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.     

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.     

Tracing ionic sources and geochemical evolution of groundwater in the Intermountain Una basin in outer NW Himalaya,Himachal Pradesh,India

The present research aims to identify sources of ions and factors controlling the geochemical evolution of groundwater in an intermountain basin, comprising hill and valley fill region, of Outer Himalaya in Himachal Pradesh, India. The groundwater samples collected from 81 tubewells and handpumps are analyzed for major ions, trace metals and stable isotopes (δ¹⁸O and δD). Geochemically the dominant hydrochemical facies in the Una basin are Ca–HCO₃, Ca–Mg–HCO₃ and Na–Cl types at few locations. A relatively lower ionic concentration in the valley fills indicates dilution and low residence time of water to interact with the aquifer mass due to high porosity and permeability. The ionic ratios of 0.9, 0.8 and 3.8 to 5.7, respectively, for (Ca?+?Mg): HCO₃, (Ca?+?Mg): (HCO₃?+?SO₄) and Na: Cl, suggests that ionic composition of groundwater is mainly controlled by rock weathering of, particularly by dissolution/precipitation of calcrete and calcite hosted in rock veins and Ca–Na feldspar hosted in conglomerate deposits derived from the Higher and Lesser Himalaya during the formation of Siwalik rocks. Although Na, K, NO₃ and SO₄ are introduced in the groundwater through agricultural practices, Na has also been introduced through ion exchange processes that have occurred during water–rock interaction, as indicated by negative CAI values. Factor analysis further suggests three major factors affecting the water chemistry of the area. The first two factors are associated with rock weathering while the third is anthropogenic processes associated with high nitrate and iron concentration. High concentrations of Fe and Mn ions that are exceeded that of WHO and BIS standards are also present at few locations. The recharge of groundwater in the Outer Himalaya is entirely through Indian Southwest Monsoon (ISM) and depleted ratios of δ¹⁸O/δD in valley region indicate infiltration from irrigation in recharging the groundwater and fractionation of isotopes of precipitation due to evaporation before infiltration. High d-excess values and inverse relation with δ¹⁸O are indicative of secondary evaporation of precipitation during recharge of groundwater.     

Calculating groundwater mixing ratios in groundwater-inrushing aquifers based on environmental stable isotopes (D, 18O) and hydrogeochemistry

Conventional hydrogeochemical data and environmental stable isotopes are used to identify the recharge sources and the water–rock interactions in the groundwater-flowing direction within the multilayer groundwater system of the Sulin coal-mining district in the north Anhui province in China. δD and δ ¹⁸O of groundwater in the mining district decrease along the groundwater-flowing direction in the recharge areas, yet in the runoff or discharge areas, they rise and fall along average δ values (δ ¹⁸O = ?8.68 ‰, δD = ?67.4 ‰), which are lower than average δ values of local atmospheric precipitation (δ ¹⁸O = ?7.80 ‰, δD = ?52.4 ‰). Principal component analysis is used to analyze the conventional hydrogeochemical data (K⁺ + Na⁺, Mg²⁺, Ca²⁺, Cl^?, SO₄ ^2?, HCO₃ ^?, CO₃ ^2?) in the groundwater. The first and second principal components have large variance contributions, and represent “pyrite oxidation or groundwater hardening” and “desulfurization or cation exchange and adsorption,” respectively. From conventional hydrogeochemical data and environmental stable isotopes, it is demonstrated that groundwater of the Sulin coal-mining district is characterized by a mixing type, which is confirmed by three recharge end-members: fresh groundwater, leaching groundwater, and retained groundwater. By means of a sample dot-encompassed triangle in the scatter diagram of load scores for Component 1–Component 2, whose vertexes stand for the three end-members, a model for calculating groundwater mixing ratio is established and applied successfully to the evaluation and management of groundwater hazards in the coal-mining districts.     

Isotopic and geochemical evolution of ground and surface waters in a karst dominated geological setting: a case study from Belize,Central America

Analysis of stable isotopes and major ions in groundwater and surface waters in Belize, Central America was carried out to identify processes that may affect drinking water quality. Belize has a subtropical rainforest/savannah climate with a varied landscape composed predominantly of carbonate rocks and clastic sediments. Stable oxygen (δ¹⁸O) and hydrogen (δD) isotope ratios for surface and groundwater have a similar range and show high d-excess (10–40.8‰). The high d-excess in water samples suggest secondary continental vapor flux mixing with incoming vapor from the Caribbean Sea. Model calculations indicate that moisture derived from continental evaporation contributes 13% to overhead vapor load. In surface and groundwater, concentrations of dissolved inorganic carbon (DIC) ranged from 5.4 to 112.9 mg C/l and δ¹³C_DIC ranged from −7.4 to −17.4‰. SO₄², Ca²⁺ and Mg²⁺ in the water samples ranged from 2–163, 2–6593 and 2–90 mg/l, respectively. The DIC and δ¹³C_DIC indicate both open and closed system carbonate evolution. Combined δ¹³C_DIC and Ca²⁺, Mg²⁺, and SO₄²⁻ suggest additional groundwater evolution by gypsum dissolution and calcite precipitation. The high SO₄²⁻content of some water samples indicates regional geologic control on water quality. Similarity in the range of δ¹⁸O, δD and δ¹³C_DIC for surface waters and groundwater used for drinking water supply is probably due to high hydraulic conductivities of the karstic aquifers. The results of this study indicate rapid recharge of groundwater aquifers, groundwater influence on surface water chemistry and the potential of surface water to impact groundwater quality and vise versa.     

Hydrogeochemical and Isotopic Study of Groundwater in a Semi-arid Region: Yeniceoba Plain (Cihanbeyli-KONYA), Central Anatolia,Turkey

Groundwater is the most important source of water supply in the Yeniceoba Plain in Central Anatolia,Turkey.An understanding of the geochemical evolution of groundwater is important for the sustainable development of water resources in this region.A hydrogeochemical investigation was conducted in the Plio-Quaternary aquifer system using stable isotopes(δ~(18)O andδD),tritium(~3H),major and minor elements(Ca,Na,K,Mg,Cl,SO_4,NO_3,HCO_3 and Br)in order to identify groundwater chemistry patterns and the processes affecting groundwater mineralization in this system.The chemical data reveal that the chemical composition of groundwater in this aquifer system is mainly controlled by rock/water interactions including dissolution of evaporitic minerals,weathering of silicates,precipitation/dissolution of carbonates,ion exchange,and evaporation.Based on the values of Cl/Br ratio(300 mg/l)in the Plio-Quaternary groundwater,dissolution of evaporitic minerals in aquifer contributes significantly to the high mineralization.The stable isotope analyses indicate that the groundwater in the system was influenced by evaporation of rainfall during infiltration.Low tritium values(generally1 tritium units)of groundwater reflect a minor contribution of recent recharge and groundwater residence times of more than three or four decades.     

Characterisation of groundwater recharge conditions and flow mechanisms in bedrock aquifers of the Johannesburg area,South Africa

Groundwater is the major source of water and a critical resource for socioeconomic development in semi-arid environments like the Johannesburg area. Environmental isotopes are employed in this study to characterise groundwater recharge and flow mechanisms in the bedrock aquifers of Johannesburg, which is known for polluted surface water. With the exception of boreholes near the Hartbeespoort Dam, groundwater in the study area was derived from meteoric water that has undergone some degree of evaporation before recharge, possibly via diffuse mechanisms. Boreholes that tap groundwater from the Transvaal Supergroup Formation show depletion in δ¹⁸O and δ²H values. This is attributed to diffuse recharge through weathering fractures at high elevation that are undergoing deep circulation or recharge from depleted rainfall from the high-latitude moisture sources. The influence of focused recharge from the Hartbeespoort Dam was observed in the boreholes north of the dam, possibly as a result of the north–south trending fault lines and the north-dipping fractures in the bedding planes of quartzites. This is also supported by a reservoir water budget method which indicated a mean annual net flux of 2,084,131 m³ from Hartbeespoort Dam recharging groundwater per annum. Using tritium in the dam and boreholes located at 750 m and 5400 m downstream, average groundwater flow velocity was estimated as 202 m/year. An open system was observed in shale, andesite and granitic-gneiss aquifers indicating soil CO₂ as a dominant source of carbon (δ¹³C) in groundwater. A closed system was also observed in dolomitic aquifers indicating carbonate dissolution as the predominant source of carbon.     

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.

     

Isotopic variations of oxygen and hydrogen in groundwater of carbonate aquifer in an arid environment

The stable isotopic characteristics were used together with the total chloride to assess changes in groundwater from recharge zones into the carbonate aquifer in an arid environment. The aquifer under study represents a major source of groundwater and thermal springs in Al-Ain city, which are located at the northern part of Jabal Hafit in the United Arab Emirates (UAE). The relationship between oxygen and hydrogen isotopic composition of groundwater is established and is described by δD?=?2.2δ¹⁸O???9.96. The lower slope and y-intercept of groundwater samples relative to the local meteoric waterline suggests that the isotopic enrichment is due to the evaporation of shallow groundwater after recharge occurs. The majority of the shallow groundwater samples have a negative deuterium excess (d-excess) which might be ascribed to high a degree of evaporation, while most of the groundwater samples from deep wells, have a positive value of d-excess which may be related to a low degree of evaporation. The δ¹⁸O values of the thermal waters suggest enrichment towards δ¹⁸O of the carbonate rocks because of the exchange with oxygen at higher temperatures. A possible mixing between thermal or hot water and shallow groundwater is evident in some samples as reflected by δD vs. Cl and d-excess vs. δ¹⁸O plots.     

Mixing of magmatic CO2 into volcano groundwater flow at Aso volcano assessed combining carbon and water stable isotopes

To understand deep groundwater flow systems and their interaction with CO₂ emanated from magma at depth in a volcanic edifice, deep groundwater samples were collected from hot spring wells in the Aso volcanic area for hydrogen, oxygen and carbon isotope analyses and measurements of the stable carbon isotope ratios and concentrations of dissolved inorganic carbon (DIC). Relations between the stable carbon isotope ratio (δ¹³C_DIC) and DIC concentrations of the sampled waters show that magma-derived CO₂ mixed into the deep groundwater. Furthermore, groundwaters of deeper areas, except samples from fumarolic areas, show higher δ¹³C_DIC values. The waters' stable hydrogen and oxygen isotope ratios (δD and δ¹⁸O) reflect the meteoric-water origin of that region's deep groundwater. A negative correlation was found between the altitude of the well bottom and the altitude of groundwater recharge as calculated using the equation of the recharge-water line and δD value. This applies especially in the Aso-dani area, where deeper groundwater correlates with higher recharge. Groundwater recharged at high altitude has higher δ¹³C_DIC of than groundwater recharged at low altitude, strongly suggesting that magmatic CO₂ is present to a much greater degree in deeper groundwater. These results indicate that magmatic CO₂ mixes into deeper groundwater flowing nearer the magma conduit or chamber.     

An appraisal of groundwater quality in Seymour and Blaine aquifers in a major agro-ecological region in Texas,USA

Aquifer-based groundwater quality assessment offers critical insight into the major hydrochemical processes, and aids in making groundwater resources management decisions. The Texas Rolling Plains (TRP), spanning over 22 counties, is a major agro-ecological region in Texas from where highest groundwater nitrate (NO₃ ^?) levels in the state have been reported. In this study, we present a comparative assessment of major hydrochemical facies pertaining to NO₃ ^? contamination and a host of species such as sulfate (SO₄ ^2?), chloride (Cl^?), and total dissolved solids (TDS) in different water use classes in the Seymour and Blaine aquifers, underlying the TRP. Aquifer-stratified groundwater quality information from 1990 to 2010 was obtained from the Texas Water Development Board and aggregated over decadal scale. High groundwater salinization was found in the municipal water use class in the Blaine aquifer with about 100, 87 and 50 % of observations exceeding the secondary maximum contaminant level for TDS, SO₄ ^2?, and Cl^?, respectively in the 2000s (2000–2010). The NO₃-contamination was more alarming in the Seymour aquifer with 82 and 61 % of observations, respectively, exceeding the maximum contaminant level (MCL) in the irrigation and municipal water use classes in the 2000s. Salinization was more influenced by SO₄ ^2? and Cl^? in the Blaine aquifer and by NO₃ ^? in the Seymour aquifer. High NO₃ ^? (>MCL) observations in the Seymour aquifer occurred in the Ca–HCO₃ and Ca–Mg–HCO₃ facies, the domains of fresh water recharge and anthropogenic influences (e.g., agricultural activities, waste disposal). High SO₄ ^2?, Cl^? and TDS observations in the Blaine aquifer dominated the Ca–Cl, Na–Cl, and mixed Ca(Mg)–SO₄(Cl) facies indicating evaporite dissolution, mixing and solute exchange, and lack of fresh recharge.     

Delineating volcanic aquifer recharge areas using geochemical and isotopic tools

Relative recharge areas are evaluated using geochemical and isotopic tools, and inverse modeling. Geochemistry and water quality in springs discharging from a volcanic aquifer system in Guatemala are related to relative recharge area elevations and land use. Plagioclase feldspar and olivine react with volcanically derived CO₂ to produce Ca-montmorillonite, chalcedony and goethite in the groundwater. Alkalinity, Mg, Ca, Na, and SiO_2(aq) are produced, along with minor increases in Cl and SO₄ concentrations. Variations in groundwater δD and δ¹⁸O values are attributed to recharge elevation and used in concert with geochemical evolution to distinguish local, intermediate, and regional flow systems. Springs with geochemically inferred short flow paths provided useful proxies to estimate an isotopic gradient for precipitation (??.67 δ¹⁸O/100?m). No correlation between spring discharge and relative flow-path length or interpreted recharge elevation was observed. The conceptual model was consistent with evidence of anthropogenic impacts (sewage and manure) in springs recharged in the lower watershed where livestock and humans reside. Spring sampling is a low-budget approach that can be used to develop a useful conceptual model of the relative scale of groundwater flow (and appropriate watershed protection areas), particularly in volcanic terrain where wells and boreholes are scarce.     

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.     

Hydrochemical and isotopic study of groundwater in the Yinchuan plain, China

The Yinchuan plain is located in the arid climate zone of NW China. The western margin of the plain is the Helan mountain connecting a series of normal slip faults. The eastern margin of the plain connects with the Yellow River and adjacents with the Ordos platform. The south of the plain is bordered by the EN fault of the Niushou mountain. The bottom of the plain is the Carboniferous, Permian, or Ordovician rocks. Based on the analysis of groundwater hydrochemical and isotopic indicators, this study aims to identify the groundwater recharge and discharge in the Yinchuan plain, China. The hydrochemical types of the groundwater are HCO₃–SO₄ in the west, HCO₃–Cl in the middle, and Cl–SO₄ in the east. The hydrochemical types are HCO₃–SO₄ in the south, HCO₃–Cl and SO₄–HCO₃ in the middle. The hydrochemical types are complex in the north, mainly SO₄–HCO₃ and Cl–SO₄. Deuterium, ¹⁸O, and tritium values of groundwater indicate that groundwater recharge sources include precipitation, bedrock fissure water, and irrigation return water. Groundwater discharges include evaporation, abstraction, and discharge to surface water. According to the EW isotopic profile, the groundwater flow system (GFS) in the Yinchuan plain can be divided into local flow systems (LFS) and regional flow systems (RFS). Groundwater has lower TDS and higher tritium in the southern Yellow River alluvial plain and groundwater age ranges from 6 to 25 years. The range of groundwater renewal rates is from 11 to 15 % a^?1. The depth of the water cycle is small, and groundwater circulates fast and has high renewal rates. Groundwater has higher TDS and lower tritium in the northern Yellow River alluvial plain. The range of groundwater age is from 45 to 57 years, and renewal rate is from 6 to 0.1 % a^?1. The depth of the water cycle is larger. Groundwater circulates slowly and has low renewal rates.     

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

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

Testing the suitability of geologic frameworks for extrapolating hydraulic properties across regional scales

The suitability of geologic frameworks for extrapolating hydraulic conductivity (K) to length scales commensurate with hydraulic data is difficult to assess. A novel method is presented for evaluating assumed relations between K and geologic interpretations for regional-scale groundwater modeling. The approach relies on simultaneous interpretation of multiple aquifer tests using alternative geologic frameworks of variable complexity, where each framework is incorporated as prior information that assumes homogeneous K within each model unit. This approach is tested at Pahute Mesa within the Nevada National Security Site (USA), where observed drawdowns from eight aquifer tests in complex, highly faulted volcanic rocks provide the necessary hydraulic constraints. The investigated volume encompasses 40 mi³ (167 km³) where drawdowns traversed major fault structures and were detected more than 2 mi (3.2 km) from pumping wells. Complexity of the five frameworks assessed ranges from an undifferentiated mass of rock with a single unit to 14 distinct geologic units. Results show that only four geologic units can be justified as hydraulically unique for this location. The approach qualitatively evaluates the consistency of hydraulic property estimates within extents of investigation and effects of geologic frameworks on extrapolation. Distributions of transmissivity are similar within the investigated extents irrespective of the geologic framework. In contrast, the extrapolation of hydraulic properties beyond the volume investigated with interfering aquifer tests is strongly affected by the complexity of a given framework. Testing at Pahute Mesa illustrates how this method can be employed to determine the appropriate level of geologic complexity for large-scale groundwater modeling.     

Using 87Sr/86Sr, δ18O and δ2H isotopes along with major chemical composition to assess groundwater salinization in lower Shire valley,Malawi

Groundwater resources in some parts of the lower section of Shire River valley, Malawi, are not useable for rural domestic water supply due to high salinity. In this study, a combined assessment of isotopic (⁸⁷Sr/⁸⁶Sr, δ¹⁸O and δ²H) and major ion composition was conducted in order to identify the hydro-geochemical evolution of the groundwater and thereby the causes of salinity. Three major end-members (representing fresh- and saline groundwater, and evaporated recharge) were identified based on major ion and isotopic composition. The saline groundwater is inferred to result from dissolution of evaporitic salts (halite) and the fresh groundwater shows influence of silicate weathering. Conservative mixing models show that brackish groundwater samples result from a three component mixture comprising the identified end-members. Hence their salinity is interpreted to result from mixing of fresh groundwater with evaporated recharge and saline groundwater. On the other hand, the groundwater with low TDS, found at some distance from areas of high salinity, is influenced by mixing of evaporated recharge and fresh groundwater only. Close to the Shire marshes, where there is shallow groundwater, composition of stable isotopes of water indicates that evaporation may also be an important factor.     

Use of multiple age tracers to estimate groundwater residence times and long-term recharge rates in arid southern Oman

Multiple age tracers were measured to estimate groundwater residence times in the regional aquifer system underlying southwestern Oman. This area, known as the Najd, is one of the most arid areas in the world and is planned to be the main agricultural center of the Sultanate of Oman in the near future. The three isotopic age tracers ⁴He, ¹⁴C and ³⁶Cl were measured in waters collected from wells along a line that extended roughly from the Dhofar Mountains near the Arabian Sea northward 400 km into the Empty Quarter of the Arabian Peninsula. The wells sampled were mostly open to the Umm Er Radhuma confined aquifer, although, some were completed in the mostly unconfined Rus aquifer. The combined results from the three tracers indicate the age of the confined groundwater is < 40 ka in the recharge area in the Dhofar Mountains, > 100 ka in the central section north of the mountains, and up to and > one Ma in the Empty Quarter. The ¹⁴C data were used to help calibrate the ⁴He and ³⁶Cl data. Mixing models suggest that long open boreholes north of the mountains compromise ¹⁴C-only interpretations there, in contrast to ⁴He and ³⁶Cl calculations that are less sensitive to borehole mixing. Thus, only the latter two tracers from these more distant wells were considered reliable. In addition to the age tracers, δ²H and δ¹⁸O data suggest that seasonal monsoon and infrequent tropical cyclones are both substantial contributors to the recharge. The study highlights the advantages of using multiple chemical and isotopic data when estimating groundwater travel times and recharge rates, and differentiating recharge mechanisms.     

Hydrogeochemical and isotopic evolution of water in the Complexe Terminal aquifer in the Algerian Sahara

The hydrogeochemical and isotopic evolution of groundwaters in the Mio–Pliocene sands of the Complexe Terminal (CT) aquifer in central Algeria are described. The CT aquifer is located in the large sedimentary basin of the Great Oriental Erg. Down-gradient groundwater evolution is considered along the main representative aquifer cross section (south–north), from the southern recharge area (Tinrhert Plateau and Great Oriental Erg) over about 700 km. Groundwater mineralisation increases along the flow line, from 1.5 to 8 g l^?1, primarily as a result of dissolution of evaporite minerals, as shown by Br/Cl and strontium isotope ratios. Trends in both major and trace elements demonstrate a progressive evolution along the flow path. Redox reactions are important and the persistence of oxidising conditions favours the increase in some trace elements (e.g. Cr) and also NO₃ ^?, which reaches concentrations of 16.8 mg l^?1 NO₃-N. The range in ¹⁴C, 0–8.4 pmc in the deeper groundwaters, corresponds with late Pleistocene recharge, although there then follows a hiatus in the data with no results in the range 10–20 pmc, interpreted as a gap in recharge coincident with hyper-arid but cool conditions across the Sahara; groundwater in the range 24.7–38.9 pmc signifies a distinct period of Holocene recharge. All δ¹⁸O compositions are enriched relative to deuterium and are considered to be derived by evaporative enrichment from a parent rainfall around ?11‰ δ¹⁸O, signifying cooler conditions in the late Pleistocene and possibly heavy monsoon rains during the Holocene.