Residence time of Chalk groundwaters in the Paris Basin and the North German Basin: a geochemical approach

The comparative geochemical and isotopic study of confined and unconfined Chalk groundwaters of the Paris Basin and the N German Basin proves a significant chemical evolution during groundwater flow from the recharge zones to the deep confined aquifer. Different time dependent geochemical parameters have been tested as dating tools: Cation ratios (Sr²⁺/Ca²⁺, Mg²⁺/Ca²⁺), N–NO⁻₃, noble gas contents as paleotemperature indicators (Ne, Ar, Kr, Xe), radiogenic He, ¹³C, ¹⁴C, ¹⁸O, ²H, ³H. Cation ratios and ¹³C show the importance of incongruent dissolution processes in the Chalk aquifer. Water–rock interactions were taken into account in a multi-step dissolution model to determine radiocarbon groundwater ages. The oldest waters in the confined part of the Paris basin Chalk with maximum ¹⁴C ages of 14,000 a B.P. contain pleistocene recharge components as can be shown by a stable isotope depletion and noble gas temperatures significantly lower than in recent groundwaters. Chalk waters at the Lägerdorf site in Northern Germany show a distinct stratification with respect to residence times and hydrochemistry.     

Hydrogeological and hydrochemical investigation of groundwater using environmental isotopes (18O, 2H, 3H, 14C) and chemical tracers: a case study of the intermediate aquifer,Sfax, southeastern Tunisia

Major element concentrations and stable (δ¹⁸O and δ²H) and radiogenic (³H and ¹⁴C) isotopes in groundwater have proved useful tracers for understanding the geochemical processes that control groundwater mineralization and for identifying recharge sources in the semi-arid region of Sfax (southeastern Tunisia). Major-ion chemical data indicate that the origins of the salinity in the groundwater are the water–rock interactions, mainly the dissolution of evaporitic minerals, as well as the cation exchange with clay minerals. The δ¹⁸O and δ²H relationships suggest variations in groundwater recharge mechanisms. Strong evaporation during recharge with limited rapid water infiltration is evident in the groundwater of the intermediate aquifer. The mixing with old groundwater in some areas explains the low stable isotope values of some groundwater samples. Groundwaters from the intermediate aquifer are classified into two main water types: Ca-Na-SO₄ and Ca-Na-Cl-SO₄. The high nitrate concentrations suggest an anthropogenic source of nitrogen contamination caused by intensive agricultural activities in the area. The stable isotopic signatures reveal three water groups: non-evaporated waters that indicate recharge by recent infiltrated water; evaporated waters that are characterized by relatively enriched δ¹⁸O and δ²H contents; and mixed groundwater (old/recent) or ancient groundwater, characterized by their depleted isotopic composition. Tritium data support the existence of recent limited recharge; however, other low tritium values are indicative of pre-nuclear recharge and/or mixing between pre-nuclear and contemporaneous recharge. The carbon-14 activities indicate that the groundwaters were mostly recharged under different climatic conditions during the cooler periods of the late Pleistocene and Holocene.

     

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.     

Using geochemical indicators to investigate groundwater mixing and residence time in the aquifer system of Djeffara of Medenine (southeastern Tunisia)

Stable isotopes (??²H, ??¹⁸O and ??¹³C) and radiocarbon (¹⁴C) have been used in conjunction with chemical data to evaluate recharge mechanisms and groundwater residence time, and to identify inter-aquifer mixing in the Djeffara multi-aquifer in semi-arid southeastern Tunisia. The southern part of this basin, the Djeffara of Medenine aquifer system, is comprised of two main aquifers of Triassic and Miocene sandstone. The Triassic aquifer presents two compartments; the first one (west of the Medenine fault system) is unconfined with a well-defined isotope fingerprint; the second compartment is deeper and confined. Multi-tracer results show groundwater of different origins, ages and salinities, and that tectonic features control groundwater flows. Fresh and brackish groundwater from the unconfined part of the Triassic aquifer was mostly recharged during the Holocene. The recharge rates of this aquifer, inferred by ¹⁴C ages, are variable and could reach 3.5?mm/year. Brackish water of the deep confined part of the Triassic aquifer has stable isotope composition and ¹⁴C content that indicates earlier recharge during late Pleistocene cold periods. Brackish to saline water of the Miocene aquifer presents variable isotope composition. Groundwater flowing through the Medenine fault system is mainly feeding the Miocene aquifer rather than the deep confined part of the Triassic aquifer.     

Hydrochemical and stable isotopic investigation of groundwater quality and its sustainability for irrigation in the Hammamet-Nabeul basin,northeastern Tunisia

The major ion hydrochemistry, sodium absorption ratio (SAR), sodium percentage, and isotopic signatures of Hammamet-Nabeul groundwaters were used to identify the processes that control the mineralization, irrigation suitability, and origin of different water bodies. This investigation highlights that groundwater mineralization is mainly influenced by water-rock interaction and pollution by the return flow of irrigation water. The comparison of groundwater quality with irrigation suitability standards proves that most parts of groundwater are unacceptable for irrigation and this long-term practice may result in a significant increase of the salinity and alkalinity in the soils. Based on isotopic signatures, the shallow aquifer groundwater samples were classified into (i) waters with depleted δ¹⁸O and δ²H contents, highlighting recharge by modern precipitation, and (ii) waters with enriched stable isotope contents, reflecting the significance of recharge by contaminated water derived from the return flow of evaporated irrigation waters. The deep-aquifer groundwater samples were also classified into (i) waters with relatively enriched isotope contents derived from modern recharge and mixed with shallow-aquifer groundwater and (ii) waters with depleted stable isotope contents reflecting a paleoclimatic origin. Tritium data permit to identify three origins of recharge, i.e., contemporaneous, post-nuclear, and pre-nuclear. Carbon-14 activities demonstrate the existence of old paleoclimatic recharge related to the Holocene and Late Pleistocene humid periods.     

Pleistocene recharge to midcontinent basins: effects on salinity structure and microbial gas generation

The hydrogeochemistry of saline-meteoric water interface zones in sedimentary basins is important in constraining the fluid migration history, chemical evolution of basinal brines, and physical stability of saline formation waters during episodes of freshwater recharge. This is especially germane for interior cratonic basins, such as the Michigan and Illinois basins. Although there are large differences in formation water salinity and hydrostratigraphy in these basins, both are relatively quiescent tectonically and have experienced repeated cycles of glaciation during the Pleistocene. Exploration for unconventional microbial gas deposits, which began in the upper Devonian-age Antrim Shale at the northern margin of the Michigan Basin, has recently extended into the age-equivalent New Albany Shale of the neighboring Illinois Basin, providing access to heretofore unavailable fluid samples. These reveal an extensive regional recharge system that has profoundly changed the salinity structure and induced significant biogeochemical modification of formation water elemental and isotope geochemistry.New-formation water and gas samples were obtained from Devonian-Mississippian strata in the Illinois Basin. These included exploration wells in the New Albany Shale, an organic-rich black shale of upper Devonian age, and formation waters from over- and underlying regional aquifer systems (Siluro-Devonian and Mississippian age). The hydrostratigraphic relations of major aquifers and aquitards along the eastern margin of the Illinois Basin critically influenced fluid migration into the New Albany Shale. The New Albany Shale formation water chemistry indicates significant invasion of meteoric water, with δD values as low as −46.05‰, into the shale. The carbon stable isotope system (δ¹³C values as high as 29.4‰), coupled with δ¹⁸O, δD, and alkalinity of formation waters (alkalinity ≤24.08 meq/kg), identifies the presence of microbial gas associated with meteoric recharge. Regional geochemical patterns identify the underlying Siluro-Devonian carbonate aquifer system as the major conduit for freshwater recharge into the fractured New Albany Shale reservoirs. Recharge from overlying Mississippian carbonates is only significant in the southernmost portion of the basin margin where carbonates directly overlie the New Albany Shale.Recharge of dilute waters (Cl⁻ <1000 mM) into the Siluro-Devonian section has suppressed formation water salinity to depths as great as 1 km across the entire eastern Illinois Basin margin. Taken together with salinity and stable isotope patterns in age-equivalent Michigan Basin formation waters, they suggest a regional impact of recharge of δ¹⁸O- and δD-depleted fluids related to Pleistocene glaciation. Devonian black shales at both basin margins have been affected by recharge and produced significant volumes of microbial methane. This recharge is also manifested in different salinity gradients in the two basins because of their large differences in original formation water salinity. Given the relatively quiet tectonic history and subdued current topography in the midcontinent region, it is likely that repeated cycles of glacial meltwater invasion across this region have induced a strong disequilibrium pattern in fluid salinity and produced a unique class of unconventional shale-hosted gas deposits.     

Stable isotopes (2H, 18O and 13C) in groundwaters from the northwestern portion of the Guarani Aquifer System (Brazil)

The groundwater flow pattern of the western part of the Guarani Aquifer System (GAS), Brazil, is characterized by three regional recharge areas in the north, and a potentiometric divide in the south, which trends north–south approximately. Groundwater flow is radial from these regional recharge areas toward the center of Paraná Sedimentary Basin and toward the western outcrop areas at the border of the Pantanal Matogrossense, because of the potentiometric divide. The isotopic composition of GAS groundwater leads to understanding the paleoclimatic conditions in the regional recharge areas. The δ¹⁸O and δ²H isotopic ratios of GAS groundwaters vary, respectively, from –9.1 to –4.8‰ V-SMOW and –58.4 to –21.7‰ V-SMOW. In the recharge zones, enriched δ¹⁸O values are observed, while in the confined zone lighter δ¹⁸O values are observed. These suggest that climatic conditions were 10°C cooler than the present during the recharge of these waters. The δ¹³C ratios in groundwater of GAS, in the study area, vary from –19.5 to –6.5‰ VPDB, increasing along the regional flow lines toward the confined zone. This variation is related to dissolution of carbonate cement in the sandstones.     

A paleotemperature record derived from dissolved noble gases in groundwater of the Aquia Aquifer (Maryland, USA)

Low ¹⁴C activities in groundwater of the confined part of the Aquia aquifer in southeastern Maryland suggest that most of this water infiltrated at least 30,000 years ago. However, radiocarbon contents of the dissolved inorganic carbon seem to be affected by isotopic exchange, possibly with secondary calcite deposits in the formation, leading to overestimated ¹⁴C ages. Whereas the geochemistry of the Aquia aquifer complicates the application of the widely used ¹⁴C dating method, the accumulation of radiogenic He seems to provide a viable alternative for establishing a chronology. The quasi-linear increase of He concentrations with flow distance observed in the Aquia aquifer can be explained entirely by accumulation of in situ produced radiogenic He. U and Th concentrations in Aquia sand were measured in order to determine the accumulation rate of ⁴He with sufficient confidence to establish a He time scale.Concentrations of dissolved atmospheric noble gases were used to derive mean annual ground temperatures at the time of infiltration. These noble gas temperatures (NGTs) clearly show the presence of water that infiltrated under much cooler conditions than at present. NGTs are correlated with chloride concentrations, corroborating the hypothesis that chloride variations in this aquifer constitute a climate signal. In contrast, the stable isotope ratios δ¹⁸0 and δD do not provide a clear record of past climatic changes in the Aquia aquifer and the correlation between NGTs and stable isotope ratios is weak. The NGT record suggests that mean annual temperatures in this midlatitude coastal site during the last glacial maximum (LGM) were (9.0 ± 0.6) °C colder than during the Holocene. This difference is slightly lower than estimates derived from pollen data for this region, but considerably larger than the rather uniform cooling of about 5°C indicated by noble gas studies in more southern locations of North America. The larger cooling is ascribed to the influence of the Laurentide ice sheet, which at its maximum extension came as close as 250 km to our study site.     

A new groundwater radiocarbon correction approach accounting for palaeoclimate conditions during recharge and hydrochemical evolution: The Ledo-Paniselian Aquifer,Belgium

The particular objective of the present work is the development of a new radiocarbon correction approach accounting for palaeoclimate conditions at recharge and hydrochemical evolution. Relevant climate conditions at recharge are atmospheric pCO₂ and infiltration temperatures, influencing C isotope concentrations in recharge waters. The new method is applied to the Ledo-Paniselian Aquifer in Belgium. This is a typical freshening aquifer where recharge takes place through the semi-confining cover of the Bartonian Clay. Besides cation exchange which is the major influencing process for the evolution of groundwater chemistry (particularly in the Bartonian Clay), also mixing with the original porewater solution (fossil seawater) occurs in the aquifer. Recharge temperatures were based on noble gas measurements. Potential infiltration water compositions, for a range of possible pCO₂, temperature and calcite dissolution system conditions, were calculated by means of PHREEQC. Then the sampled groundwaters were modelled starting from these infiltration waters, using the computer code NETPATH and considering a wide range of geochemical processes. Fitting models were selected on the basis of correspondence of calculated δ¹³C with measured δ¹³C. The ¹⁴C modelling resulted in residence times ranging from Holocene to Pleistocene (few hundred years to over 40 ka) and yielded consistent results within the uncertainty estimation. Comparison was made with the δ¹³C and Fontes and Garnier correction models, that do not take climate conditions at recharge into account. To date these are considered as the most representative process-oriented existing models, yet differences in calculated residence times of mostly several thousands of years (up to 19 ka) are revealed with the newly calculated ages being mostly (though not always) younger. Not accounting for climate conditions at recharge (pCO₂ and temperature) is thus producing substantial error on deduced residence times. The derived ¹⁴C model ages are correlated with He concentrations measured in the groundwater of the aquifer. The obtained residence times show a gap between about 14 and 21 ka indicating possible permafrost conditions which inhibited any groundwater recharge.     

Groundwater flow patterns in the San Luis Valley,Colorado, USA revisited: an evaluation of solute and isotopic data

Groundwater systems in the San Luis Valley, Colorado, USA have been re-evaluated by an analysis of solute and isotopic data. Existing stream, spring, and groundwater samples have been augmented with 154 solute and isotopic samples. Based on geochemical stratification, three groundwater regimes have been identified within 1,200 m of the surface: unconfined, upper active confined, and lower active confined with maximum TDS concentrations of 35,000, 3,500 and 600 mg/L, respectively. The elevated TDS of northern valley unconfined and upper active confined systems result from mineral dissolution, ion exchange and methanogenesis of organic and evaporate lake sediments deposited in an ancient lake, herein designated as Lake Sipapu. Chemical evolutions along flow paths were modeled with NETPATH. Groundwater ages, and δ¹³C, δ²H and δ¹⁸O compositions and distributions, suggest that mountain front recharge is the principle recharge mechanism for the upper and lower confined aquifers with travel times in the northern valley of more than 20,000 and 30,000 ¹⁴C years, respectively. Southern valley confined aquifer travel times are 5,000 ¹⁴C years or less. The unconfined aquifer contains appreciable modern recharge water and the contribution of confined aquifer water to the unconfined aquifer does not exceed 20%.     

Groundwater origins and mixing pattern in the multilayer aquifer system of the Gafsa-south mining district: a chemical and isotopic approach

Major ion geochemistry and environmental isotopes were used to identify the origins and the mineralisation processes of groundwater flowing within the three aquifer levels of the multilayer system of the Gafsa-south mining district (Southwestern Tunisia). It has been demonstrated that groundwaters are characterised by a Ca–Mg–SO₄ water type. Geochemical pattern is mainly controlled by the dissolution of halite, gypsum and/or anhydrite as well as by the incongruent dissolution of dolomite. δ¹⁸O and δ²H values are much lower than the isotopic signature of regional precipitation and fall close to the meteoric water lines, indicating that groundwaters have not been significantly affected by evaporation or mineral–water reactions. The distribution of stable and radiogenic isotopes (δ¹⁸O, δ²H, δ¹³C and ¹⁴C) within the aquifer levels suggests that the deep confined aquifer receives a significant modern recharge at higher altitudes, while, the shallow unconfined aquifer has been mainly recharged under cooler paleoclimatic condition, likely during Late Pleistocene and Early Holocene humid periods. However, waters from the intermediate confined/unconfined aquifer have composite isotopic signatures, highlighting that they are derived from a mixture of the two first end-members.     

Analysis of noble gases in water using a quadrupole mass spectrometer in static mode

A quadrupole-based mass spectrometer used in static mode has been employed to determine noble gas concentrations of water samples by isotope dilution. Water samples are degassed and spiked with minor isotopes of each noble gas. After separation of the various gas components, the isotopic ratios are measured in the mass spectrometer. Because a spike is added to each sample, the recovery of each gas component does not have to be quantitative. Equilibration temperatures are calculated from the gas concentrations, based on noble gas solubility data. An accuracy of ±1°C, from the air equilibration temperature, is attainable for air-saturated water samples prepared under controlled conditions in the laboratory. The method has been applied to groundwaters from the London Basin Chalk aquifer. The noble-gas-derived temperatures are consistent with climatic conditions prevailing at the periods of recharge.     

A geochemical and stable isotope investigation of groundwater/surface-water interactions in the Velenje Basin,Slovenia

The geochemical and isotopic composition of surface waters and groundwater in the Velenje Basin, Slovenia, was investigated seasonally to determine the relationship between major aquifers and surface waters, water–rock reactions, relative ages of groundwater, and biogeochemical processes. Groundwater in the Triassic aquifer is dominated by HCO₃ ^–, Ca²⁺, Mg²⁺ and δ¹³C_DIC indicating degradation of soil organic matter and dissolution of carbonate minerals, similar to surface waters. In addition, groundwater in the Triassic aquifer has δ¹⁸O and δD values that plot near surface waters on the local and global meteoric water lines, and detectable tritium, likely reflecting recent (<50 years) recharge. In contrast, groundwater in the Pliocene aquifers is enriched in Mg²⁺, Na⁺, Ca²⁺, K⁺, and Si, and has high alkalinity and δ¹³C_DIC values, with low SO₄ ^2– and NO₃ ^– concentrations. These waters have likely been influenced by sulfate reduction and microbial methanogenesis associated with coal seams and dissolution of feldspars and Mg-rich clay minerals. Pliocene aquifer waters are also depleted in ¹⁸O and ²H, and have ³H concentrations near the detection limit, suggesting these waters are older, had a different recharge source, and have not mixed extensively with groundwater in the Triassic aquifer.     

Geochemical and isotopic characterization of groundwater from shallow and deep limestone aquifers system of Aleppo basin (north Syria)

Stable isotopes (δ¹⁸O, δ²H and ¹³C) and radioactivity (³H, ¹⁴C) have been used in conjunction with chemical data to evaluate the processes generating the chemical composition, reconstruct the origin of the water and groundwater residence time. The Aleppo basin is comprised of two main limestone aquifers: the first one is unconfined of Paleogene age and the second is confined of Upper Cretaceous age. The chemical data indicate that the dissolution of minerals and evaporation are the main processes controlling groundwater mineralization. The groundwater from the two aquifers is characterized by distinctive stable isotope signatures. This difference in water isotopes is interpreted in terms of difference origin and recharge period. Fresh and brackish shallow groundwater were mostly recharged during the Holocene period. The presence of ³H in several groundwater samples of this aquifer gives evidence that groundwater recharge is going on. Brackish water of the deep confined aquifer has depleted stable isotope composition and very low ¹⁴C activity that indicates recharge during the late Pleistocene cold period.     

The deep Cretaceous aquifer in the Aleppo and Steppe basins of Syria: assessment of the meteoric origin and geographic source of the groundwater

A drilling project was carried out in Syria to assess the potential of the deep groundwater resources of the Cretaceous aquifer, composed of Cenomanian-Turonian limestones and dolomites. In this context, isotope (¹⁴C, ³H, δ¹³C, δ¹⁸O, δ²H) and hydrochemical analyses were performed on wells in and around the Aleppo and Steppe basins. The interpretation includes complementary results from published and unpublished literature. The results provide evidence that many new wells pump mixed groundwater from the Cretaceous aquifer and the overlying Paleogene aquifer. Radiocarbon measurements confirmed dominating Pleistocene groundwater in the Cretaceous aquifer and mainly Holocene groundwater in the Paleogene aquifer. Most groundwater in the Cretaceous aquifer seems to be recharged in the western limestone ridges, stretching from Jebel az Zawiyah (south of Idlep) via Jebel Samane (south of Afrin and A’zaz) to the region north of Aleppo, and in the Northern Palmyrides mountain belt. Some recharge also occurs around the basalt plateau of the Jebel al Hass, south east of Aleppo. It is concluded that the Taurus Mountains and the Euphrates River do not recharge the Cretaceous aquifer. The sources of recharge seem to be occasionally occurring intensive winter storms that approach from Siberia.     

Climatic change recorded by stable isotopes and trace elements in a British Holocene tufa

Combined stable isotope (δ¹⁸O and δ¹³C) and trace element (Mg, Sr) geochemistry from bulk tufa calcite and ostracod shell calcite from an early Holocene British tufa reveal clear records of Holocene palaeoclimatic change. Variation in δ¹⁸O is caused principally by change in the isotopic composition of Holocene rainfall (recharge), itself caused mainly by change in air temperature. The δ¹³C variability through much of the deposit reflects increasing influence of soil‐zone CO₂, owing to progressive woodland soil development. Bulk tufa Mg/Ca and Sr/Ca are controlled by their concentrations in the spring water. Importantly, Mg/Ca ratios are not related to δ¹⁸O values and thus show no temperature dependence. First‐order sympathetic relationships between δ¹³C values and Mg/Ca and Sr/Ca are controlled by aquifer processes (residence times, CO₂ degassing and calcite dissolution/reprecipitation) and probably record intensity of palaeorainfall (recharge) effects. Stable isotope records from ostracod shells show evidence of vital effects relative to bulk tufa data. The ostracod isotopic records are markedly ‘spiky’ because the ostracods record ‘snapshots’ of relatively short duration (years), whereas the bulk tufa samples record averages of longer time periods, probably decades. The δ¹⁸O record appears to show early Holocene warming, a thermal maximum at ca. 8900 cal. yr BP and the global 8200 yr BP cold event. Combined δ¹³C, Mg/Ca and Sr/Ca data suggest that early Holocene warming was accompanied by decreasing rainfall intensity. The Mg/Ca data suggest that the 8200 yr BP cold event was also dry. Warmer and wetter conditions were re‐established after the 8200 yr BP cold event until the top of the preserved tufa sequence at ca. 7100 cal. yr BP. Copyright © 2004 John Wiley & Sons, Ltd.     

Controls on δ34S and δ18O of dissolved sulfate in aquifers of the Murray Basin,Australia and their use as indicators of flow processes

The usefulness of stable isotopes of dissolved SO₄ (δ³⁴S and δ¹⁸O) to study recharge processes and to identify areas of significant inter-aquifer mixing was evaluated in a large, semi-arid groundwater basin in south-eastern Australia (the Murray Basin). The distinct isotopic signatures in the oxidizing unconfined Murray Group Aquifer and the deeper reducing Renmark Group confined aquifer may be more sensitive than conventional chemical tracers in establishing aquifer connections. δ³⁴S values in the unconfined Murray Group Aquifer in the south and central part of the study area decrease along the hydraulic gradient from 20.8 to 0.3‰. The concomitant increasing SO₄/Cl ratios, as well as relatively low δ¹⁸O_SO4 values, suggest that vertical input of biogenically derived SO₄ via diffuse recharge is the predominant source of dissolved SO₄ to the aquifer. Further along the hydraulic gradient towards the discharge area near the River Murray, δ³⁴S values in the unconfined Murray Group Aquifer increase, and SO₄/Cl ratios decrease, due to upward leakage of waters from the confined Renmark Group Aquifer which has a distinctly low SO₄/Cl and high δ³⁴S (14.9–56.4‰). Relatively positive δ³⁴S and δ¹⁸O_SO4 values, and low SO₄/Cl in the Renmark Group Aquifer is typical of SO₄ removal by bacterial reduction. The S isotope fractionation between SO₄ and HS⁻ of ∼24‰ estimated for the confined aquifer is similar to the experimentally determined chemical fractionation factor for the reduction process but much lower than the equilibrium fractionation (∼70‰) even though the confined groundwater residence time is >300 Ka years. Mapping the spatial distribution of δ³⁴S and SO₄/Cl of the unconfined Murray Group Aquifer provides an indicative tool for identifying the approximate extent of mixing, however the poorly defined end-member isotopic signatures precludes quantitative estimates of mixing fractions.     

Source and origin of active and fossil thermal spring systems,northern Upper Rhine Graben,Germany

Thermal water samples and related young and fossil mineralization from a geothermal system at the northern margin of the Upper Rhine Graben have been investigated by combining hydrochemistry with stable and Sr isotope geochemistry. Actively discharging thermal springs and mineralization are present in a structural zone that extends over at least 60 km along strike, with two of the main centers of hydrothermal activity being Wiesbaden and Bad Nauheim. This setting provides the rare opportunity to link the chemistry and isotopic signatures of modern thermal waters directly with fossil mineralization dating back to at least 500–800 ka. The fossil thermal spring mineralization can be classified into two major types: barite-(pyrite) fracture filling associated with laterally-extensive silicification; and barite, goethite and silica impregnation mineralization in Tertiary sediments. Additionally, carbonatic sinters occur around active springs. Strontium isotope and trace element data suggest that mixing of a hot (>100 °C), deep-sourced thermal water with cooler groundwater from shallow aquifers is responsible for present-day thermal spring discharge and fossil mineralization. The correlation between both Sr and S isotope ratios and the elevation of the barite mineralization relative to the present-day water table in Wiesbaden is explained by mixing of deep-sourced thermal water having high ⁸⁷Sr/⁸⁶Sr and low δ³⁴S with shallow groundwater of lower ⁸⁷Sr/⁸⁶Sr and higher δ³⁴S. The Sr isotope data demonstrate that the hot thermal waters originate from an aquifer in the Variscan crystalline basement at depths of 3–5 km. The S isotope data show that impregnation-type mineralization is strongly influenced by mixing with SO₄ that has high δ³⁴S values. The fracture style mineralization formed by cooling of the thermal waters, whereas impregnation-type mineralization precipitated by mixing with SO₄-rich groundwater percolating through the sediments.     

Isotopic and noble gas study of Chalk groundwater in the London Basin, England

The chemical and isotopic composition of groundwater from 52 sites in the London (U.K.) area was determined as part of a project aimed at assessing the spatial variation in the age of Chalk groundwater, and in determining the relationship between fracture and matrix groundwater in this dual porosity system.Systematic changes in groundwater chemistry take place in the downgradient direction in response to several chemical processes. These processes include early concentration by evaporation and congruent dissolution of calcite followed by widespread incongruent dissolution and ion exchange in addition to local oxidation-reduction reactions, gypsum dissolution and saline intrusion. As a result of the above processes, Chalk groundwater follows an evolutionary path from Ca bicarbonate type to Na bicarbonate type.The age of Chalk groundwater was modelled using¹⁴C, δ¹³C,³H, δ²H and δ¹⁸0. There is a general increase in the groundwater age in a downgradient direction with the oldest water found in N central areas of the basin. Groundwater in the unconfined zones and in areas S of the Greenwich fault is almost entirely of unevolved, modem composition. Carbon-14 modelling suggests that Chalk groundwater in the S basin is generally less than 10000 a old while that in the north is generally between 10000 and 25000 a old. The presence of³H in concentrations of up to 7 TU in groundwater which yields ages of several 1000 a, however, indicates that mechanisms exist for the rapid introduction of recent groundwater to the confined aquifer. Results of palaeorecharge temperature determinations using δ²H, δ¹⁸0 and noble gas analytical results suggest that significant Devensian recharge did indeed occur in the aquifer.A model of the development of the Chalk recognizes that it is a classic dual porosity aquifer in which groundwater flow occurs predominantly in the fracture system. The upper 50 m of the aquifer was flushed with fresh water during the 2–3 × 10⁶ a of the Quaternary and therefore meteoric water largely replaced the Tertiary and Cretaceous marine water that previously saturated the system. Most processes which control the chemistry of the groundwater occur in the matrix where the surface area is exceptionally high. Although fracture flow dominates the flow regime, diffusion from the matrix into the fracture porosity controls the chemistry of Chalk groundwater.     

Groundwater recharge and evolution in the Dunhuang Basin,northwestern China

Groundwater recharge and evolution in the Quaternary aquifer beneath the Dunhuang Basin was investigated using chemical indicators, stable isotopes, and radiocarbon data to provide guidance for regional water management. The quality of groundwater and surface water is generally good with low salinity and it is unpolluted. The dissolution of halite and sylvite from fine-grained sediments controls concentrations of Na⁺ and K⁺ in the groundwater, but Na⁺/Cl⁻ molar ratios >1 in all samples are also indicative of weathering of feldspar contributing to excess Na⁺. The dissolution of carbonate minerals yields Ca²⁺ to the groundwater, thereby exerting a strong influence on groundwater salinity. The δ¹⁸O and δ²H values in unconfined groundwater are enriched along the groundwater flow path from SW to NE. In contrast, confined groundwater was depleted in heavy isotopes, with mean values of −10.4‰ δ¹⁸O and −74.4‰ δ²H. Compared with the precipitation values, all of the groundwater samples were strongly depleted in heavy isotopes, indicating that modern direct recharge to the groundwater aquifers in the plains area is quite limited. The unconfined water is generally young with radiocarbon values of 64.9–79.6 pmc. In the northern basin, radiocarbon content in the confined groundwater is less than 15 pmc and an uncorrected age of ∼15 ka, indicates that this groundwater was recharged during a humid climatic phases of the late Pleistocence or early Holocene. The results have important implications for inter-basin water allocation programmes and groundwater management in the Dunhuang Basin.