that isotopic fractionation during secondary precipitation is larger (at least −23‰), suggesting a major role for different secondary phases, such as iron oxides that maybe incorporate Li with a higher isotope fractionation.     

The formation of natural cryogenic brines

The source of salts in the Ca-chloridic, hypersaline brines (up to 190 g Cl L⁻¹) occurring in crystalline basement rocks in the Canadian, Fennoscandian and Bohemian Shields and their evolution have been investigated and reported. The Cl-Br-Na relationship indicates that these waters have been concentrated from seawater, by freezing during glacial times. The Na/Cl ratio (0.25 to 0.35) in the more saline fluids is compatible with cooling down to −30°C, where the most saline waters have been concentrated by a factor of 25 to 30 relative to the parent seawater.The brines formed from seawater within cryogenic troughs, along the subarctic continental margins, around ice sheets. The depressions within which the brines formed are the cryogenic analogues of the classic, evaporitic lagoon. One million years suffice to saturate with brine a 2000km-radius by 1km-depth rock volume at an H₂O removal rate of only 2.8 mm/yr. Density-induced brine migration on a continental scale takes place via fissures below the ice.Our calculations, that were performed on a hypothetical ice sheet with dimensions compatible with the Laurentide ice sheet, demonstrate that during 1m.y., a 60m thick cryogenic sediment section could have formed. However, the precipitated minerals (mirabilite and hydrohalite) are repeatedly dispersed by the advance and retreat of the ice sheet, dissolved by melt water-seawater mixtures, and eroded during postglacial uplift, leaving almost no trace in the geological record.The cryogenic brines formed intermittently during and between glacial periods. The repeating advance and retreat of the ice sheets exerted a major control on the direction and intensity of brine flow. The cryogenic concentration of seawater and the migration of brine towards the center of the glaciostatic depression occurred mainly during the build up of the ice sheet, while reversal of the water flow from the center of the cryogenic basin outwards happened upon deglaciation. The flow of the waters in the subsurface was, inevitably, accompanied by significant dilution with melt water from the ice sheets.Using a “granitic” U concentration of 4 ppm and a (Ca-Mg mass balance based) rock/water ratio anywhere between 3.4 and 6.8 kg L⁻¹, a few hundred thousand years of brine-rock interaction are sufficient for the growth of ¹²⁹I in the most saline Canadian Shield brine to its present concentration (3.4×10⁸ atoms ¹²⁹I L⁻¹). Hence, both the formation of the saline fluids and their emplacement in their present sites occurred most likely within the Pleistocene.The young age calculated for cryogenic brines in crystalline shields and the dynamic water flow therein should raise concern about the planning and construction of high-grade nuclear waste repositories in such rocks, which are already under way.     

The evolution of marine evaporitic brines in inland basins: The Jordan-Dead Sea Rift valley

Marine-evaporitic brines frequently display Na, Cl and Br concentrations that significantly deviate from seawater evaporation paths, yielding markedly conflicting degrees of evaporation calculated for a specific brine. Here we present 493 new and 33 previously reported analyses of Ca-chloridic waters of Neogene age from the Dead Sea Rift (DSR) valley to explain such offsets. The DSR brines plot along an almost perfect mixing line (R² = 0.990) on a Br/Cl-Na/Cl diagram, extending between two end members A and B. Points A and B are located at Na/Cl = 0.804 and Br/Cl = 0.00193, and at Na/Cl = 0.00773 and Br/Cl = 0.0155, respectively, within the halite and bischofite stability fields.Brines A and B originated in a dual-mode evaporation basin. Brine A formed under the classic lagoon scenario (mode A), with seawater inflow and brine outflow at steady state. Occasional drops in water level, imposed by climatic or tectonic causes, resulted in outflow cutoff and in rapid concentration buildup. The second mode (B) initiated upon equilibration of the activity of water in the brine with the overlying relative humidity, resulting in composition and salinity approaching that of brine B, sustaining it until the next reversal to mode A.Thick evaporite deposits inhibited infiltration of brines A and B into the subsurface terrain, a process that was enabled only when the brine reached the permeable carbonate rock rim and border faults of the basin. Hence, brines that formed during the relatively short shifts from mode A to mode B could not penetrate into the deep subsurface, and bittern minerals that were formed during the frequent mode shifts were dissolved and flushed out into the sea upon the next resumption of outflow.The proposed model accounts for the deviations of brines from the marine evaporitic evolution curve by brine mixing, rather than due to a change in ocean chemistry. It also explains the absence of bittern minerals in the thick halite and gypsum/anhydrite succession, and the compositional gap between the widely different end member hypersaline fluids. This model applies directly to the studied DSR brines and evaporites, but it may be relevant to other inland evaporitic basins.     

Geothermal waters from the Taupo Volcanic Zone,New Zealand: Li,B and Sr isotopes characterization

Chemical and isotopic data for 23 geothermal water samples collected in New Zealand within the Taupo Volcanic Zone (TVZ) are reported. Major and trace elements including Li, B and Sr and their isotopic compositions (δ⁷Li, δ¹¹B, ⁸⁷Sr/⁸⁶Sr) were determined in high temperature geothermal waters collected from deep boreholes in different geothermal fields (Ohaaki, Wairakei, Mokai, Kawerau and Rotokawa geothermal systems). Lithium concentrations are high (from 4.5 to 19.9 mg/L) and Li isotopic compositions (δ⁷Li) are homogeneous, ranging between −0.5‰ and +1.4‰. In particular, it is noteworthy that, except for the samples from the Kawerau geothermal field having slightly higher δ⁷Li values (+1.4%), the other geothermal waters have a near constant δ⁷Li signature around a mean value of 0‰ ± 0.6 (2σ, n = 21). Boron concentrations are also high and relatively homogeneous for the geothermal samples, falling between 17.5 and 82.1 mg/L. Boron isotopic compositions (δ¹¹B) are all negative, and display a range between −6.7‰ and −1.9‰. These B isotope compositions are in agreement with those of the Ngawha geothermal field in New Zealand. Lithium and B isotope signatures are in a good agreement with a fluid signature mainly derived from water/rock interaction involving magmatic rocks with no evidence of seawater input. On the other hand, Sr concentrations are lower and more heterogeneous and fall between 2 and 165 μg/L. The ⁸⁷Sr/⁸⁶Sr ratios range from 0.70549 to 0.70961. These Sr isotope compositions overlap those of the Rotorua geothermal field in New Zealand, confirming that some geothermal waters (with more radiogenic Sr) have interacted with bedrocks from the metasedimentary basement. Each of these isotope systems on their own reveals important information about particular aspects of either water source or water/rock interaction processes, but, considered together, provide a more integrated understanding of the geothermal systems from the TVZ in New Zealand.