Environmental isotopes (18O, 2H, and 87Sr/86Sr) as a tool in groundwater investigations in the Keta Basin, Ghana

Analyses of environmental isotopes (¹⁸O, ²H, and ⁸⁷Sr/⁸⁶Sr) are applied to groundwater studies with emphasis on saline groundwater in aquifers in the Keta Basin, Ghana. The ⁸⁷Sr/⁸⁶Sr ratios of groundwater and surface water of the Keta Basin primarily reflect the geology and the mineralogical composition of the formations in the catchments and recharge areas. The isotopic compositions of ¹⁸O and ²H of deep groundwater have small variations and plot close to the global meteoric water line. Shallow groundwater and surface water have considerably larger variations in isotopic compositions, which reflect evaporation and preservation of seasonal fluctuations. A significant excess of chloride in shallow groundwater in comparison to the calculated evaporation loss is the result of a combination of evaporation and marine sources. Groundwaters from deep wells and dug wells in near-coastal aquifers are characterized by relatively high chloride contents, and the significance of marine influence is evidenced by well-defined mixing lines for strontium isotopes, and hydrogen and oxygen stable isotopes, with isotopic compositions of seawater as one end member. The results derived from environmental isotopes in this study demonstrate that a multi-isotope approach is a useful tool to identify the origin and sources of saline groundwater. Electronic Publication     

Tracing the sources of strontium in karst groundwater in Chongqing, China: a combined hydrogeochemical approach and strontium isotope

Groundwater quality in karst regions is largely controlled by natural processes and anthropogenic activities. Over the past 10?years, dissolved Sr and its radiogenic isotope, ⁸⁷Sr/⁸⁶Sr, were widely used to trace the sources of solutes in groundwater. However, there is little research about hydrogeochemistry and Sr isotopic compositions of the karst groundwater in Chongqing karst area. In this paper, thirty-five representative karst groundwater samples were collected from different aquifers (limestone and dolomite) and various land use types. Hydrochemical types of karst groundwater in Chongqing were mainly of the Ca-HCO₃ type or Ca(Mg)-HCO₃ type. The dissolved Sr concentrations of the studied groundwater ranged from 0.57 to 15.06???mmol/L, and the ⁸⁷Sr/⁸⁶Sr varied from 0.70751 to 0.71627. The groundwater samples from different aquifers and land use types showed distinctive dissolved Sr concentrations and ⁸⁷Sr/⁸⁶Sr. The very positive relationship between Ca/Sr and Mg/Sr in dolomite and limestone aquifers suggests that Ca, Mg and Sr element come mainly from the release of carbonate rock under the groundwater?Crock?CCO₂ gas interaction. According to the ⁸⁷Sr/⁸⁶Sr ratio, the Sr element in karst groundwater in Chongqing was controlled by the weathering of limestone, dolomite and silicate rock (allogenic water in a non-karst area). The relationship ⁸⁷Sr/⁸⁶Sr versus Sr²⁺/[K⁺?+?Na⁺] shows that the anthropogenic inputs also obviously contribute to the Sr contents. The research results show that the karst groundwater in Chongqing is facing serious crisis of water quality, and needs to be protected further.     

Strontium isotopic evidence on the chemical evolution of pore waters in the Milk River Aquifer,Alberta, Canada

Strontium isotope ratios were measured on 13 rock, 18 leachate and 28 pore-water samples from the Milk River aquifer, the confining argillaceous formations, and the glacial till mantling the recharge area. Strontium isotope ratios (⁸⁷Sr/⁸⁶Sr) of pore waters from the aquifer, confining units, and the glacial till ranged from 0.7069 to 0.7082. The ⁸⁷Sr/⁸⁶Sr ratios in aquifer pore waters decrease with increasing distance from the aquifer recharge area, and this is interpreted to be the result of mixing and water–rock interaction within the aquifer.The solute composition of the recharging groundwater is modified by the local lithology, causing distinct geochemical patterns along different flow paths within the aquifer. Whole-rock ⁸⁷Sr/⁸⁶Sr ratios indicate that the shales and till are generally more radiogenic than the aquifer sandstone. The authigenic carbonate cements and rock-forming minerals comprising the major lithologic units had little apparent influence on the pore-water Sr chemistry. Carbonate cement leachates from the till and the aquifer sandstone are more radiogenic than those from the confining shale formations. Feldspar separates from the aquifer sandstone have relatively radiogenic Sr isotope ratios, whereas bentonites from the Milk River and Colorado Shale Formations have whole-rock and leachate Sr isotope ratios that are relatively unradiogenic. Ratios of most Milk River aquifer pore waters are lower than those of any leachates or whole rocks analyzed, except the bentonites.The ⁸⁷Sr/⁸⁶Sr ratios of exchangeable Sr in the bentonites are similar to ratios found in the more evolved pore waters. Simple rock–water interaction models calculated for the whole-rock, leachate, and exchangeable-ion/pore-water pairs indicate that ion exchange with bentonite clays within the Milk River and Colorado Shale Formations appears to influence the isotopic evolution of the pore-water Sr in each of these units.     

The use of O,H, B,Sr and S isotopes for tracing the origin of dissolved boron in groundwater in Central Macedonia,Greece

The groundwater B concentration in Mesozoic karst, Neogene and alluvial aquifers in the West part of Chalkidiki province in Central Macedonia, Greece reaches 6.45 mg L⁻¹, which exceeds the limit of 1 mg L⁻¹, set by the European Union for drinking water. The high B contents have been detected in this area, not only near the shoreline, where seawater intrusion occurs, but also in the inland part of the basin. Multi isotope (²H, ¹⁸O, ³⁴S, ¹⁸O_(SO4), ¹¹B, ⁸⁷Sr/⁸⁶Sr) data from borehole and thermal water springs allow identification of the possible B sources. The B dissolved in groundwater in the Chalkidiki area is mainly geogenic. The low δ¹¹B values, 0–1‰, similar to those of thermal fluids from continental geothermal fields, and the low Cl/B ratio compared to seawater both indicate a geothermal origin for B and reflect deep circulation and interaction with igneous rocks. The ⁸⁷Sr/⁸⁶Sr ratio also indicates that the deep-aquifer granodiorite is the predominant rock source of Sr, while the shallow limestone unit has negligible effects on the dissolved Sr budget in these thermal karst waters which O and H isotopes show to be of meteoric origin. The main source of high B in borehole water is mainly mixing with B-rich geothermal water. The mixing between geothermal water and water from the Neogene aquifer is also reflected by isotopic contents of SO₄.     

Mineral dissolution in the Cape Cod aquifer, Massachusetts, USA: I . Reaction stoichiometry and impact of accessory feldspar and glauconite on strontium isotopes, solute concentrations, and REY distribution

To compare relative reaction rates of mineral dissolution in a mineralogically simple groundwater aquifer, we studied the controls on solute concentrations, Sr isotopes, and rare earth element and yttrium (REY) systematics in the Cape Cod aquifer. This aquifer comprises mostly carbonate-free Pleistocene sediments that are about 90% quartz with minor K-feldspar, plagioclase, glauconite, and Fe-oxides. Silica concentrations and pH in the groundwater increase systematically with increasing depth, while Sr isotopic ratios decrease. No clear relationship between ⁸⁷Sr/⁸⁶Sr and Sr concentration is observed. At all depths, the ⁸⁷Sr/⁸⁶Sr ratio of the groundwater is considerably lower than the Sr isotopic ratio of the bulk sediment or its K-feldspar component, but similar to that of a plagioclase-rich accessory separate obtained from the sediment. The Si-⁸⁷Sr/⁸⁶Sr-depth relationships are consistent with dissolution of accessory plagioclase. In addition, solutes such as Sr, Ca, and particularly K show concentration spikes superimposed on their respective general trends. The K-Sr-⁸⁷Sr/⁸⁶Sr systematics suggests that accessory glauconite is another major solute source to Cape Cod groundwater. Although the authigenic glauconite in the Cape Cod sediment is rich in Rb, it is low in in-grown radiogenic ⁸⁷Sr because of its young Pleistocene age. The low ⁸⁷Sr/⁸⁶Sr ratios are consistent with equilibration of glauconite with seawater. The impact of glauconite is inferred to vary due to its variable abundance in the sediments. In the Cape Cod groundwater, the variation of REY concentrations with sampling depth resembles that of K and Rb, but differs from that of Ca and Sr. Shale-normalized REY patterns are light REY depleted, show negative Ce anomalies and super-chondritic Y/Ho ratios, but no Eu anomalies. REY input from feldspar, therefore, is insignificant compared to input from a K-Rb-bearing phase, inferred to be glauconite. These results emphasize that interpretation of groundwater chemistry, even in relatively simple aquifers, may be complicated by solute contributions from “exotic” accessory minerals such as glauconite. To detect such peculiarities, groundwater studies should combine the study of elemental concentration and isotopic composition of several solutes that show different geochemical behavior.     

Controls on the spatial and temporal variability of vadose dripwater geochemistry: Edwards aquifer, central Texas

A 4-yr study of spatial and temporal variability in the geochemistry of vadose groundwaters from caves within the Edwards aquifer region of central Texas offers new insights into controls on vadose groundwater evolution, the relationship between vadose and phreatic groundwaters, and the fundamental influence of soil composition on groundwater geochemistry. Variations in Sr isotopes and trace elements (Mg/Ca and Sr/Ca ratios) of dripwaters and soils from different caves, as well as phreatic groundwaters, provide the potential to distinguish between local variability and regional processes controlling fluid geochemistry, and a framework for understanding the links between climatic and hydrologic processes.The Sr isotope compositions of vadose cave dripwaters (mean ⁸⁷Sr/⁸⁶Sr = 0.7087) and phreatic groundwaters (mean ⁸⁷Sr/⁸⁶Sr = 0.7079) generally fall between values for host carbonates (mean ⁸⁷Sr/⁸⁶Sr = 0.7076) and exchangeable Sr in overlying soils (mean ⁸⁷Sr/⁸⁶Sr = 0.7088). Dripwaters have lower Mg/Ca and Sr/Ca ratios, and higher ⁸⁷Sr/⁸⁶Sr values than phreatic groundwaters. Dripwater ⁸⁷Sr/⁸⁶Sr values also inversely correlate with both Mg/Ca and Sr/Ca ratios. Mass-balance modeling combined with these geochemical relationships suggest that variations in fluid compositions are predominantly controlled by groundwater residence times, and water-rock interaction with overlying soils and host aquifer carbonate rocks. Consistent differences in dripwater geochemistry (i.e., ⁸⁷Sr/⁸⁶Sr, Mg/Ca, and Sr/Ca) between individual caves are similar to compositional differences in soils above the caves. While these differences appear to exert significant control on local fluid evolution, geochemical and isotopic variations suggest that the controlling processes are regionally extensive. Temporal variations in ⁸⁷Sr/⁸⁶Sr values and Mg/Ca ratios of dripwaters from some sites over the 4-yr interval correspond with changes in both aquifer and climatic parameters. These results have important implications for the interpretation of trace element and isotopic variations in speleothems as paleoclimate records, as well as the understanding of controls on water chemistry for both present-day and ancient carbonate aquifers.     

Groundwater recharge and salinization in the arid coastal plain aquifer of the Wadi Watir delta,Sinai, Egypt

The Quaternary coastal plain aquifer down gradient of the Wadi Watir catchment is the main source of potable groundwater in the arid region of south Sinai, Egypt. The scarcity of rainfall over the last decade, combined with high groundwater pumping rates, have resulted in water-quality degradation in the main well field and in wells along the coast. Understanding the sources of groundwater salinization and amount of average annual recharge is critical for developing sustainable groundwater management strategies for the long-term prevention of groundwater quality deterioration. A combination of geochemistry, conservative ions (Cl and Br), and isotopic tracers (^87/86Sr, δ⁸¹Br, δ³⁷Cl), in conjunction with groundwater modeling, is an effective method to assess and manage groundwater resources in the Wadi Watir delta aquifers. High groundwater salinity, including high Cl and Br concentrations, is recorded inland in the deep drilled wells located in the main well field and in wells along the coast. The range of Cl/Br ratios for shallow and deep groundwaters in the delta (∼50–97) fall between the end member values of the recharge water that comes from the up gradient watershed, and evaporated seawater of marine origin, which is significantly different than the ratio in modern seawater (228). The ^87/86Sr and δ⁸¹Br isotopic values were higher in the recharge water (0.70,723 < ^87/86Sr < 0.70,894, +0.94 < δ⁸¹Br < +1.28‰), and lower in the deep groundwater (0.70,698 < ^87/86Sr < 0.70,705, +0.22‰ < δ⁸¹Br < +0.41‰). The δ³⁷Cl isotopic values were lower in the recharge water (−0.48 < δ³⁷Cl < −0.06‰) and higher in the deep groundwater (−0.01 < δ³⁷Cl < +0.22‰). The isotopic values of strontium, chloride, and bromide in groundwater from the Wadi Watir delta aquifers indicate that the main groundwater recharge source comes from the up gradient catchment along the main stream channel entering the delta. The solute-weighted mass balance mixing models show that groundwater in the main well field contains 4–10% deep saline groundwater, and groundwater in some wells along the coast contain 2–6% seawater and 18–29% deep saline groundwater.A three-dimensional, variable-density, flow-and-transport SEAWAT model was developed using groundwater isotopes (⁸⁷Sr/⁸⁶Sr, δ³⁷Cl and δ⁸¹Br) and calibrated using historical records of groundwater level and salinity. δ¹⁸O was used to normalize the evaporative effect on shallow groundwater salinity for model calibration. The model shows how groundwater salinity and hydrologic data can be used in SEAWAT to understand recharge mechanisms, estimate groundwater recharge rates, and simulate the upwelling of deep saline groundwater and seawater intrusion. The model indicates that most of the groundwater recharge occurs near the outlet of the main channel. Average annual recharge to delta alluvial aquifers for 1982 to 2009 is estimated to be 2.16 × 10⁶ m³/yr. The main factors that control groundwater salinity are overpumping and recharge availability.     

The integrated impacts of natural processes and human activities on groundwater salinization in the coastal aquifers of Beihai,southern China

Salinization in coastal aquifers is usually related to both seawater intrusion and water–rock interaction. The results of chemical and isotopic methods were combined to identify the origin and processes of groundwater salinization in Daguansha area of Beihai, southern China. The concentrations of the major ions that dominate in seawater (Cl^?, Na⁺, Ca²⁺, Mg²⁺ and SO ₄ ^2– ), as well as the isotopic content and ratios (²H, ¹⁸O, ⁸⁷Sr/⁸⁶Sr and ¹³C), suggest that the salinization occurring in the aquifer of the coastal plain is related to seawater and that the prevailing hydrochemical processes are evaporation, mixing, dissolution and ion exchange. For the unconfined aquifer, groundwater salinization has occurred in an area that is significantly influenced by land-based sea farming. The integrated impacts of seawater intrusion from the Beibuwan Gulf and infiltration of seawater from the culture ponds are identified in the shallowest confined aquifer (I) in the middle of the area (site BBW2). Leakage from this polluted confined aquifer causes the salinization of groundwater in the underlying confined aquifer (II). At the coastal monitoring site (BBW3), confined aquifer I and lower confined aquifer II are heavily contaminated by seawater intrusion. The weak connectivity between the upper aquifers, and the seaward movement of freshwater, prevents saltwater from encroaching the deepest confined aquifer (III). A conceptual model is presented. Above all, understanding of the origin and processes of groundwater salinization will provide essential information for the planning and sustainable management of groundwater resources in this region.     

87Sr/86Sr in waters from the Lincolnshire Limestone aquifer,England, and the potential of natural strontium isotopes as a tracer for a secondary recovery seawater injection process in oilfields

The Sr isotope composition of formation waters is a sensitive indicator of diagenetic processes in the host sediments, mixing processes between different bodies of water, and the connectivity of hydrological systems. The⁸⁷Sr/⁸⁶Sr ratio of present seawater is constant worldwife, while formation waters in hydrocarbon reservoirs have various values, depending on the aforementioned effects, in most cases different from modern seawater. This forms the basis of anatural tracer technique for seawater injection projects, involving characterization of the⁸⁷Sr/⁸⁶Sr ratios and Sr contents of formation waters in the reservoir before injection commences, followed by monitoring of these parameters in the produced water as injection proceeds. This method is best suited to reservoirs in which the formation waters have low Sr concentrations and⁸⁷Sr/⁸⁶Sr ratios much higher or lower than seawater. Available data for reservoir formation waters suggest that breakthrough recognition could be expected at <10% seawater in many sandstone reservoirs, while the method would be less sensitive in carbonate reservoir or situations where the formation waters had interacted with evaporites, as the associated waters tend to have high Sr contents. In heterogeneous but well-mapped reservoirs, it may be possible to obtain information about flow paths/mechanismsbefore breakthrough. Combination with other chemical and isotopic tracers creates a very powerful tool, the Sr method acting as a safeguard should the batch of water containing the conventional tracers be overtaken by subsequently injected seawater. The Sr method could also be used for injection projects that were begun without the addition of tracers. A natural analogue of a water injection process is found in the Jurassic Lincolnshire Limestone aquifer in England, where rapidly moving fresh meteoric water mixes progressively with an older saline formation water. The⁸⁷Sr/⁸⁶Sr data enable quantitative modelling of this mixing process. The infiltrating fresh water becomes progressively modified by dissolution of detrital carbonate and calcite cement in the limestone, with depth becoming increasingly dominated by Sr derived from the more soluble detrital components. The saline formation water contains water molecules of meteoric origin and an⁸⁷Sr/⁸⁶Sr ratio much higher than Jurassic seawater or marine carbonate; the solute content has been influence by interaction of the water with non-carbonate phases.     

Neodymium isotopes in the Mediterranean Sea: comparison between seawater and sediment signals

Nine depth-profiles of dissolved Nd concentrations and isotopic ratios (ε_Nd) were obtained in the Levantine Basin, the Ionian, the Aegean, the Alboran Seas and the Strait of Gibraltar. Thirteen core-top sediments and Nile River particle samples were also analyzed (leached with 1 N HCl, acetic acid or hydroxylamine hydrochloride). The seawater ε_Nd values become more radiogenic during the eastward circulation in the Mediterranean Sea. The relationship between salinity and the seawater ε_Nd shows that the Nd isotopic signature is more conservative than salinity in the Mediterranean Sea. The water mass with the highest ε_Nd (−4.8) is found at about 200 m in the easternmost Levantine basin. The average ε_Nd value for deep waters is −7.0 in the eastern basin, 2.5 ε-units higher than in the western basin. By examining the sensitivity of seawater ε_Nd to Nd inputs from the Nile, we conclude that the most significant radiogenic Nd source is partially dissolved Nile River particles. The Nd flux from the Nile River water has a minor influence on the Mediterranean seawater ε_Nd. Except for the easternmost Levantine Basin, the leachate ε_Nd values are consistent with the seawater values. In the easternmost Levantine Basin, the leachate ε_Nd values obtained with HCl leaching are systematically higher than the seawater values. The relationship between leachate and residual ε_Nd values indicates that the HCl leaching partially dissolves lithogenic Nd, so the dissolution of Nile River particles is the cause of the observed shift. Some ε_Nd values obtained with hydroxylamine hydrochloride leaching are higher than those obtained with HCl leaching. Although the reason for this shift is not clear, ⁸⁷Sr/⁸⁶Sr successfully detects the presence of a nonmarine component in the leachate. Our results suggest that leaching performance may vary with the mineralogy of marine sediments, at least in the case of the Mediterranean Sea.     

Boron and lithium isotopes as groundwater tracers: a study at the Fresh Kills Landfill,Staten Island,New York,USA

A study was conducted at the Fresh Kills landfill, Staten Island, New York to investigate the use of B and Li isotopes as tracers of mixing and flow in the groundwater environment. Four end-member waters are present at the Fresh Kills: freshwater, seawater, a geochemically distinct transitional groundwater (that occurs in the zone of mixing between seawater and freshwater) and landfill leachate. The δ¹¹B and δ⁶Li values of end-member waters are distinct and have isotopic compositions that reflect the solute sources: freshwater δ¹¹B∼+30‰, δ⁶Li∼−22‰; transition zone groundwaters δ¹¹B∼+20‰, δ⁶Li∼−27‰; seawater δ¹¹B+40 to +75‰, δ⁶Li−37 to−44‰; leachate δ¹¹B∼+10‰ (δ⁶Li not determined). Those wells influenced by seawater exhibited a clear chemical mixing trend, with seawater contributions ranging from 3 to 85%. Well waters with a high percentage of seawater (>30%) had δ¹¹B values that were within 1‰ of the seawater value (+40‰), whereas a trend of increasing δ¹¹B values (+55 to +75‰) was observed for wells with a lower percentage of seawater (<30%). δ⁶Li values for well waters impacted by mixing with seawater ranged from−37 to−44‰, significantly more negative than pure seawater (−31‰). This deviation from the isotopic composition of seawater, for both δ¹¹B and δ⁶Li values, represents non-conservative behavior and is likely the result of isotopic fractionation during ion exchange reactions. The wide range of δ¹¹B and δ⁶Li values and the distinct isotopic compositions of end-member waters makes B and Li isotopes useful for recognizing solute sources, however isotopic fractionation may limit their use as simple tracers of groundwater flow and mixing.     

Origin and evolution of formation water at the Jujo–Tecominoacán oil reservoir,Gulf of Mexico. Part 2: Isotopic and field-production evidence for fluid connectivity

The chemical and isotopic characterization of formation water from 18 oil production wells, extracted from 5200 to 6100 m b.s.l. at the Jujo–Tecominoacán carbonate reservoir in SE-Mexico, and interpretations of historical production records, were undertaken to determine the origin and hydraulic behavior of deep groundwater systems. The infiltration of surface water during Late Pleistocene to Early Holocene time is suggested by ¹⁴C-concentrations from 2.15 to 31.86 pmC, and by ⁸⁷Sr/⁸⁶Sr-ratios for high-salinity formation water (0.70923–0.70927) that are close to the composition of Holocene to modern seawater. Prior to infiltration, the super-evaporation of seawater reached maximum TDS concentrations of 385 g/L, with lowest δ¹⁸O values characterizing the most hypersaline samples. Minor deviations of formation water and dolomite host rocks from modern and Jurassic ⁸⁷Sr/⁸⁶Sr-seawater composition, respectively, suggest ongoing water–rock interaction, and partial isotopic equilibration between both phases. The abundance of ¹⁴C in all sampled formation water, ⁸⁷Sr/⁸⁶Sr-ratios for high-salinity water close to Holocene – present seawater composition, a water salinity distribution that is independent of historic water-cut, and a total water extraction volume of 2.037 MMm³ (1/83–4/07) excludes a connate, oil-leg origin for the produced water of the Jurassic–Cretaceous mudstone-dolomite sequence. Temporal fluctuations of water chemistry in production intervals, the accelerated migration of water fronts from the reservoir flanks, and isotopic mixing trends between sampled wells confirms the existence of free aquifer water below oil horizons. Vertical and lateral hydraulic mobility has probably been accelerated by petroleum extraction.     

Integration of geochemical and isotopic tracers for elucidating water sources and salinization of shallow aquifers in the sub-Saharan Drâa Basin,Morocco

In the arid sub-Saharan of southern Morocco, groundwater salinization poses a direct threat for agricultural production in six oases’ basins that are irrigated by water imported from the High Atlas Mountains. Here the geospatial distribution of salinity is evaluated in shallow groundwater, springs and surface waters in the Drâa Basin, integrating major and trace element geochemistry and isotopic tracers (O, H, Sr and B). The data show that water discharge from the High Atlas Mountains to the Upper section of the Drâa Basin is characterized by both low and high salinity, a distinctive low δ¹⁸O and δ²H composition (as low as −9‰ and −66‰, respectively), typical for meteoric water from high elevation, a ⁸⁷Sr/⁸⁶Sr range of 0.7078–0.7094, and δ¹¹B of 12–17‰. The Ca–Mg–HCO₃, Na–Cl–SO₄, and Ca–SO₄ compositions as well as the Br/Cl, ⁸⁷Sr/⁸⁶Sr, and δ¹¹B values of the saline water suggest dissolution of Lower Jurassic carbonates and evaporite rocks in the High Atlas Mountain catchment. Storage and evaporation of the imported water in a man-made open reservoir causes an enrichment of the stable isotope ratios with a δ¹⁸O/δ²H slope of <8 but no change in the Sr and B isotope fingerprints. Downstream from the reservoir, large salinity variations were documented in the shallow groundwater from the six Drâa oases, with systematically higher salinity in the three southern oases, up to 12,000 mg/L. The increase of the salinity is systematically associated with a decrease of the Br/Cl ratio, indicating that the main mechanism of groundwater salinization in the shallow aquifers in the Drâa oases is via salt dissolution (gypsum, halite) in the unsaturated zone. Investigation of shallow groundwater that flows to the northern Drâa oases revealed lower salinity (TDS of 500–4225) water that is characterized by depleted ¹⁸O and ²H (as low as −9‰ and −66‰, respectively) and higher ⁸⁷Sr/⁸⁶Sr ratios (∼0.7107–0.7115) relative to irrigation water and groundwater flow from the Upper Drâa Basin. This newly-discovered low-saline groundwater with a different isotopic imprint flows from the northeastern Anti-Atlas Jabel Saghro Mountains to the northern oases of the Lower Drâa Basin. This adjacent subsurface flow results in a wide range of Sr isotope ratios in the shallow oases groundwater (0.7084–0.7131) and appears to mitigate salinization in the three northern Drâa oases. In contrast, in the southern oases, the higher salinity suggests that this mitigation is not as affective and increasing salinization through cycles of water irrigation and salt dissolution appears inevitable.     

Origin of groundwater salinity (current seawater vs. saline deep water) in a coastal karst aquifer based on Sr and Cl isotopes. Case study of the La Clape massif (southern France)

In this study a typical coastal karst aquifer, developed in lower Cretaceous limestones, on the western Mediterranean seashore (La Clape massif, southern France) was investigated. A combination of geochemical and isotopic approaches was used to investigate the origin of salinity in the aquifer. Water samples were collected between 2009 and 2011. Three groundwater groups (A, B and C) were identified based on the hydrogeological setting and on the Cl⁻ concentrations. Average and maximum Cl⁻ concentrations in the recharge waters were calculated (Cl_Ref. and Cl_Ref.Max) to be 0.51 and 2.85 mmol/L, respectively). Group A includes spring waters with Cl⁻ concentrations that are within the same order of magnitude as the Cl_Ref concentration. Group B includes groundwater with Cl⁻ concentrations that range between the Cl_Ref and Cl_Ref.Max concentrations. Group C includes brackish groundwater with Cl⁻ concentrations that are significantly greater than the Cl_Ref.Max concentration. Overall, the chemistry of the La Clape groundwater evolves from dominantly Ca–HCO₃ to NaCl type. On binary diagrams of the major ions vs. Cl, most of the La Clape waters plot along mixing lines. The mixing end-members include spring waters and a saline component (current seawater or fossil saline water). Based on the Br/Cl_molar ratio, the hypothesis of halite dissolution from Triassic evaporites is rejected to explain the origin of salinity in the brackish groundwater.Groundwaters display ⁸⁷Sr/⁸⁶Sr ratios intermediate between those of the limestone aquifer matrix and current Mediterranean seawater. On a Sr mixing diagram, most of the La Clape waters plot on a mixing line. The end-members include the La Clape spring waters and saline waters, which are similar to the deep geothermal waters that were identified at the nearby Balaruc site. The ³⁶Cl/Cl ratios of a few groundwater samples from group C are in agreement with the mixing hypothesis of local recharge water with deep saline water at secular equilibrium within a carbonate matrix. Finally, PHREEQC modelling was run based on calcite dissolution in an open system prior to mixing with the Balaruc type saline waters. Modelled data are consistent with the observed data that were obtained from the group C groundwater. Based on several tracers (i.e. concentrations and isotopic compositions of Cl and Sr), calculated ratios of deep saline water in the mixture are coherent and range from 3% to 16% and 0% to 3% for groundwater of groups C and B, respectively.With regard to the La Clape karst aquifer, the extension of a lithospheric fault in the study area may favour the rise of deep saline water. Such rises occur at the nearby geothermal Balaruc site along another lithospheric fault. At the regional scale, several coastal karst aquifers are located along the Gulf of Lion and occur in Mezosoic limestones of similar ages. The ⁸⁷Sr/⁸⁶Sr ratios of these aquifers tend toward values of 0.708557, which suggests a general mixing process of shallow karst waters with deep saline fossil waters. The occurrence of these fossil saline waters may be related to the introduction of seawater during and after the Flandrian transgression, when the highly karstified massifs invaded by seawater, formed islands and peninsulas along the Mediterranean coast.     

Non-uniqueness and interpretation of the seawater Sr/Sr curve

Variations in the seawater ⁸⁷Sr/⁸⁶Sr curve through time can be caused by fluctuations in the strontium flux or variations in the isotopic ratio from at least six different sources and sinks. Thus, 12 or more parameters control each single measurement although widely accepted assumptions allow this to be reduced to typically six unknowns. Interpreting the causes of time-variation in the seawater ⁸⁷Sr/⁸⁶Sr curve is therefore hampered by inherent non-uniqueness. However, this problem is under-constrained rather than unconstrained. As a result, whilst there are an infinite number of possible interpretations, these all come from a few families of very similar solutions. Using this insight, it is possible to find solutions having the smallest possible variations in source flux or source ⁸⁷Sr/⁸⁶Sr ratio. Thus, lower-bounds can be placed upon the source variations responsible for the observed fluctuations in the seawater ⁸⁷Sr/⁸⁶Sr curve. When applied to the evolution of the Early Jurassic ⁸⁷Sr/⁸⁶Sr seawater curve, this approach demonstrates that a short-lived Toarcian event is genuine since it is present in all models, regardless of the values chosen for the unknown source fluxes and unknown source isotope ratios. However, the variations in strontium flux or isotopic ratio necessary to explain the Toarcian event may be significantly smaller than would be predicted assuming modern values for the unknown parameters.     

Determination of Sr/Sr mass-dependent isotopic fractionation and radiogenic isotope variation of Sr/Sr in the Neoproterozoic Doushantuo Formation

We measured both mass-dependent isotope fractionation of δ⁸⁸Sr (⁸⁸Sr/⁸⁶Sr) and radiogenic isotopic variation of Sr (⁸⁷Sr/⁸⁶Sr) for the Neoproterozoic Doushantuo Formation that deposited as a cap carbonate immediately above the Marinoan-related Nantuo Tillite. The δ⁸⁸Sr and ⁸⁷Sr/⁸⁶Sr compositions showed three remarkable characteristics: (1) high radiogenic ⁸⁷Sr/⁸⁶Sr values and gradual decrease in the ⁸⁷Sr/⁸⁶Sr ratios, (2) anomalously low δ⁸⁸Sr values at the lower part cap carbonate, and (3) a clear correlation between ⁸⁷Sr/⁸⁶Sr and δ⁸⁸Sr values. These isotopic signatures can be explained by assuming an extreme greenhouse condition after the Marinoan glaciation. Surface seawater, mixed with a large amount of freshwater from continental crusts with high ⁸⁷Sr/⁸⁶Sr and lighter δ⁸⁸Sr ratios, was formed during the extreme global warming after the glacial event. High atmospheric CO₂ content caused sudden precipitation of cap carbonate from the surface seawater with high ⁸⁷Sr/⁸⁶Sr and lighter δ⁸⁸Sr ratios. Subsequently, the mixing of the underlying seawater, with unradiogenic Sr isotope compositions and normal δ⁸⁸Sr ratios, probably caused gradual decrease of the ⁸⁷Sr/⁸⁶Sr ratios of the seawater and deposition of carbonate with normal δ⁸⁸Sr ratios. The combination of ⁸⁷Sr/⁸⁶Sr and δ⁸⁸Sr isotope systematics gives us new insights on the surface evolution after the Snowball Earth.     

The groundwater geochemistry of the Bengal Basin: Weathering, chemsorption, and trace metal flux to the oceans

Sixty-eight groundwater samples from the Ganges-Brahmaputra floodplain in the Bengal Basin were analyzed to assess the groundwater geochemistry, the subsurface hydrology, the buffering effects of sediments on trace metal concentrations and their isotopic compositions, and the magnitude of the subsurface trace element flux to the Bay of Bengal and to the global ocean. Samples obtained from depths of 10 to 350 m were measured for major and trace elements, dissolved gas, and tritium. On the basis of the ³He/³H ages, the groundwater at depth (30-150 m) appears to be continually replenished, indicating that this recharge of groundwater to depth must ultimately be balanced by a significant quantity of submarine discharge into the Bay of Bengal. Using the ³He/³H groundwater age-depth relationship to calculate a recharge rate of 60 ± 20 cm/yr, we estimate a subsurface discharge into the Bay of Bengal of 1.5 ± 0.5 × 10¹¹ m³/yr, or 15% of the surface Ganges-Brahmaputra river (GBR) flux. Several trace elements, especially Sr and Ba, display elevated concentrations averaging 7 to 9 times the surface GBR water values. The submarine groundwater fluxes of Sr and Ba to the oceans are 8.2 ± 2 × 10⁸ and 1.5 ± 0.3 × 10⁸ mol/yr, or 3.3 and 1.2%, respectively, of the world total, or equal to the surface GBR Sr and Ba estimated fluxes. Our groundwater flux for Ba agrees with the estimate of Moore (1997) (3 × 10⁸-3 × 10⁹ mol/yr), on the basis of measured Ba and Ra excesses in the Bay of Bengal. Other trace metals, such as U and Mo, are at low but measurable levels and are not major contributors to the global flux in this river system. A comparison of the Sr and Ba concentrations, plus ⁸⁷Sr/⁸⁶Sr ratios in groundwater to the oxalate extractable fractions of a coastal sediment core, suggests that weathering of carbonates and minor silicates, coupled with cation exchange plus adsorption and desorption reactions, controls the trace element concentrations and ⁸⁷Sr/⁸⁶Sr isotopic compositions in both the groundwater and river water. Our data also imply that other coastal floodplains (e.g., the Mekong and the Irrawaddy rivers) that have high precipitation rates and rapid accumulation of immature sediments are likely to make significant contributions to the global oceanic trace metal budgets and have an impact on the Sr isotopic evolution in seawater.     

Hydrogeochemical evolution of confined groundwater in northeastern Osaka Basin,Japan: estimation of confined groundwater flux based on a cation exchange mass balance method

A confined aquifer system has developed in argillaceous marine and freshwater sediments of Pliocene–Holocene age in the northeastern Osaka Basin (NEOB) in central Japan. The shallow groundwater (<100 m) in the system is recharged in a northern hilly to mountainous area with dominantly Ca-HCO₃ type water, which changes as it flows toward the SW to Mg-HCO₃ type and then to Na-HCO₃ type water. Comparison of the chemical and Sr isotopic compositions of the groundwater with those of the bulk and exchangeable components of the underground sediments indicates that elements leached from the sediments contribute negligibly to the NEOB aquifer system. Moreover, model calculations show that contributions of paleo-seawater in the deep horizon and of river water at the surface are not major factors of chemical change of the groundwater. Instead, the zonal pattern of the HCO₃-dominant groundwater is caused by the loss of Ca²⁺ from the water as it is exchanged for Mg²⁺ in clays, followed by loss of Mg + Ca as they are exchanged for Na + K in clays between the Ca-HCO₃ type recharge water and the exchangeable cations in the clay layers, which were initially enriched in Na⁺. Part of this process was reproduced in a chromatographic experiment in which Na type water with high ⁸⁷Sr/⁸⁶Sr was obtained from Mg type water with low ⁸⁷Sr/⁸⁶Sr by passing it through marine clay packed in a column. The flux of recharge water into the confined aquifer system according to this chromatographic model is estimated to be 0.99 mm/day, which is compatible with the average recharge flux to unconfined groundwater in Japan (1 mm/day).     

Chemostratigraphy and detrital zircon geochronology of the Neoproterozoic Khorbusuonka Group,Olenek Uplift,Northeastern Siberian platform

This study provides ⁸⁷Sr/⁸⁶Sr, δ¹³C and δ¹⁸O data from the best-preserved limestone and dolomite of the Ediacaran carbonate-dominated Khorbusuonka Group of the Olenek Uplift, NE Siberian Craton, as well as detrital zircon geochronological data from both underlying and overlying sandstones. The Maastakh Formation is characterized by ⁸⁷Sr/⁸⁶Sr ratios of ca. 0.70822 and δ¹³C values between + 4.8 and + 6.0‰. ⁸⁷Sr/⁸⁶Sr ratios in limestones of the Khatyspyt Formation are fairly uniform, ranging from 0.70783 to 0.70806. The carbon isotopic composition slowly decreases from bottom (+ 3.7‰) to top (− 0.2‰) of section. The Sr isotopic composition of the Turkut Formation varies from 0.70824 to 0.70914, value of δ¹³C is about zero: − 0.7…+0.7 ‰. The youngest population of detrital zircons from Maastakh Formation indicates that these rocks were formed not later than 630 Ma. U–Pb detrital zircons data of Kessyusa Group has a single peak at about 543 Ma, which is almost identical to the earlier dating. Based on biostratigraphy and isotopic data, the Sr isotopic compositions from the Khatyspyt Formation (⁸⁷Sr/⁸⁶Sr = 0.70783–0.70806) represent the composition of seawater at 560–550 Ma. Such low values of ⁸⁷Sr/⁸⁶Sr ratio in Ediacaran water were probably caused by the quick opening of Iapetus Ocean.     

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.