Establishing constraints on groundwater ages with Cl,C, H,and noble gases: A case study in the eastern Paris basin,France

Groundwaters from the Tithonian/Kimmeridgian, Oxfordian and Upper Dogger aquifers, within the eastern part of the Paris basin (France), were characterised using ³H, ¹⁴C and ³⁶Cl, and noble gases tracers, to evaluate their residence times and determine their recharge period. This information is an important prerequisite to evaluating the confinement properties of the Callovo-Oxfordian clay formation sandwiched between the Oxfordian aquifer and the Dogger aquifer, currently being investigated by the French nuclear waste management agency (Andra) for radioactive waste disposal. Data presented in this paper are used to test 4 hypotheses.     

Water circulation control on carbonate-δO records in a low permeability clay formation and surrounding limestones: The Upper Dogger–Oxfordian sequence from the eastern Paris basin, France

Upper Dogger to Oxfordian Formations in the eastern part of the Paris basin (France) are currently being investigated by the French nuclear waste management agency (Andra), testing the feasibility of long-term deep nuclear waste disposal in the Callovo-Oxfordian claystones. Characterising the hydrogeological behaviour of the Callovo-Oxfordian claystones is, therefore, essential in evaluating its potential as a geological barrier. In order to evaluate and quantify water/rock interactions experienced over geological time by these Formations, bulk carbonate δ¹³C and δ¹⁸O were measured and calculations of water-rock ratios were used to explain carbonate-δ¹⁸O changes. Meteoric porewater and a maximum temperature reached of about 40 °C were considered. The Jurassic marine carbonate δ¹³C was preserved in the Callovo-Oxfordian claystones and in the overlying limestones (−0.28‰ to 3.39‰/PDB), while the δ¹⁸O values are lower by 0-5‰ (−6.25‰ to −1.32‰/PDB). Calculations show that Upper Dogger and Oxfordian Limestone δ¹⁸O data:

(i)

have random-like distribution through theoretical δ¹⁸O-W/R curves and

(ii)

suggest that water/rock ratios (0.08-0.4) needed to explain δ¹⁸O changes are higher by a factor of about 2-20 compared to the present-day water/rock ratio.

These features indicate advection in both aquifers. According to the history of the Paris basin, this hydrogeological behaviour could have been effective since Jurassic/Cretaceous transition times. Inversely, the carbonate-δ¹⁸O content trends observed for the Callovo-Oxfordian data show that changes were controlled by post-depositional fluid-rock interaction with water/rock ratio (0.02-0.15) similar to the present-day porewater/rock ratio. The 130 m thick Callovo-Oxfordian claystone appears remarkably homogenous regarding its hydrogeological properties. This study suggests an initial marine porewater replacement by meteoric water only after porosity was reduced to its present value, thus demonstrating that the Callovo-Oxfordian clay has mainly been isolated from advective meteoric water circulation. Only the upper 20 m of the Callovo-Oxfordian claystone Formation underwent heterogeneous water-rock exchange (W/R from 0.01 to 0.3), probably as a result of its mineralogical heterogeneity and proximity to the advective Oxfordian Limestone aquifer.This study of carbonate-δ¹⁸O confirms the hydrogeological barrier properties of the Callovo-Oxfordian clay and suggests that it has been a natural hydrological barrier since the earliest times of its diagenesis.     

Stable isotope geochemistry of dissolved chloride in relation to hydrogeology of the strongly exploited Quaternary aquifers,North China Plain

Deep Quaternary groundwater is the main source for industrial, domestic, and agricultural water supply in the North China Plain (NCP). There is currently a regional decline of groundwater levels, deterioration of water quality and environmental geological problems induced by increasing exploitation of the NCP Quaternary aquifer system. To trace sources and transport processes of dissolved Cl⁻ in a regional aquifer system and to reveal hydrogeological characteristics of Quaternary complexes, δ³⁷Cl, δ¹⁸O and δD, and chemical compositions (including F⁻, Cl⁻, Br⁻) of the deep groundwater sampled from the northern flow system of the NCP were measured along the west–east groundwater flow paths. The measured δ³⁷Cl values decreased from 0.39‰ to −2.22‰ (SMOC) along the groundwater flow direction, with increasing Cl⁻ concentrations. Marine aerosol input via rainfall is the main source of Cl⁻ in the deep groundwater near the recharge areas, and subsequent evaporation/evapotranspiration appears to be responsible for Cl⁻ accumulation. Mixing of recharge water with water of high-Cl⁻ and low-δ³⁷Cl accounts for the pattern of δ³⁷Cl and Cl⁻ concentration observed in Aquifer-3 along the west–east transect. The water with high-Cl and low-δ³⁷Cl is likely from pore water released from compacted clays induced by over-exploitation of deep groundwater, suggesting that clay is a dominant subsurface source of Cl⁻ for groundwater where a regional depression cone is present in the Quaternary aquifers. The groundwater of Aquifer-4 in the Huang-Hua depression is potentially mixed with an upward flux of Cl⁻ from the Neogene aquifer through subvertical faults. Diffusion and ion filtration are two mechanisms invoked to explain the highly negative δ³⁷Cl data for groundwater of Aquifer-4 in the Yanshan–Haixing areas, which provides new insight into solute migration and the hydraulic relationship in the strongly exploited groundwater system. This study using the conservative solute Cl⁻ provides additional important information for further investigations of the geochemistry of a wide range of reactive solutes in the Quaternary aquifer system, so guiding water resource management.     

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.     

Origin and history of waters associated with coalbed methane: I, Cl, and stable isotope results from the Fruitland Formation, CO and NM

The Fruitland Formation of the San Juan Basin was deposited during the late Cretaceous and is associated with significant reservoirs of coalbed methane (CBM). The purpose of this study is to determine the origin and history of waters associated with the formation, using long-lived cosmogenic and stable isotope systems. Ratios of ¹²⁹I/I and stable isotope values (δD and δ¹⁸O) were determined in waters from close to 100 wells, ³⁶Cl/Cl ratios for a subset of these samples. A significant group of samples has ¹²⁹I/I ratios between 100 × 10⁻¹⁵ and 200 × 10⁻¹⁵, indicating minimum iodine ages close to 60 Ma. If these ages are corrected for the addition of fissiogenic ¹²⁹I, they are compatible with the depositional age of the Fruitland Formation (Late Cretaceous).Several sets of waters are clearly present within the data. A group dominated by infiltration of recent surface waters is restricted to the uplifted basin margins, with a lateral extent of less than 5 km from outcrop, and is characterized by ¹²⁹I/I ratios in excess of 1500 × 10⁻¹⁵ and meteoric δD, δ¹⁸O, and ³⁶Cl/Cl signatures. The rest of the basin is characterized by several subsets of formation waters which have undergone variable degrees of iodine enrichment through diagenesis as well as variable degrees of dilution. The first subgroup is found in coals of relatively low vitrinite reflectance and moderate enrichment of iodine. This subgroup predominantly consists of entrapped pore fluids, although it may also contain waters which infiltrated the coals at the time of the Laramide uplift, between 25 and 30 Ma. A second subgroup consists of formation waters associated with coals of high vitrinite reflectance. Despite subsequent uplift, the high iodine concentrations and low ¹²⁹I/I ratios of this subgroup, as well as a moderate depletion of deuterium relative to ¹⁸O, suggest that these waters were not significantly altered since the time when diagenetic reactions occurred in the deepest portion of the basin. A third subgroup, with higher δD and δ¹⁸O values as well as higher ¹²⁹I/I ratios, extends roughly west to east at the New Mexico-Colorado state line and corresponds to a region of extensive fracturing of the coalbeds. In this case, the higher ¹²⁹I/I ratios are probably due to contributions of fissiogenic ¹²⁹I through fracture flow, perhaps from deeper formation waters. Our results do not support models of subsequent basin-wide groundwater migration in the Fruitland Formation. The combined use of ¹²⁹I and ³⁶Cl with stable isotope studies provides valuable information as to the hydrologic history of coalbed methane deposits, as well as their potential for commercial exploitation.     

Cl,N, C isotopic analysis of common agro-chemicals for identifying non-point source agricultural contaminants

The isotopic compositions of commercially available herbicides were analyzed to determine their respective ¹⁵N, ¹³C and ³⁷Cl signatures for the purposes of developing a discrete tool for tracing and identifying non-point source contaminants in agricultural watersheds. Findings demonstrate that of the agrochemicals evaluated, chlorine stable isotopes signatures range between δ³⁷Cl = −4.55‰ and +3.40‰, whereas most naturally occurring chlorine stable isotopes signatures, including those of road salt, sewage sludge and fertilizers, vary in a narrow range about the Standard Mean Ocean Chloride (SMOC) between −2.00‰ and +1.00‰. Nitrogen stable isotope values varied widely from δ¹⁵N = −10.86‰ to +1.44‰ and carbon stable isotope analysis gave an observed range between δ¹³C = −37.13‰ and −21.35‰ for the entire suite of agro-chemicals analyzed. When nitrogen, carbon and chlorine stable isotope analyses were compared in a cross-correlation analysis, statistically independent isotopic signatures exist suggesting a new potential tracer tool for identifying herbicides in the environment.     

Control of Cl production in carbonaceous shales by phosphate minerals

When using ³⁶Cl to date very old groundwater in regional aquifer systems, knowledge of the subsurface ³⁶Cl input into the aquifer system is essential. Although ³⁶Cl can be produced through nuclear reactions in the subsurface, in many situations, the input of ³⁶Cl into sedimentary aquifer systems by this avenue of production can be neglected. This is a valid assumption when investigating long-flowpath groundwater systems composed of sandstones, limestones, and shales of typical composition. These rock types are not sufficiently enriched in radioactive elements to produce significant ³⁶Cl in the deep subsurface. Carbonaceous shales, on the other hand, can concentrate the radioactive elements necessary to produce significant ³⁶Cl in the deep subsurface. Chlorine-36 ratios (³⁶Cl/Cl) for a suite of Late Devonian and Pennsylvanian carbonaceous shales were calculated from bulk-rock chemistry as well as measured using accelerator mass spectrometry. The poor agreement between calculated and measured ratios is the result of the assumption of chemical homogeneity used by the calculation algorithm, an assumption that was not satisfied by the carbonaceous shales. In these shales, organic matter, clay minerals, and accessory minerals are heterogeneously distributed and are physically distinct on a micron-order scale. Although organic matter and clay minerals constitute the overwhelming bulk of the shales, it is the phosphate minerals that are most important in enhancing, and suppressing, ³⁶Cl production. Minerals such as apatite and carbonate-apatite (francolite)—by including uranium, rare earth elements (REEs), and halogens—have an important impact on both neutron production and thermal neutron absorption. By incorporating both uranium and fluorine, phosphate minerals act as neutron production centers in the shale, increasing the probability of ³⁶Cl production. By incorporating REEs and chlorine, phosphate minerals also act to shield ³⁵Cl from the thermal neutron flux, effectively suppressing the production of ³⁶Cl. To reconcile the measured ³⁶Cl ratios with the ratios calculated assuming chemical homogeneity, the shales were artificially split into three fractions: organic, clay mineral, and phosphate mineral. Neutron production was calculated separately for each fraction, and the calculation results demonstrated that the phosphate fraction exerted much more control on the ³⁶Cl ratio than the organic or clay mineral fractions. By varying the uranium and chlorine contents in the phosphate fraction, a new, heterogeneous ³⁶Cl ratio was calculated that agreed with the measured ratio for the overwhelming majority of the carbonaceous shales. When using rock chemistry to calculate the ³⁶Cl ratio, rock types that show mineralogical heterogeneity on a micron scale can be divided into bulk fractions and accessory fractions for separate calculations of neutron production and neutron absorption. In this manner, a more accurate, heterogeneous ³⁶Cl ratio can be calculated for the rock as a whole.     

Chlorine isotopic composition in seafloor serpentinites and high-pressure metaperidotites. Insights into oceanic serpentinization and subduction processes

Bulk-rock chlorine content and isotopic composition (δ³⁷Cl) were determined in oceanic serpentinites, high-pressure metaperidotites and metasediments in order to gain constraints on the global chlorine cycle associated with hydrothermal alteration and subduction of oceanic lithosphere. The distribution of insoluble chlorine in oceanic serpentinites was also investigated by electron microprobe. The hydrothermally-altered ultramafic samples were dredged along the South West Indian Ridge and the Mid-Atlantic Ridge. The high-pressure metamorphic samples were collected in the Western Alps: metaperidotites in the Erro-Tobbio unit and metasediments in the Schistes Lustrés nappe.Oceanic serpentinites show relatively large variations of bulk-rock Cl contents and δ³⁷Cl values with mean values of 1105 ± 596 ppm and −0.7 ± 0.4‰, respectively (n = 8; 1σ). Serpentines formed after olivine (meshes) show lower Cl content than those formed after orthopyroxene (bastites). In bastites of two different samples, Cl is positively correlated with Al₂O₃ and negatively correlated with SiO₂. These relationships are interpreted as reflecting preferential Cl-incorporation into the bastite structure distorted by Al (substituted for Si) rather than different alteration conditions between olivine and orthopyroxene minerals. High-pressure metaperidotites display relatively homogeneous Cl contents and δ³⁷Cl values with mean values of 467 ± 88 ppm and −1.4 ± 0.1‰, respectively (n = 7; 1σ). A macroscopic high-pressure olivine-bearing vein, formed from partial devolatilization of serpentinites at ∼2.5 GPa and 500-600 °C, shows a Cl content and a δ³⁷Cl value of 603 ppm and −1.6‰, respectively. Metasediments (n = 2) show low whole-rock Cl contents (<15 ppm Cl) that did not allow Cl isotope analyses to be obtained.The range of negative δ³⁷Cl values observed in oceanic serpentinites is likely to result from water-rock interaction with fluids that have negative δ³⁷Cl values. The homogeneity of δ³⁷Cl values from the high-pressure olivine-bearing vein and the metaperidotite samples implies that progressive loss of Cl inherited from oceanic alteration throughout subduction did not significantly fractionate Cl isotopes. Chlorine recycled in subduction zones via metaperidotites should thus show a range of δ³⁷Cl values similar to the range found in oceanic serpentinized peridotites.     

The Middle to Upper Jurassic stable isotope record of Madagascar: Linking temperature changes with plate tectonics during the break-up of Gondwana

Stable isotope (δ¹⁸O, δ¹³C) analyses were performed on well preserved belemnites, oysters, and rhynchonellid brachiopods from the Middle to Upper Jurassic of the Morondava Basin in southern Madagascar. Both brachiopods and oysters indicate similar average temperatures of 18.7 to 19.3 °C in the Early Callovian, followed by a temperature decrease towards the Middle Oxfordian (13.9 °C) and a minimum in the Early Kimmeridgian (12.3 °C). In contrast, belemnites from the Oxfordian show lower average temperatures of 10.0 °C, which is likely caused by specific conditions for these organisms (e.g., different fractionation or life habits). Additionally, three oysters from the Upper Oxfordian and Lower Kimmeridgian were used for high-resolution stable isotope analyses. The data show seasonal fluctuations of >6 °C around averages between 14.4 and 14.7 °C. Latitudinal temperature gradients for the Callovian and Kimmeridgian are similar to today at the examined low latitudes of the southern hemisphere. The observed cooling of around 5 °C from the Callovian to the Oxfordian/Kimmeridgian can be attributed to a concurrent southward drift of Madagascar during the break-up of Gondwana. Thus, the study underlines the importance of considering palaeogeography in interpreting stable isotope data as well as the potential of detecting and timing palaeogeographic events by using stable isotope analyses.     

Magnesium isotope systematics of the lithologically varied Moselle river basin, France

Magnesium and strontium isotope signatures were determined during different seasons for the main rivers of the Moselle basin, northeastern France. This small basin is remarkable for its well-constrained and varied lithology on a small distance scale, and this is reflected in river water Sr isotope compositions. Upstream, where the Moselle River drains silicate rocks of the Vosges mountains, waters are characterized by relatively high ⁸⁷Sr/⁸⁶Sr ratios (0.7128-0.7174). In contrast, downstream of the city of Epinal where the Moselle River flows through carbonates and evaporites of the Lorraine plateau, ⁸⁷Sr/⁸⁶Sr ratios are lower, down to 0.70824.Magnesium in river waters draining silicates is systematically depleted in heavy isotopes (δ²⁶Mg values range from −1.2 to −0.7‰) relative to the value presently estimated for the continental crust and a local diorite (−0.5‰). In comparison, δ²⁶Mg values measured in soil samples are higher (∼0.0‰). This suggests that Mg isotope fractionation occurs during mineral leaching and/or formation of secondary clay minerals. On the Lorraine plateau, tributaries draining marls, carbonates and evaporites are characterized by low Ca/Mg (1.5-3.2) and low Ca/Sr (80-400) when compared to local carbonate rocks (Ca/Mg = 29-59; Ca/Sr = 370-2200), similar to other rivers draining carbonates. The most likely cause of the Mg and Sr excesses in these rivers is early thermodynamic saturation of groundwater with calcite relative to magnesite and strontianite as groundwater chemistry progressively evolves in the aquifer. δ²⁶Mg of the dissolved phases of tributaries draining mainly carbonates and evaporites are relatively low and constant throughout the year (from −1.4‰ to −1.6‰ and from −1.2‰ to −1.4‰, respectively), within the range defined for the underlying rocks. Downstream of Epinal, the compositions of the Moselle River samples in a δ²⁶Mg vs. ⁸⁷Sr/⁸⁶Sr diagram can be explained by mixing curves between silicate, carbonate and evaporite waters, with a significant contribution from the Vosgian silicate lithologies (>70%). Temporal co-variation between δ²⁶Mg and ⁸⁷Sr/⁸⁶Sr for the Moselle River throughout year is also observed, and is consistent with a higher contribution from the Vosges mountains in winter, in terms of runoff and dissolved element flux. Overall, this study shows that Mg isotopes measured in waters, rocks and soils, coupled with other tracers such as Sr isotopes, could be used to better constrain riverine Mg sources, particularly if analytical uncertainties in Mg isotope measurements can be improved in order to perform more precise quantifications.     

Sr-isotope stratigraphy of the Upper Jurassic of central Portugal (Lusitanian Basin) based on oyster shells

Strontium isotope stratigraphy was performed on oyster shells from the Late Jurassic of the Lusitanian Basin (central Portugal). This represents the first approach to obtain numerical ages for these strata. The new chronostratigraphic data provide a more precise age determination of several units. After a basin-wide hiatus sedimentation in the Late Jurassic is proven in the Cabo Mondego and Cabaços formations to resume as early as the Middle Oxfordian. The Alcobaça formation can be placed in the latest Late Oxfordian to Late Kimmeridgian, while data from the upper part of the Abadia Formation indicate an Early to Late Kimmeridgian age. The Farta Pao formation ranges from the latest Kimmeridgian to the latest Tithonian. The largely synchronous Sobral, Arranhó I, and Arranhó II members are overlain by the late Early to Late Tithonian Freixial Member. The brief, local carbonate incursion of the Arranhó I member marks the Kimmeridgian–Tithonian boundary. Oysters are shown once more to be suitable for strontium isotope studies. Their calcitic shells are often unaffected by diagenesis. In particular for marginal marine Jurassic and Cretaceous strata, where belemnites are usually absent, oysters may serve as a valuable tool for isotope stratigraphy.     

Stable chlorine isotopic signatures and fractionation mechanism of groundwater in Anyang,China

The present work provides an online Bench II-IRMS technique for the measurement of stable chlorine isotope ratio, which is used to measure the δ³⁷Cl of 38 groundwater samples from the Karst and Quaternary aquifers in Anyang area. The regional distribution and signature of δ³⁷Cl value are characterized on the base of isotopic data. The results suggest that the δ³⁷Cl value of Quaternary groundwater decreases with increasing Cl^? concentration, and has no correlation with δ¹⁸O and δD values, but closely correlates with the depth to water table. The fractionation mechanism of the chlorine isotope is expounded according to the type of groundwater. The δ³⁷Cl value of karst water is generally positive, which is relevant to the dissolution of evaporite (gypsum mine), and may be caused by the mixing of groundwater and precipitation. The groundwater of Quaternary unconfined aquifer is mainly recharged by precipitation, and the δ³⁷Cl value of groundwater is generally negative. The δ³⁷Cl value of groundwater in Quaternary confined aquifer is more negative with increasing the depth to water level and elevated Cl^? concentration, which is possible to result from the isotope fractionation of ion filtration. The groundwater with inorganic pollutants in Quaternary unconfined aquifer has generally a positive δ³⁷Cl value.     

Mineralogical and isotopic record of biotic and abiotic diagenesis of the Callovian-Oxfordian clayey formation of Bure (France)

The Callovian-Oxfordian (COx) clayey unit is being studied in the Eastern part of the Paris Basin at depths between 400 and 500 m depth to assess of its suitability for nuclear waste disposal. The present study combines new mineralogical and isotopic data to describe the sedimentary history of the COx unit. Petrologic study provided evidence of the following diagenetic mineral sequence: (1) framboidal pyrite and micritic calcite, (2) iron-rich euhedral carbonates (ankerite, sideroplesite) and glauconite (3) limpid calcite and dolomite and celestite infilling residual porosity in bioclasts and cracks, (4) chalcedony, (5) quartz/calcite. Pyrite in bioturbations shows a wide range of δ³⁴S (−38‰ to +34.5‰), providing evidence of bacterial sulphate reduction processes in changing sedimentation conditions. The most negative values (−38‰ to −22‰), measured in the lower part of the COx unit indicate precipitation of pyrite in a marine environment with a continuous sulphate supply. The most positive pyrite δ³⁴S values (−14‰ up to +34.5‰) in the upper part of the COx unit indicate pyrite precipitation in a closed system. Celestite δ³⁴S values reflect the last evolutionary stage of the system when bacterial activity ended; however its deposition cannot be possible without sulphate supply due to carbonate bioclast dissolution. The ⁸⁷Sr/⁸⁶Sr ratio of celestite (0.706872-0.707040) is consistent with deposition from Jurassic marine-derived waters. Carbon and oxygen isotopic compositions of bulk calcite and dolomite are consistent with marine carbonates. Siderite, only present in the maximum clay zone, has chemical composition and δ¹⁸O consistent with a marine environment. Its δ¹³C is however lower than those of marine carbonates, suggesting a contribution of ¹³C-depleted carbon from degradation of organic matter. δ¹⁸O values of diagenetic chalcedony range between +27‰ and +31‰, suggesting precipitation from marine-derived pore waters. Late calcite crosscutting a vein filled with chalcedony and celestite, and late euhedral quartz in a limestone from the top of the formation have lower δ¹⁸O values (∼+19‰), suggesting that they precipitated from meteoric fluids, isotopically close to present-day pore waters of the formation. Finally, the study illustrates the transition from very active, biotic diagenesis to abiotic diagenesis. This transition appears to be driven by compaction of the sediment, which inhibited movement of bacterial cells by reduction of porosity and pore sizes, rather than a lack of inorganic carbon or sulphates.     

Geochemistry and14C dating of groundwaters from Jurassic aquifers of North Aquitaine Basin (France)

Twenty-seven samples from a confined Lower-Middle Jurassic aquifer and an unconfined Oxfordian aquifer of the North Aquitaine Basin (France) have been analysed for their major elements, Br⁻,¹⁸O,²H,¹³C and¹⁴C contents. Hydrochemistry indicates (1) a dissolution of carbonate and anhydrite near the recharge zone and (2) a dilution of a saline water derived from a seawater/halite mixing in the deeper part of the aquifer. The mixing is also visible in a δ¹⁸O vs Cl⁻ diagram in which two different groups appear: recent waters and old waters indicating a mixing process between fresh and saline groundwaters. The composition of the saline water is likely to be 34,100±11,200 ppm in Cl, 70±20 ppm in Br and more than −3.5±07‰ vs SMOW in¹⁸O.¹³C contents indicate (1) a C exchange with CaCO₃ matrix for groundwaters near the recharge zone and (2) a participation of organic matter in the deep part of the aquifer.Residence times for waters near the area of the aquifer outcrop correspond to Holocene and Late Pleistocene periods. The depletion in stable isotopes of 10 to 15,000 y B.P. waters show a late glacial period infiltration to the aquifer. After a distance of about 10 km in the aquifer, the¹⁴C activities are 0 pmc showing the presence of ‘old’ groundwaters.     

The transport of U- and Th-series nuclides in sandy confined aquifers

Abundances of ²³⁸U, ²³⁴U, ²³²Th, ²²⁶Ra, ²²⁸Ra, ²²⁴Ra, and ²²²Rn were measured in groundwaters of the Ojo Alamo aquifer in northwest New Mexico. This is an arid area with annual precipitation of ∼22 cm. The purpose was to investigate the transport of U-Th series nuclides and their daughter products in an old, slow-moving groundwater mass as a means of understanding water-rock interactions and to compare the results with a temperate zone aquifer. It was found that ²³²Th is approximately at saturation and supports the view of Tricca et al. (2001) that Th is precipitated irreversibly upon weathering, leaving surface coatings of ²³²Th and ²³⁰Th on aquifer grains. Uranium in the aquifer waters has very high [²³⁴U/²³⁸U] ∼ 9 and low ²³⁸U concentrations. These levels can be explained by low weathering rates in the aquifer (w_238U ∼ 2 × 10⁻¹⁸ to 2 × 10⁻¹⁷s⁻¹) using a continuous flow, water-rock interaction model. The Ra isotopes are roughly in secular equilibrium despite their very different mean lifetimes. The ²²²Rn and ²²⁸Ra isotopes in the aquifer correspond to ∼10% of the net production rate of the bulk rock. This is interpreted to reflect an earlier formed irreversible surface coating of Th that provides Ra and Rn to the aquifer waters. The surface waters that appear to be feeding the aquifer have low [²³⁴U/²³⁸U] and high ²³⁸U concentrations. The flow model shows that it is not possible to obtain the high [²³⁴U/²³⁸U] and low [²³⁸U] values in the aquifer from a source like the present vadose zone input. It follows that the old aquifer waters studied cannot be fed by the present vadose zone input unless they are greatly diluted with waters with very low U concentrations. If the present sampling of vadose zone sources is representative of the present input, then this requires that there was a major change in water input with much larger rainfall some several thousand years ago. This may represent a climatic change in the Southwest.     

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.     

Oxygen and carbon isotope and Sr/Ca signatures of high-latitude Permian to Jurassic calcite fossils from New Zealand and New Caledonia

Calcite fossils from New Zealand and New Caledonia provide insight into the Permian to Jurassic climatic history of Southern High Latitudes (southern HL) and Triassic Southern Intermediate Latitudes (southern IL). These results permit comparison with widely studied, coeval sections in Low Latitudes (LL) and IL. Oxygen isotope ratios of well-preserved shell materials indicate a partially pronounced Sea Surface Temperature (SST) gradient in the Permian, whereas for the Triassic no indication of cold climates in the southern HL is found. The Late Jurassic of New Zealand is characterized by a slight warming in the Oxfordian–Kimmeridgian and a subsequent cooling trend in the Tithonian. Systematic variations in the δ¹³C values of southern HL samples are in concert with those from LL sections and confirm the global nature of the carbon isotope signature and changes in the long-term carbon cycle reported earlier.Systematic changes of Sr/Ca ratios in Late Triassic brachiopods, falling from 1.19 mmol/mol in the Oretian (early Norian) to 0.67 mmol/mol in the Warepan (late Norian) and subsequently increasing to 1.10 mmol/mol in the Otapirian (~ Rhaetian), are observed. Also Sr/Ca ratios of Late Jurassic belemnite genera Belemnopsis and Hibolithes show synchronous changes in composition that may be attributed to secular variations in the seawater Sr/Ca ratio. For the two belemnite genera an increase from 1.17 mmol/mol in the Middle Heterian (~ Oxfordian) to 1.78 mmol/mol in the Mangaoran (~ late Middle Tithonian) and a subsequent decrease to 1.51 mmol/mol in the Waikatoan (~ Late Tithonian) is documented.     

Genesis of arsenic/fluoride-enriched soda water: A case study at Datong,northern China

The high As and F⁻ groundwaters from Datong Basin are mostly soda waters with a Na/(Cl+SO₄) (meq) ratio greater than unity, As and F⁻ up to 1550 μg/L and 10.4 mg/L, respectively, and with pH between 7.6 and 9.1. Geochemical modeling indicates that the waters are oversaturated with respect to calcite and clay minerals such as kaolinite, and undersaturated with respect to primary rock-forming minerals such as anorthite and albite. The water chemistry also is affected by evapotranspiration. The degree of evaporative enrichment is up to 85 in terms of Cl⁻. Results of the hydrogeochemical studies indicate that the occurrence of soda water at Datong is the result of incongruent dissolution of aluminosilicates at one stage of their interaction with groundwater when the water is oversaturated with respect to calcite and evapotranspiration-related salt accumulation is not too strong. Studying the genesis of soda waters provides new insights into mechanism of As and F⁻ enrichment in the aquifer system. Due to CaF₂ solubility control and OH⁻–F⁻ exchange reactions, F⁻ can be enriched in soda water. And the high pH condition of soda water favors As desorption from oxyhydroxide surfaces, thereby increasing the concentration of As in the aqueous phase.     

Stable isotope and Rare Earth Element evidence for recent ironstone pods within the Archean Barberton greenstone belt, South Africa

There is considerable debate about the mode and age of formation of large (up to ∼200 m long) hematite and goethite ironstone bodies within the 3.2 to 3.5 Ga Barberton greenstone belt. We examined oxygen and hydrogen isotopes and Rare Earth Element (REE) concentrations of goethite and hematite components of the ironstones to determine whether these deposits reflect formation from sea-floor vents in the Archean ocean or from recent surface and shallow subsurface spring systems. Goethite δ¹⁸O values range from −0.7 to +1.0‰ and δD from −125 to −146‰, which is consistent with formation from modern meteoric waters at 20 to 25 °C. Hematite δ¹⁸O values range from −0.7 to −2.0‰, which is consistent with formation at low to moderate temperatures (40-55 °C) from modern meteoric water. REE in the goethite and hematite are derived from the weathering of local sideritic ironstones, silicified ultramafic rocks, sideritic black cherts, and local felsic volcanic rocks, falling along a mixing line between the Eu/Eu* and shale-normalized HREE_Avg/LREE_Avg values for the associated silicified ultramafic rocks and felsic volcanic rocks. Contrasting positive Ce/Ce* of 1.3 to 3.5 in hematite and negative Ce/Ce* of 0.2 to 0.9 in goethite provides evidence of oxidative scavenging of Ce on hematite surfaces during mineral precipitation. These isotopic and REE data, taken together, suggest that hematite and goethite ironstone pods formed from relatively recent meteoric waters in shallow springs and/or subsurface warm springs.     

Sr chemostratigrphy, δ<Superscript>13</Superscript>C,and δ<Superscript>18</Superscript>O of rocks in the Crimean carbonate platform (Late Jurassic,northern Peri-Tethys)

The paper presents the results of study of the Sr, C, and O isotope compositions in Upper Jurassic carbonate rocks of the Baidar Valley and Demerdzhi Plateau in the Crimean Mountains represented by different facies of the carbonate platform at the northern active margin of the Tethys. The ⁸⁷Sr/⁸⁶Sr value in them varies from 0.70699 to 0.70728. Based on the Sr chemostratigraphic correlation, the age of massive and layered limestones in the western part of the Ai-Petri and Baidar yailas (pastures) is estimated as late Kimmeridgian–early Tithonian, whereas the age of flyschoids of the Baidar Valley are estimated as late Tithonian–early Berriasian. The nearly synchronous formation of carbonate breccias of the Baidar Valley and Demerdzhi Plateau in late Tithonian–early Berriasian is substantiated. A summary section of Upper Jurassic rocks is compiled based on the Sr chemostratigraphic data. It has been established that δ¹⁸O values in the studied carbonate sediments vary from–2.9 to 1.3‰ (V-PDB). At the same time, shallow-water sediments in the internal part and the edge of the Crimean carbonate platform are depleted in ¹⁸O (–2.9 to +0.1‰) relative to sediments on the slope and foothill (–0.5 to +1.3‰). It is demonstrated that δ¹³C values do not depend on the facies properties and decrease in younger carbonate sediments from 3–3.5‰ to 1–1.5‰ in line with the Late Jurassic general trend. The δ¹³C values obtained for the Crimean carbonate platform turned out to be 0.5–1‰ higher than the values typical of the deep-water marine setting at the western margin of the Tethys. These discrepancies are likely related to peculiarities of water circulation and high bioproductivity in marine waters of the northern Peri-Tethys.