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.     

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

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

Groundwater flow system as an archive of palaeotemperature: Noble gas, radiocarbon, stable isotope and geochemical study in the Pannonian Basin, Hungary

To establish the increase in temperature and the time span of the transition between the Late Glacial Maximum (LGM) and the Holocene, the noble gas content, ¹⁸O, ²H, ¹³C δ values, ³H and ¹⁴C activity and chemistry were studied in a groundwater flow system in Quaternary sediments in Hungary. The study area is a sub-basin of the Pannonian Basin, where the C isotope ratios are not influenced by carbonate reactions along the flow path, because the only water-rock interaction is ion exchange. The δ¹⁸O and δ²H values indicate a cold infiltration period, followed by warming, and, finally, warm temperature conditions. The noble gas data show that the average infiltration temperature was 3.3 °C in the cold, 12.9 °C in the warm, and intermediate in the transitional stage. Using the noble gas temperatures, geochemical batch modelling was performed to simulate the chemical processes. Based on the geochemical model, δ¹³C and ¹⁴C₀ (initial radiocarbon activity) in the recharging water were calculated. Transport modelling was used to simulate the distribution of chemical components, δ¹⁸O, δ²H and ¹⁴C₀, along the flow path. It was found that the main processes determining the chemical composition of the groundwater were dissolution/precipitation of calcite and dolomite during infiltration near the surface, and ion exchange along the flow path. In the recharge area the δ¹³C and ¹⁴C₀ were controlled by dissolution and precipitation of carbonate minerals, C speciation, and fractionation processes. All these processes were influenced by the recharge temperature. NGTs calculated from the dissolved noble gas concentrations showed an average of 3.3 °C for cold, and 12.9 °C for warm infiltration, i.e. for the LGM and for the Holocene. The temperature difference was thus 9.1 ± 0.8 °C, which is one of the largest degree of warming detected by noble gases so far. The alkalinity indicates that carbonate reactions were unimportant along the flow path. Owing to the temperature dependence of the equilibrium constants, temperature conditions during infiltration have to be taken into consideration in radiocarbon age calculation. Dispersive transport along the flow path modified the chemical and isotopic composition of infiltrated water. The contribution of the old pore water, which was free of the ¹⁴C isotope, resulted in uncertainties in radiocarbon age determination. It was concluded that determination of the radiocarbon age or mean residence time requires detailed knowledge of the hydraulic conditions of groundwater.     

Interaction between shallow and deep aquifers in the Tivoli Plain (Central Italy) enhanced by groundwater extraction: A multi-isotope approach and geochemical modeling

In the Tivoli Plain (Rome, Central Italy) the interaction between shallow and deep groundwater flow systems enhanced by groundwater extraction has been investigated using isotopic and chemical tracers. A conceptual model of the groundwater flowpaths has been developed and verified by geochemical modeling. A combined hydrogeochemical and isotopic investigation using ion relationships such as DIC/Cl⁻, Ca/(Ca + Mg)/SO₄/(SO₄ + HCO₃), and environmental isotopes (δ¹⁸O, δ²H, ⁸⁷Sr/⁸⁶Sr, δ³⁴S and δ¹³C) was carried out in order to determine the sources of recharge of the aquifer, the origin of solutes and the mixing processes in groundwater of Tivoli Plain. Multivariate statistical methods such as principal component analysis and Cluster analyses have confirmed the existence of different geochemical facies and the role of mixing in the chemical composition of the groundwater.     

Constraining flow paths of saline groundwater at basin margins using hydrochemistry and environmental isotopes: Lake Cooper,Murray Basin,Australia

Solutes in saline groundwater (total dissolved solids up to 37 000 mg/L) in the Lake Cooper region in the southern margin of the Riverine Province of the Murray Basin are derived by evapotranspiration of rainfall with minor silicate, carbonate and halite dissolution. The distribution of hydraulic heads, salinity, percentage modern carbon (pmc) contents, and Cl/Br ratios imply that the groundwater system is complex with vertical flow superimposed on lateral flow away from the basin margins. Similarities in major ion composition, stable (O, H, and C) isotope, and ⁸⁷Sr/⁸⁶Sr ratios between groundwater from the shallower Shepparton Formation and the deeper Calivil – Renmark aquifer also imply that these aquifers are hydraulically interconnected. Groundwater in the deeper Calivil – Renmark aquifer in the Lake Cooper region has residence times of up to 25 000 years, implying that pre-land-clearing recharge rates were <1 mm/y. As in other regions of the Murray Basin, the low recharge rates account for the occurrence of high-salinity groundwater. Shallow (<20 m) groundwater yields exclusively modern ¹⁴C ages and shows a greater influence of evaporation over transpiration. Both these observations reflect the rise of the regional water-table following land clearing over the last 200 years and a subsequent increase in recharge to 10 – 20 mm/y. The rise of the regional water-table also has increased vertical and horizontal hydraulic gradients that may ultimately lead to the export of salt from the Lake Cooper embayment into the adjacent fresher groundwater resources.     

Using hydrogeochemistry to understand inter-aquifer mixing in the on-shore part of the Gippsland Basin,southeast Australia

Groundwater in the Latrobe Valley in the Gippsland Basin of southeast Australia is important for domestic, agricultural and industrial uses. This sedimentary basin contains a number of aquifers that are used for water supply, dewatered for open pit coal mining, and which are potentially influenced by off-shore oil and gas production. Major ion chemistry together with stable and Sr isotope data imply that the main hydrogeochemical processes are evapotranspiration with minor silicate and carbonate weathering; methanogenesis and SO₄ reduction in reduced groundwater associated with coal deposits have also occurred. Groundwater has estimated ¹⁴C ages of up to 36 ka and is largely ³H free. Carbon-14 ages are irregularly distributed and poorly correlated with depth and distance from the basin margins. The observations that the geochemistry of groundwater in aquifers with different mineralogies are similar and the distribution of ¹⁴C ages is irregular implies that the aquifers are hydraulically connected and horizontal as well as vertical inter-aquifer mixing occurs. The connection of shallow and deeper aquifers poses a risk for the groundwater resources in Gippsland as contaminants can migrate across aquifers and dewatering of shallow units may impact deeper parts of the groundwater system.     

A multi-isotope (δD, δO,Sr/Sr,and δB) approach for identifying saltwater intrusion and resolving groundwater evolution along the Western Caprock Escarpment of the Southern High Plains,New Mexico

Declining water levels in arid and semi-arid regions increase an aquifer’s vulnerability to natural and anthropogenic influences. A multi-isotope (δD, δ¹⁸O, ⁸⁷Sr/⁸⁶Sr, and δ¹¹B) approach was used to resolve the geochemical evolution of groundwater in a declining aquifer in a semi-arid region of the southwestern USA as groundwater composition reacts to source-water mixing, cross-formational flow including saltwater intrusion, water–rock interaction, and likely agricultural recharge. Sub-aquifers or local flow systems are present in the Southern High Plains aquifer along the Western Caprock Escarpment in New Mexico, and the study site’s local flow system contains a Na–Cl, high dissolved-solids groundwater that flows from the escarpment until it mixes with a high quality regional aquifer or regional flow system. The local flow system contains water that is similar in composition to the underlying, upper Dockum Group aquifer. Saltwater found in the upper Dockum Group aquifer likely originates in the adjacent Pecos River Basin and crosses beneath or possibly through the hydrologic divide of the Western Caprock Escarpment. Strontium concentrations of 0.9–31 mg/L and a ⁸⁷Sr/⁸⁶Sr range of 0.70845–0.70906 were sufficient to estimate source-water fractions, mixing patterns, and contributions from chemical weathering through mass balance inverse calculations. Boron concentrations (59–1740 mg/L) and δ¹¹B values (+6.0–+46.0‰) were used to confirm source-water mixing, further evaluate water–rock interaction, and examine the influence of possible agricultural recharge. Alteration of B concentrations and δ¹¹B values in an area of likely agricultural recharge indicated the loss of B and decrease in δ¹¹B values likely from plant uptake, adsorption, and weathering contributions in the soil/vadose zone prior to recharge. The effectiveness of ⁸⁷Sr/⁸⁶Sr and δ¹¹B for resolving the geochemical influences in groundwater in the Southern High Plains along the Western Caprock Escarpment allowed for the reinterpretation of the isotopic composition of water that has been shown to be highly variable in the Southern High Plains. This study shows the utility of a multi-isotope approach for resolving the geochemical evolution of groundwater in an aquifer that has a complex relationship with underlying aquifers and the applicability of these isotopes as indicators of the alteration of source waters from natural or anthropogenic influences.     

Helium, radon and radiocarbon studies on a regional aquifer system of the North Gujarat-Cambay region, India

The study reports the age evolution of groundwater as it flows from the recharge area through a regional alluvial aquifer system in North Gujarat-Cambay region in western India. Radiocarbon (¹⁴C), ⁴He and ⁴He / ²²²Rn dating methods have been employed. Sediments from a drill core in the Cambay Basin were also analysed for uranium (U) and thorium (Th) concentrations and the measured values have been used to estimate the ⁴He and ²²²Rn production rate for groundwater age calculations. Additionally, factors controlling the distribution of ²²²Rn, ⁴He and temperature anomalies in groundwater, vis-à-vis their relation to the tectonic framework and lithology of the study area, have also been examined.The multi-isotope study indicated a reasonable correspondence in groundwater age estimates by the three methods employed. The groundwater ¹⁴C ages increased, progressively, in the groundwater flow direction: from the foothills of Aravalli Mountains in the east, and reached a value of ∼35 ka towards the region of lowest elevation, linking Little Rann of Kachchh (LRK)-Nalsarovar (NS)-Gulf of Khambhat (GK) in the western part of the study area. In this region, groundwater ages obtained for free flowing thermal wells and springs employing ⁴He and ⁴He / ²²²Rn systematics are in the order of million years. Such anomalous ages are possibly due to enhanced mobilisation and migration of ‘excess helium’ from hydrothermal circulation vents along deep-seated faults. Excluding such anomalous cases and considering all uncertainties, presently estimated ⁴He and ⁴He / ²²²Rn groundwater ages are in reasonable agreement with ¹⁴C age estimates in the Cambay Basin for helium release factor (Λ_He) value of 0.4 ± 0.3. The ⁴He method also indicated west-southwards progression of groundwater ages up to ∼100 ka beyond the Cambay Basin.Large ‘excess helium’ concentrations are also seen to be generally associated with anomalous groundwater temperatures (> 35 °C) and found to overlie some of the basement faults in the study area, particularly along the east and the west flanks of the Cambay Basin. Groundwater ²²²Rn activities in most of the study area are 800 ± 400 dpm/l. But, a thermal spring at Tuwa on the east flank of the Cambay Basin, having granitic basement at shallow depth, recorded the highest ²²²Rn activity (∼63,000 dpm/l).     

Using 3H and 14C to constrain the degree of closed-system dissolution of calcite in groundwater

This study uses ³H concentrations, ¹⁴C activities (a¹⁴C), ⁸⁷Sr/⁸⁶Sr ratios, and δ¹³C values to constrain calcite dissolution in groundwater from the Ovens catchment SE Australia. Taken in isolation, the δ¹³C values of dissolved organic C (DIC) and ⁸⁷Sr/⁸⁶Sr ratios in the Ovens groundwater imply that there has been significant calcite dissolution. However, the covariance of ³H and ¹⁴C and the calculated initial ¹⁴C activities (a₀¹⁴C) imply that most groundwater cannot have dissolved more than 20% of ¹⁴C-free calcite under closed-system conditions. Rather, calcite dissolution must have been partially an open-system process allowing ¹³C and ¹⁴C to re-equilibrate with CO₂ in the unsaturated zone. Recognising that open-system calcite dissolution has occurred is important for dating deeper groundwater that is removed from its recharge area in this and other basins. The study is one of the first to use ¹⁴C and ³H to constrain the degree of calcite dissolution and illustrates that it is a valuable tool for assessing geochemical processes in recharge areas.     

Radiocarbon application in dating “complex” hot and cold CO2-rich mineral water systems: A review of case studies ascribed to the northern Portugal

The use of radioactive isotopes plays a very important role in dating groundwater, providing an apparent age of the systems in the framework of the aquifers conceptual modelling making available important features about the water fluxes, such as recharge, horizontal flow rates and discharge. In this paper, special emphasis has been put on isotopic constraints in the use of δ¹³C and ¹⁴C content as a dating tool in some hot (76 °C) and cold (17 °C) CO₂-rich mineral waters discharging in the Vilarelho da Raia–Pedras Salgadas region (N-Portugal). The radiocarbon content determined in these CO₂-rich mineral waters (¹⁴C activity from 4.3 up to 9.9 pmc) is incompatible with the systematic presence of ³H (from 1.7 to 7.9 TU). The δ¹³C values of the studied CO₂-rich mineral waters indicate that the total C in the recharge waters is being masked by larger quantities of CO₂ (¹⁴C-free) introduced from deep-seated (upper mantle) sources. This paper demonstrates that a good knowledge of mineral water systems is essential to allow hydrologists to make sound conclusions on the use of C isotopic data in each particular situation.     

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.     

Application of the water balance model J2000 to estimate groundwater recharge in a semi-arid environment: a case study in the Zarqa River catchment, NW-Jordan

Pollution and overexploitation of scarce groundwater resources is a serious problem in the Zarqa River catchment, Jordan. To estimate this resource’s potential, the amount and spatial distribution of groundwater recharge was calculated by applying the hydrological model J2000. The simulation period is composed of daily values gathered over a 30-year period (July 1977 to June 2007). The figure finally obtained for estimated groundwater recharge of the Zarqa River catchment is 105 × 10⁶ m³ per year (21 mm a^?1). This is 19 % higher than the value previously assumed to be correct by most Jordanian authorities. The average ratio of precipitation to groundwater recharge is 9.5 %. To directly validate modelled groundwater recharge, two independent methods were applied in spring catchments: (1) alteration of stable isotope signatures (δ¹⁸O, δ²H) between precipitation and groundwater and (2) the chloride mass balance method. Recharge rates determined by isotopic investigations are 25 % higher, and recharge rates determined by chloride mass balance are 9 % higher than the modelled results for the corresponding headwater catchments. This suggests a reasonably modelled safe yield estimation of groundwater resources.     

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.     

Using fossil spring deposits in the Death Valley region,USA to evaluate palaeoflowpaths

Spring deposits reveal the timing and environment of past groundwater discharge. Herein, however, the potential for fossil spring deposits to infer water sources and palaeoflowpaths through trace elements and stable and radiogenic isotopes is examined. Past discharge (70 to 285 ka) in the Tecopa Basin in the Death Valley region of southeastern California is represented by tufa deposits, including mounds, pools, cemented ledges and rare calcite feeder veins. δ¹⁸O values indicate that spring discharge was a mixture of far‐travelled (regional) water with a significant, and perhaps dominant contribution of local recharge on a nearby range front and alluvial pediment, rather than simply representing an elevated regional water table. δ¹³C values indicate regional water had a high TDS, whereas solute data imply low overall solute contents, consistent with dilution by a large component of local recharge. Radiogenic isotope data (U‐series, ⁸⁷Sr/⁸⁶Sr) for tufa indicate that siliciclastic rocks (a regional aquitard) interacted with discharging water. To access this aquitard, regional flow was probably partitioned into a permeable north–south damage zone of a north–south range‐bounding fault along the foot of the Resting Spring Range, which ultimately controlled the location of groundwater discharge. Existing models for modern discharge in the Tecopa Basin, by contrast, call upon westward interbasin flow in carbonate rocks from the Spring Mountains through the intervening (and nearly perpendicular) Nopah and Resting Spring Ranges. Understanding the controls on regional groundwater flow is critical in this and other arid regions where water is, by definition, a scarce resource. Thus, although it is a case study, this report highlights a fruitful approach to palaeohydrology that can be widely applied. Copyright © 2007 John Wiley & Sons, Ltd.     

Note on the isotopic geochemistry of fossil-lacustrine tufas in carbonate plateau—A study from Dungul region (SW Egypt)

Lithological, chemical, and stable isotope data are used to characterize lacustrine tufas dating back to pre-late Miocene and later unknown times, capping different surfaces of a Tertiary carbonate (Sinn el-Kedab) plateau in Dungul region in the currently hyperarid south-western Egypt. These deposits are composed mostly of calcium carbonate, some magnesium carbonate and clastic particles plus minor amounts of organic matter. They have a wide range of (Mg/Ca)_molar ratios, from 0.03 to 0.3. The bulk-tufa carbonate has characteristic isotope compositions: (δ¹³C_mean = −2.49 ± 0.99‰; δ¹⁸O_mean = −9.43 ± 1.40‰). The δ¹³C values are consistent with a small input from C4 vegetation or thinner soils in the recharge area of the tufa-depositing systems. The δ¹⁸O values are typical of fresh water carbonates. Covariation between δ¹³C and δ¹⁸O values probably is a reflection of climatic conditions such as aridity. The tufas studied are isotopically similar to the underlying diagenetic marine chalks, marls and limestones (δ¹³C_mean = −2.06 ± 0.84‰; δ¹⁸O_mean = −10.06 ± 1.39‰). The similarity has been attributed to common meteoric water signatures. This raises large uncertainties in using tufas (Mg/Ca)_molar, δ¹³C and δ¹⁸O records as proxies of paleoclimatic change and suggests that intrinsic compositional differences in material sources within the plateau may mask climatic changes in the records.     

Hydrogeochemical and isotopic evidence of groundwater evolution and recharge in aquifers in Beijing Plain, China

An investigation was conducted in Beijing to identify the groundwater evolution and recharge in the quaternary aquifers. Water samples were collected from precipitation, rivers, wells, and springs for hydrochemical and isotopic measurements. The recharge and the origin of groundwater and its residence time were further studied. The groundwater in the upper aquifer is characterized by Ca-Mg-HCO₃ type in the upstream area and Na-HCO₃ type in the downstream area of the groundwater flow field. The groundwater in the lower aquifer is mainly characterized by Ca-Mg-HCO₃ type in the upstream area and Ca-Na-Mg-HCO₃ and Na-Ca-Mg-HCO₃ type in the downstream area. The δD and δ¹⁸O in precipitation are linearly correlated, which is similar to WMWL. The δD and δ¹⁸O values of river, well and spring water are within the same ranges as those found in the alluvial fan zone, and lay slightly above or below LMWL. The δD and δ¹⁸O values have a decreasing trend generally following the precipitation → surface water → shallow groundwater → spring water → deep groundwater direction. There is evidence of enrichment of heavy isotopes in groundwater due to evaporation. Tritium values of unconfined groundwater give evidence for ongoing recharge in modern times with mean residence times <50 a. It shows a clear renewal evolution along the groundwater flow paths and represents modern recharge locally from precipitation and surface water to the shallow aquifers (<150 m). In contrast, according to ¹⁴C ages in the confined aquifers and residence time of groundwater flow lines, the deep groundwater is approximately or older than 10 ka, and was recharged during a period when the climate was wetter and colder mainly from the piedmont surrounding the plain. The groundwater exploitation is considered to be “mined unsustainably” because more water is withdrawn than it is replenished.     

Major-ion chemistry, ��13C and 87Sr/86Sr as indicators of hydrochemical evolution and sources of salinity in groundwater in the Yuncheng Basin, China

Processes controlling hydrogeochemistry in the Yuncheng Basin, China, were characterised using major-ion chemistry, ⁸⁷Sr/⁸⁶Sr ratios and ??¹³C values. Evapotranspiration during recharge increased solute concentrations by factors of ??5?C50 in deep palaeowaters, while higher degrees of evapotranspiration have occurred in shallow, modern groundwater. Aquifer sediments (loess) contain approximately 15 weight% calcite; trends in groundwater HCO₃ concentrations and ??¹³C values (ranging from ?16.4 to ?8.2??) indicate that carbonate weathering is a significant source of DIC. Groundwater ⁸⁷Sr/⁸⁶Sr ratios (0.7110?C0.7162, median of 0.7116) are similar to those in both loess carbonate (0.7109?C0.7116) and local rainfall (0.7112), and are significantly lower than Sr in aquifer silicates (0.7184?C0.7251). Despite evidence for substantial carbonate dissolution, groundwater is generally Ca-poor (<?10% of total cations) and Na-rich, due to cation exchange. Saturation with respect to carbonate minerals occurs during or soon after recharge (all calcite and dolomite saturation indices are positive). Subsequent carbonate dissolution in the deep aquifer must occur as a second-stage process, in response to Ca loss (by ion exchange) and/or via incongruent dissolution of dolomite and impure calcite. The latter is consistent with positive correlations between ??¹³C values and Mg/Ca and Sr/Ca ratios (r ²?=?0.32 and 0.34).     

Geochemistry and residence time estimation of groundwater from the upper aquifer of the Chihuahua desert (Comarca Lagunera, Northern Mexico)

178 groundwater and surface waters have been sampled from April to September 1994 in an endoreic basin located in the N of Mexico (Comarca Lagunera). In this area, groundwater has been exploited over the past century mainly for irrigation and cattle supply. Recent intensive pumping has caused the lowering of the water table at a rate of 1 m a⁻¹ Chemical analyses have been performed on all collected samples and 37 of them have been selected for isotopic measurements (¹⁸O,²H,¹³C and¹⁴C). Water stable isotope contents (¹⁸O,²H) show an increasing evaporation of the groundwater towards the Nazas river. They also indicate that the recharge occurs from the Nazas river and from the mountains surrounding the depression (Sierra Madre Occidental). Water presents a large spatial variability of the chemical facies (SO₄Ca, SO₄ClNa, HCO₃-Ca and HCO₃-Na) which is in relation with (i) their interaction with the geological formations of the basin (carbonates, gypsum and various silicates) and (ii) evaporation. This evaporation occurs in the upper part of the unsaturated zone during infiltration especially for the groundwater sampled near the Nazas river. The¹⁴C activity varies between 110.4 (± 1.1) and 4.0 (±0.2) pmc. The¹³C contents of the total dissolved inorganic C (TDIC) range between −11.0 and −3.6‰. The calculated¹³C contents of the CO₂ in equilibrium with the TDIC, varying between −18.4%0 to −10.9% indicate two origins of C in solution: the carbonate matrix (δ¹³C= +0.9‰) and the soil CO₂ (δ¹³C from −27.7‰ to −21.7‰ for the cultivated areas). Mean residence times have been determined after correction of the initial activities for dead C from the rock matrix. The mean residence times confirm a modern recharge of the groundwater from the Nazas and indicate the presence of palaeowaters in the northern and southern parts of the basin (up to 30 ka BP).