A 17-Year Record of Environmental Tracers in Spring Discharge,Shenandoah National Park,Virginia, USA: Use of Climatic Data and Environmental Conditions to Interpret Discharge,Dissolved Solutes,and Tracer Concentrations

A 17-year record (1995–2012) of a suite of environmental tracer concentrations in discharge from 34 springs located along the crest of the Blue Ridge Mountains in Shenandoah National Park (SNP), Virginia, USA, reveals patterns and trends that can be related to climatic and environmental conditions. These data include a 12-year time series of monthly sampling at five springs, with measurements of temperature, specific conductance, pH, and discharge recorded at 30-min intervals. The monthly measurements include age tracers (CFC-11, CFC-12, CFC-113, CFC-13, SF₆, and SF₅CF₃), dissolved gases (N₂, O₂, Ar, CO₂, and CH₄), stable isotopes of water, and major and trace inorganic constituents. The chlorofluorocarbon (CFC) and sulfur hexafluoride (SF₆₎ concentrations (in pptv) in spring discharge closely follow the concurrent monthly measurements of their atmospheric mixing ratios measured at the Air Monitoring Station at Big Meadows, SNP, indicating waters 0–3 years in age. A 2-year (2001–2003) record of unsaturated zone air displayed seasonal deviations from North American Air of ±10 % for CFC-11 and CFC-113, with excess CFC-11 and CFC-113 in peak summer and depletion in peak winter. The pattern in unsaturated zone soil CFCs is a function of gas solubility in soil water and seasonal unsaturated zone temperatures. Using the increase in the SF₆ atmospheric mixing ratio, the apparent (piston flow) SF₆ age of the water varied seasonally between about 0 (modern) in January and up to 3 years in July–August. The SF₆ concentration and concentrations of dissolved solutes (SiO₂, Ca²⁺, Mg²⁺, Na⁺, Cl^?, and HCO₃ ^?) in spring discharge demonstrate a fraction of recent recharge following large precipitation events. The output of solutes in the discharge of springs minus the input from atmospheric deposition per hectare of watershed area (mol ha^?1 a^?1) were approximately twofold greater in watersheds draining the regolith of Catoctin metabasalts than that of granitic gneisses and granitoid crystalline rocks. The stable isotopic composition of water in spring discharge broadly correlates with the Oceanic Niño Index. Below normal precipitation and enriched stable isotopic composition were observed during El Niño years.     

Determining the groundwater potential recharge zone and karst springs catchment area: Saldoran region,western Iran

Assessing the groundwater recharge potential zone and differentiation of the spring catchment area are extremely important to effective management of groundwater systems and protection of water quality. The study area is located in the Saldoran karstic region, western Iran. It is characterized by a high rate of precipitation and recharge via highly permeable fractured karstic formations. Pire-Ghar, Sarabe-Babaheydar and Baghe-rostam are three major karstic springs which drain the Saldoran anticline. The mean discharge rate and electrical conductivity values for these springs were 3, 1.9 and 0.98 m³/s, and 475, 438 and 347 μS/cm, respectively. Geology, hydrogeology and geographical information system (GIS) methods were used to define the catchment areas of the major karstic springs and to map recharge zones in the Saldoran anticline. Seven major influencing factors on groundwater recharge rates (lithology, slope value and aspect, drainage, precipitation, fracture density and karstic domains) were integrated using GIS. Geology maps and field verification were used to determine the weights of factors. The final map was produced to reveal major zones of recharge potential. More than 80 % of the study area is terrain that has a recharge rate of 55–70 % (average 63 %). Evaluating the water budget of Saldoran Mountain showed that the total volume of karst water emerging from the Saldoran karst springs is equal to the total annual recharge on the anticline. Therefore, based on the geological and hydrogeological investigations, the catchment area of the mentioned karst springs includes the whole Saldoran anticline.     

Groundwater recharge mechanism in an integrated tableland of the Loess Plateau,northern China: insights from environmental tracers

Assessing groundwater recharge characteristics (recharge rate, history, mechanisms (piston and preferential flow)) and groundwater age in arid and semi-arid environments remains a difficult but important research frontier. Such assessments are particularly important when the unsaturated zone (UZ) is thick and the recharge rate is limited. This study combined evaluations of the thick UZ with those of the saturated zone and used multiple tracers, such as Cl, NO₃, Br, ²H, ¹⁸O, ¹³C, ³H and ¹⁴C, to study groundwater recharge characteristics in an integrated loess tableland in the Loess Plateau, China, where precipitation infiltration is the only recharge source for shallow groundwater. The results indicate that diffuse recharge beneath crops, as the main land use of the study area, is 55–71 mm yr^?1 based on the chloride mass balance of soil profiles. The length of time required for annual precipitation to reach the water table is 160–400 yrs. The groundwater is all pre-modern water and paleowater, with corrected ¹⁴C age ranging from 136 to 23,412 yrs. Most of the water that eventually becomes recharge originally infiltrated in July–September. The Cl and NO₃ contents in the upper UZ are considerably higher than those in the deep UZ and shallow groundwater because of recent human activities. The shallow groundwater has not been in hydraulic equilibrium with present near-surface boundary conditions. The homogeneous material of the UZ and relatively old groundwater age imply that piston flow is the dominant recharge mechanism for the shallow groundwater in the tableland.     

Groundwater age,mixing and flow rates in the vicinity of large open pit mines,Pilbara region,northwestern Australia

Determining groundwater ages from environmental tracer concentrations measured on samples obtained from open bores or long-screened intervals is fraught with difficulty because the sampled water represents a variety of ages. A multi-tracer technique (Cl, ¹⁴C, ³H, CFC-11, CFC-12, CFC-113 and SF₆) was used to decipher the groundwater ages sampled from long-screened production bores in a regional aquifer around an open pit mine in the Pilbara region of northwest Australia. The changes in tracer concentrations due to continuous dewatering over 7 years (2008–2014) were examined, and the tracer methods were compared. Tracer concentrations suggest that groundwater samples are a mixture of young and old water; the former is inferred to represent localised recharge from an adjacent creek, and the latter to be diffuse recharge. An increase in ¹⁴C activity with time in wells closest to the creek suggests that dewatering of the open pit to achieve dry mining conditions has resulted in change in flow direction, so that localised recharge from the creek now forms a larger proportion of the pumped groundwater. The recharge rate prior to development, calculated from a steady-state Cl mass balance, is 6 mm/y, and is consistent with calculations based on the ¹⁴C activity. Changes in CFC-12 concentrations with time may be related to the change in water-table position relative to the depth of the well screen.     

Spatial and temporal constraints on regional-scale groundwater flow in the Pampa del Tamarugal Basin,Atacama Desert,Chile

Aquifers within the Pampa del Tamarugal Basin (Atacama Desert, northern Chile) are the sole source of water for the coastal city of Iquique and the economically important mining industry. Despite this, the regional groundwater system remains poorly understood. Although it is widely accepted that aquifer recharge originates as precipitation in the Altiplano and Andean Cordillera to the east, there remains debate on whether recharge is driven primarily by near-surface groundwater flow in response to periodic flood events or by basal groundwater flux through deep-seated basin fractures. In addressing this debate, the present study quantifies spatial and temporal variability in regional-scale groundwater flow paths at 20.5°S latitude by combining a two-dimensional model of groundwater and heat flow with field observations and δ¹⁸O isotope values in surface water and groundwater. Results suggest that both previously proposed aquifer recharge mechanisms are likely influencing aquifers within the Pampa del Tamarugal Basin; however, each mechanism is operating on different spatial and temporal scales. Storm-driven flood events in the Altiplano readily transmit groundwater to the eastern Pampa del Tamarugal Basin through near-surface groundwater flow on short time scales, e.g., 10⁰–10¹ years, but these effects are likely isolated to aquifers in the eastern third of the basin. In addition, this study illustrates a physical mechanism for groundwater originating in the eastern highlands to recharge aquifers and salars in the western Pampa del Tamarugal Basin over timescales of 10⁴–10⁵ years.     

Use and application of CFC-11,CFC-12,CFC-113 and SF_6 as environmental tracers of groundwater residence time:A review

Groundwater residence time is a fundamental property of groundwater to understand important hydrogeological issues,such as deriving sustainable abstraction volumes,or,the evolution of groundwater quality.The anthropogenic trace gases chlorofluorocarbons(CFC-11,CFC-12 and CFC-113)and sulphur hexafluoride(SF_6)are ideal in this regard because they have been released globally at known rates and become dissolved in groundwater following Henry's Law,integrating over large spatial(global)and temporal(decades)scales.The CFCs and SF_6 are able to date groundwater up to～100 years old with the caveat of certain simplifying assumptions.However,the inversion of environmental tracer concentrations(CFCs and SF_6)to derive groundwater age rests on the accurate determination of groundwater recharge parameters,namely temperature,elevation,salinity and excess air,in addition to resolving the potential for contamination,degradation and unsaturated zone effects.This review explores the fundamentals of CFC-11,CFC-12,CFC-113 and SF_6 as environmental tracers of groundwater age and recommends complementary techniques throughout.Once this relatively simple and inexpensive technique has been used to determine initial concentrations at the recharge zone,setting the groundwater dating'clock' to zero,this review then explores the meaning of groundwater'age' in relation to measured environmental tracer concentrations.It is shown that the CFCs and SF_6 may be applied to a wide-range of hydrogeological problems and suggests that environmental tracers are particularly powerful tools when integrated with numerical flow and transport models.     

Comparison of age distributions estimated from environmental tracers by using binary-dilution and numerical models of fractured and folded karst: Shenandoah Valley of Virginia and West Virginia, USA

Measured concentrations of environmental tracers in spring discharge from a karst aquifer in the Shenandoah Valley, USA, were used to refine a numerical groundwater flow model. The karst aquifer is folded and faulted carbonate bedrock dominated by diffuse flow along fractures. The numerical model represented bedrock structure and discrete features (fault zones and springs). Concentrations of ³H, ³He, ⁴He, and CFC-113 in spring discharge were interpreted as binary dilutions of young (0–8  years) water and old (tracer-free) water. Simulated mixtures of groundwater are derived from young water flowing along shallow paths, with the addition of old water flowing along deeper paths through the model domain that discharge to springs along fault zones. The simulated median age of young water discharged from springs (5.7  years) is slightly older than the median age estimated from ³H/³He data (4.4  years). The numerical model predicted a fraction of old water in spring discharge (0.07) that was half that determined by the binary-dilution model using the ³H/³He apparent age and ³H and CFC-113 data (0.14). This difference suggests that faults and lineaments are more numerous or extensive than those mapped and included in the numerical model.     

Groundwater flow in an ‘underfit’ carbonate aquifer in a semiarid climate: application of environmental tracers to the Salt Basin,New Mexico (USA)

The Salt Basin is a semiarid hydrologically closed drainage basin in southern New Mexico, USA. The aquifers in the basin consist largely of Permian limestone and dolomite. Groundwater flows from the high elevations (～2,500 m) of the Sacramento Mountains south into the Salt Lakes, which are saline playas. The aquifer is ‘underfit’ in the sense that depths to groundwater are great (～300 m), implying that the aquifer could transmit much more water than it does. In this study, it is speculated that this characteristic is a result of a geologically recent reduction in recharge due to warming and drying at the end of the last glacial period. Water use is currently limited, but the basin has been proposed for large-scale groundwater extraction and export projects. Wells in the basin are of limited utility for hydraulic testing; therefore, the study focused on environmental tracers (major-ion geochemistry, stable isotopes of O, H, and C, and ¹⁴C dating) for basin analysis. The groundwater evolves from a Ca–HCO₃ type water into a Ca–Mg (Na) – HCO₃–Mg (Cl) water as it flows toward the center of the basin due to dedolomitization driven by gypsum dissolution. Carbon-14 ages corrected for dedolomitization ranged from less than 1,000 years in the recharge area to 19,000 years near the basin center. Stable isotopes are consistent with the presence of glacial-period recharge that is much less evaporated than modern. This supports the hypothesis that the underfit nature of the aquifer is a result of a geologically recent reduction in recharge.     

Environmental isotopic and hydrochemical study of water in the karst aquifer and submarine springs of the Syrian coast

The groundwater of major karst systems and submarine springs in the coastal limestone aquifer of Syria has been investigated using chemical and isotopic techniques. The δ¹⁸O values of groundwater range from ?6.8 to ?5.05‰, while those for submarine springs vary from ?6.34 to +1.08‰ (eastern Mediterranean seawater samples have a mean of +1.7‰). Groundwater originates from the direct infiltration of atmospheric water. Stable isotopes show that the elevation of the recharge zones feeding the Banyas area (400–600 m a.s.l.) is higher than that feeding the Amrit area (100–300 m a.s.l.). The ¹⁸O_extracted (¹⁸O content of the seawater contribution) for the major submarine springs suggests a mean recharge area elevation of 600–700 m a.s.l., and lower than 400 m a.s.l. for the spring close to Amrit. Based on the measured velocity and the percentage of fresh water at the submarine springs outlet, the estimated discharge rate is 350 million m³/year. The tritium concentrations in groundwater (1.6–5.9 TU) are low and very close to the current rainfall values (2.9–5.6 TU). Adopting a model with exponential time distribution, the mean turnover time of groundwater in the Al-sen spring was evaluated to be 60 years. A value of about 3.7 billion m³ was obtained for the maximum groundwater reservoir size.     

Evaluation of the recharge processes and impacts of irrigation on groundwater using CFCs and radiogenic isotopes in the Silao-Romita basin, Mexico

The recharge processes in the overexploited aquifer of the Silao Romita basin, central Mexico, were investigated by means of gaseous tracers (chlorofluorocarbons, CFCs) and radioactive isotopes (C-14, tritium). CFC concentrations varied between 0.06 and 12 pmol/l (CFC-11), 0.03 and 1.7 pmol/l (CFC-12), and <0.01 and 0.23 pmol/l (CFC-113). CFC concentrations are controlled by irrigation return flow which became apparent by the comparison with tritium. Tritium activities ranged from 0 to 3.5 TU. The calculated mean residence times of 70 to more than 300 years are considerably lower than the ages estimated based on the CFCs data. These data showed that CFCs were not appropriate for groundwater dating in this particular area but the CFCs were suitable as a qualitative measure of the magnitude of irrigation return flow which proved to be a significant source of recharge in the irrigated areas. Radiocarbon activities were in the range of 6–109 pmC. Carbon-13 values varied between –11.9 and –7.2‰ VPDB. Modelling of carbon isotopes with NETPATH along a plausible flow path reveals considerable influences of exchange with soil CO₂ and carbonate dissolution. Radiocarbon data indicate, at least in one case, the existence of groundwaters with residence times of more than 10,000 years.     

Evaluation of groundwater residence time in a high mountain aquifer system (Sacramento Mountains,USA): insights gained from use of multiple environmental tracers

The New Mexico Bureau of Geology and Mineral Resources (USA) has conducted a regional investigation of groundwater residence time within the southern Sacramento Mountains aquifer system using multiple environmental tracers. Results of the tracer surveys indicate that groundwater in the southern Sacramento Mountains ranges in age from less than 1 year to greater than 50 years, although the calculated ages contain uncertainties and vary significantly depending on which tracer is used. A distinctive feature of the results is discordance among the methods used to date groundwater in the study area. This apparent ambiguity results from the effects of a thick unsaturated zone, which produces non-conservative behavior among the dissolved gas tracers, and the heterogeneous character and semi-karstic nature of the aquifer system, which may yield water from matrix porosity, fractures, solution-enlarged conduits, or a combination of the three. The data also indicate mixing of groundwater from two or more sources, including recent recharge originating from precipitation at high elevations, old groundwater stored in the matrix, and pre-modern groundwater upwelling along fault zones. The tracer data have also been influenced by surface-water/groundwater exchange via losing streams and lower elevation springs (groundwater recycling). This study highlights the importance of using multiple tracers when conducting large-scale investigations of a heterogeneous aquifer system, and sheds light on characteristics of groundwater flow systems that can produce discrepancies in calculations of groundwater age.     

Geochemical characterization and origins of the thermal springs in southern Gaoligong Mountains,China

Hydrogeochemistry and environmental isotope data were utilized to understand origins and characteristics of the thermal springs in southern Gaoligong Mountains, China. The groundwater at the thermal springs has low values of total dissolved solids, and its main water types are Na-HCO₃. The thermal springs are mainly recharged from meteoric precipitations. The recharge areas are located near the springs at an approximate elevation of 1,800 m. The groundwater of the thermal springs is immature and partially equilibrated with a strong mixture of the shallow cold waters during the flow process. The shallow cold water accounts for more than 90 %. The temperatures of thermal reservoir that feed the springs are between 146 and 260 °C, and the calculated groundwater circulation depths range from 2,000 to 5,700 m below ground surface.     

Dynamics and anthropogenic impacts of multiple karst flow systems in a mountainous area of South China

The Xiangxi River basin, South China, is a steep terrane with well-developed karst features and an important Cambrian-Ordovician aquifer. Meteoric water in this mountainous area features a mean δ¹⁸O elevation gradient of –2.4?‰/km. This gradient was used to estimate mean recharge elevations of 760 m for Shuimoxi (SMX) spring, 1,060 m for Xiangshuidong (XSD) spring, and 1,430 m for drill hole ZK03, indicating multiple flow paths in the Cambrian-Ordovician karst aquifer. Mean residence times of 230 and 320 days and ～2 years were estimated for these features, respectively, using the damped running average model that predicts the isotopic variations in groundwater from those in precipitation. Groundwater in the regional karst flow system has the longest residence time, the highest recharge elevation, the longest flow paths, the lowest addition of anthropogenic components, and the greatest amount of water–rock interaction as indicated by its higher dissolved solids, Mg²⁺ concentrations and Mg/Ca ratios than the springs. In contrast, the local and shallow karst flow systems respond rapidly to recharge events. Artificial tracer tests prove that these shallow karst systems can also quickly transmit anthropogenic contaminants, indicating that they are highly vulnerable to human impacts, which include the enrichment of NO₃ ^–. The intensity of water–rock interaction and groundwater vulnerability are mainly determined by the structure and dynamics of the multiple karst flow systems.     

Estimation of groundwater recharge in arid, data scarce regions; an approach as applied in the El Hawashyia basin and Ghazala sub-basin (Gulf of Suez, Egypt)

In this study, an approach for runoff and recharge estimations that can be applied in arid regions which suffer from lack of data is presented. Estimating groundwater recharge in arid regions is an extremely important but difficult task, the main reason is the scarcity of data in arid regions. This is true for the Eastern Egyptian Desert where groundwater is used for irrigation purposes in agricultural reclamation along the Red Sea coast line. As a result of the scarcity of hydrologic information, the relation between rainfall and runoff was calculated depending on the paleo-flood hydrology information. Two models were used to calculate the rainfall–runoff relationships for El Hawashyia basin and Ghazala sub-basin. Two computer programs known as Gerinne (meaning channel in German) and SMADA6 (Stormwater Management and Design Aid, version 6) were conjunctively used for this purpose. As a result of the model applied to El Hawashyia basin, a rainfall event of a total of 18.3 mm with duration 3 h at the station of Hurghada, which has an exceedance probability of 5–10 %, produces a discharge volume of 10.2 × 10⁶ m³ at the delta, outlet of the basin, as 4.7 mm of the rainfall infiltrates (recharge). For the Ghazala sub-basin, the model yields a runoff volume of 3.16 × 10⁶ m³ transferred from a total rainfall of 25 mm over a period of 3 h, as 3.2 mm of it was lost as infiltration.     

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.     

Radiocarbon age distribution of groundwater in the Konya Closed Basin, central Anatolia, Turkey

Annual abstraction of 2.6?×?10⁹ m³ of groundwater in the 53,000 km² Konya Closed Basin of central Turkey has caused a head decline of 1 m/year over the last few decades. Therefore, understanding the hydrogeology of this large endorheic basin, in a semi-arid climate, is important to sustainable resource management. For this purpose, the groundwater’s radiocarbon age distribution has been investigated along a 150-km transect parallel to regional flow. Results show that the groundwater ranges in age from Recent at the main recharge area of the Taurus Mountains in the south, to about 40,000 years around the terminal Salt Lake located in the north. In this predominantly confined flow system, radiocarbon ages increase linearly by distance from the main recharge area and are in agreement with the hydraulic ages. The mean velocity of regional groundwater flow (3 m/year) is determined by the rate of regional groundwater discharge into the Salt Lake. Calcite dissolution, dedolomitization and geogenic carbon dioxide influx appear to be the dominant geochemical processes that determine the carbon isotope composition along the regional flow path. The groundwater’s oxygen-18 content indicates more humid and cooler paleorecharge. A maximum drop of 5°C is inferred for the past recharge temperature.     

Oxygen, hydrogen, and helium isotopes for investigating groundwater systems of the Cape Verde Islands, West Africa

Stable isotopes (δ¹⁸O, δ²H), tritium (³H), and helium isotopes (³He, ⁴He) were used for evaluating groundwater recharge sources, flow paths, and residence times of three watersheds in the Cape Verde Islands (West Africa). Stable isotopes indicate the predominance of high-elevation precipitation that undergoes little evaporation prior to groundwater recharge. In contrast to other active oceanic hotspots, environmental tracers show that deep geothermal circulation does not strongly affect groundwater. Low tritium concentrations at seven groundwater sites indicate groundwater residence times of more than 50 years. Higher tritium values at other sites suggest some recent recharge. High ⁴He and ³He/⁴He ratios precluded ³H/³He dating at six sites. These high ³He/⁴He ratios (R/R_a values of up to 8.3) are consistent with reported mantle derived helium of oceanic island basalts in Cape Verde and provided end-member constraints for improved dating at seven other locations. Tritium and ³H/³He dating shows that São Nicolau Island’s Ribeira Fajã Basin has groundwater residence times of more than 50 years, whereas Fogo Island’s Mosteiros Basin and Santo Antão Island’s Ribeira Paul Basin contain a mixture of young and old groundwater. Young ages at selected sites within these two basins indicate local recharge and potential groundwater susceptibility to surface contamination and/or salt-water intrusion.     

Watershed-scale response of groundwater recharge to inter-annual and inter-decadal variability in precipitation (Alberta,Canada)

Groundwater recharge sets a constraint on aquifer water balance in the context of water management. Historical data on groundwater and other relevant hydrological processes can be used to understand the effects of climatic variability on recharge, but such data sets are rare. The climate of the Canadian prairies is characterized by large inter-annual and inter-decadal variability in precipitation, which provides opportunities to examine the response of groundwater recharge to changes in meteorological conditions. A decadal study was conducted in a small (250 km²) prairie watershed in Alberta, Canada. Relative magnitude of annual recharge, indicated by water-level rise, was significantly correlated with a combination of growing-season precipitation and snowmelt runoff, which drives depression-focussed infiltration of meltwater. Annual precipitation was greater than vapour flux at an experimental site in some years and smaller in other years. On average precipitation minus vapour flux was 10 mm y^?1, which was comparable to the magnitude of watershed-scale groundwater recharge estimated from creek baseflow. Average baseflow showed a distinct shift from a low value (4 mm y^?1) in 1982–1995 to a high value (15 mm y^?1) in 2003–2013, indicating the sensitivity of groundwater recharge to a decadal-scale variability of meteorological conditions.     

Hydrochemical and isotopic evidence of recharge,apparent age,and flow direction of groundwater in Mayo Tsanaga River Basin,Cameroon: bearings on contamination

Unplanned exploitation of groundwater constitutes emerging water-related threats to MayoTsanaga River Basin. Shallow groundwater from crystalline and detrital sediment aquifers, together with rain, dams, springs, and rivers were chemically and isotopically investigated to appraise its evolution, recharge source and mechanisms, flow direction, and age which were used to evaluate the groundwater susceptibility to contamination and the basin’s stage of salinization. The groundwater which is Ca–Na–HCO₃ type is a chemically evolved equivalent of surface waters and rain water with Ca–Mg–Cl–SO₄ chemistry. The monsoon rain recharged the groundwater preferentially at an average rate of 74 mm/year, while surface waters recharge upon evaporation. Altitude effect of rain and springs show a similar variation of −0.4‰ for δ¹⁸O/100 m, but the springs which were recharged at 452, 679, and 773 m asl show enrichment of δ¹⁸O through evaporation by 0.8‰ corresponding to 3% of water loss during recharge. The groundwater which shows both local and regional flow regimes gets older towards the basins` margin with coeval enrichment in F⁻ and depletion in NO₃ ⁻. Incidentally, younger groundwaters are susceptible to anthropogenic contamination and older groundwaters are sinks of lithologenic fluoride. The basins salinization is still at an early stage.     

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.