Data‐Driven Approach for Analyzing Hydrogeology and Groundwater Quality Across Multiple Scales

Recent trends of assimilating water well records into statewide databases provide a new opportunity for evaluating spatial dynamics of groundwater quality and quantity. However, these datasets are scarcely rigorously analyzed to address larger scientific problems because they are of lower quality and massive. We develop an approach for utilizing well databases to analyze physical and geochemical aspects of groundwater systems, and apply it to a multiscale investigation of the sources and dynamics of chloride (Cl^?) in the near‐surface groundwater of the Lower Peninsula of Michigan. Nearly 500,000 static water levels (SWLs) were critically evaluated, extracted, and analyzed to delineate long‐term, average groundwater flow patterns using a nonstationary kriging technique at the basin‐scale (i.e., across the entire peninsula). Two regions identified as major basin‐scale discharge zones—the Michigan and Saginaw Lowlands—were further analyzed with regional‐ and local‐scale SWL models. Groundwater valleys (“discharge” zones) and mounds (“recharge” zones) were identified for all models, and the proportions of wells with elevated Cl^? concentrations in each zone were calculated, visualized, and compared. Concentrations in discharge zones, where groundwater is expected to flow primarily upwards, are consistently and significantly higher than those in recharge zones. A synoptic sampling campaign in the Michigan Lowlands revealed concentrations generally increase with depth, a trend noted in previous studies of the Saginaw Lowlands. These strong, consistent SWL and Cl^? distribution patterns across multiple scales suggest that a deep source (i.e., Michigan brines) is the primary cause for the elevated chloride concentrations observed in discharge areas across the peninsula.     

Characterization of the groundwater flow regime and hydrochemistry of groundwater from the Buem formation,Eastern Ghana

This study demonstrates the application of multivariate statistical methods in definition of groundwater recharge and discharge areas in a sedimentary basin in Ghana. Q‐mode hierarchical cluster analysis (HCA) was applied to 57 hydrochemical data from the Buem formation in the northern part of the Volta Region in Ghana. R‐mode HCA and R‐mode factor analysis were then applied to the same dataset to reveal the processes controlling the hydrochemistry of groundwater from this hydrogeological formation. Results of both the Q‐ and R‐mode analyses were backed by graphical methods. The analyses revealed two major water types, differentiated by salinity levels into four spatial groundwater associations. The characteristics of the four groundwater types are discussed. The recharge areas are characterized by Ca? HCO₃ low salinity waters which evolve through rock–water interactions to Na? HCO₃ high salinity waters in the discharge areas. This study finds that the hydrochemistry of groundwater from this formation is mainly controlled by the weathering of minerals, principally silicates in the aquifer matrix. The effects of the chemistry of recharging precipitation are higher in the recharge areas, while mineral weathering tends to be severe close to the discharge areas in the groundwater flow regime. All the four spatial groundwater associations have low sodium content, but salinity levels increase towards the discharge areas, such that some of wells in the discharge areas may not be acceptable for irrigation on grounds of high salinities which might affect the osmotic potentials of plants. Copyright © 2011 John Wiley & Sons, Ltd.     

Groundwater–surface water interactions in a large semi‐arid floodplain: implications for salinity management

Flow regulation and water diversion for irrigation have considerably impacted the exchange of surface water between the Murray River and its floodplains. However, the way in which river regulation has impacted groundwater–surface water interactions is not completely understood, especially in regards to the salinization and accompanying vegetation dieback currently occurring in many of the floodplains. Groundwater–surface water interactions were studied over a 2 year period in the riparian area of a large floodplain (Hattah–Kulkyne, Victoria) using a combination of piezometric surface monitoring and environmental tracers (Cl⁻, δ²H, and δ¹⁸O). Despite being located in a local and regional groundwater discharge zone, the Murray River is a losing stream under low flow conditions at Hattah–Kulkyne. The discharge zone for local groundwater, regional groundwater and bank recharge is in the floodplain within ∼1 km of the river and is probably driven by high rates of transpiration by the riparian Eucalyptus camaldulensis woodland. Environmental tracers data suggest that the origin of groundwater is principally bank recharge in the riparian zone and a combination of diffuse rainfall recharge and localized floodwater recharge elsewhere in the floodplain. Although the Murray River was losing under low flows, bank discharge occurred during some flood recession periods. The way in which the water table responded to changes in river level was a function of the type of stream bank present, with point bars providing a better connection to the alluvial aquifer than the more common clay‐lined banks. Understanding the spatial variability in the hydraulic connection with the river channel and in vertical recharge following inundations will be critical to design effective salinity remediation strategies for large semi‐arid floodplains. Copyright © 2005 John Wiley & Sons, Ltd.     

Stable isotopic and geochemical identification of groundwater evolution and recharge sources in the arid Shule River Basin of Northwestern China

Stable isotopic (δD_VSMOW and δ¹⁸O_VSMOW) and geochemical signatures were employed to constrain the geochemical evolution and sources of groundwater recharge in the arid Shule River Basin, Northwestern China, where extensive groundwater extraction occurs for agricultural and domestic supply. Springs in the mountain front of the Qilian Mountains, the Yumen‐Tashi groundwater (YTG), and the Guazhou groundwater (GZG) were Ca‐HCO₃, Ca‐Mg‐HCO₃‐SO₄ and Na‐Mg‐SO₄‐Cl type waters, respectively. Total dissolved solids (TDS) and major ion (Mg²⁺, Na⁺, Ca²⁺, K⁺, SO₄^2?, Cl^? and NO₃^?) concentrations of groundwater gradually increase from the mountain front to the lower reaches of the Guazhou Basin. Geochemical evolution in groundwater was possibly due to a combination of mineral dissolution, mixing processes and evapotranspiration along groundwater flow paths. The isotopic and geochemical variations in melt water, springs, river water, YTG and GZG, together with the end‐member mixing analysis (EMMA) indicate that the springs in the mountain front mainly originate from precipitation, the infiltration of melt water and river in the upper reaches; the lateral groundwater from the mountain front and river water in the middle reaches are probably effective recharge sources for the YTG, while contribution of precipitation to YTG is extremely limited; the GZG is mainly recharged by lateral groundwater flow from the Yumen‐Tashi Basin and irrigation return flow. The general characteristics of groundwater in the Shule River Basin have been initially identified, and the results should facilitate integrated management of groundwater and surface water resources in the study area. Copyright © 2015 John Wiley & Sons, Ltd.     

Multivariate statistical analysis of geochemical data as indicative of the hydrogeochemical evolution of groundwater in a sedimentary rock aquifer system

The study of groundwater hydrogeochemistry of the Paleozoic Basses-Laurentides sedimentary rock aquifer system in Québec produced a large geochemical dataset. Groundwater samples were collected at 153 sites over a 1500 km² study area and analyzed for major and minor ions. The large number of data can lead to difficulties in the integration, interpretation and representation of the results. Two multivariate statistical methods, hierarchical cluster analysis (HCA) and principal components analysis (PCA), were applied to a subgroup of the dataset to evaluate their usefulness to classify the groundwater samples, and to identify geochemical processes controlling groundwater geochemistry. This subgroup consisted of 144 samples and 14 parameters (Ca²⁺, Mg²⁺, Na⁺, K⁺, , Cl⁻, , Fe²⁺, Mn²⁺, Br⁻, Sr²⁺, F⁻, Ba²⁺, HS⁻). Seven geochemically distinct clusters, C1–C7, resulted from the HCA. Samples from clusters C3, C4, C6 and C7 are mostly located in preferential recharge areas. The majority of these samples have Ca–Mg–HCO₃ recharge groundwater (C3, C6, C7) and Na–HCO₃ evolved groundwater (C4). Samples from the other three clusters (C1, C2, C5) are characteristic of an aquifer system under confined conditions. The majority of these samples have Na–HCO₃ evolved groundwater (C1, C5) and Na–Cl ancient groundwater that exhibits elevated concentrations in Br⁻ (C2). In addition to recognizing the importance of hydrogeological conditions on groundwater geochemistry, the distribution of clusters also showed the importance of the geological formations on minor and trace elements, such as Fe²⁺, Mn²⁺, Sr²⁺, F⁻ and Ba²⁺. The first five components of the PCA account for 78.3% of the total variance in the dataset. Component 1 is defined by highly positive loadings in Na⁺, Cl⁻ and Br⁻ and is related to groundwater mixing with Champlain Sea water and solute diffusion from the marine clay aquitard. The high positive loadings in Ca²⁺ and Mg²⁺ of component 2 suggest the importance of dissolution of carbonate rocks in this aquifer system. From their characteristic loadings, the first two components are defined as the “salinity” and “hardness” components, respectively. Components 3–5 are related to more local and geological effects. The integration of the HCA and the PCA, with conventional classification of groundwater types, as well as with the hydrogeological and geological contexts, allowed the division of the region into four main geochemical areas, providing an improved regional picture of the aquifer system dynamics and hydrogeochemical evolution of groundwater. The following factors were recognized as influencing the evolution of groundwater identified in every geochemical area: (1) geological characteristics including sedimentary rock type and till mineralogy; (2) hydrogeological characteristics represented by the level of confinement and the hydraulic gradient; and (3) the geological history including the latest glaciation and the Champlain Sea invasion. With its integrated approach, this hydrogeochemical study contributes to the characterization and understanding of complex groundwater flow systems, and provides an example of the long-term geochemical evolution of hydrogeological systems after a major perturbation, in this case seawater invasion.     

Water-rock interactions drive chemostasis

The western U.S. is experiencing shifts in recharge due to climate change, and it is currently unclear how hydrologic shifts will impact geochemical weathering and stream concentration–discharge (C–Q) patterns. Hydrologists often use C–Q analyses to assess feedbacks between stream discharge and geochemistry, given abundant stream discharge and chemistry data. Chemostasis is commonly observed, indicating that geochemical controls, rather than changes in discharge, are shaping stream C–Q patterns. However, few C–Q studies investigate how geochemical reactions evolve along groundwater flowpaths before groundwater contributes to streamflow, resulting in potential omission of important C–Q controls such as coupled mineral dissolution and clay precipitation and subsequent cation exchange. Here, we use field observations—including groundwater age, stream discharge, and stream and groundwater chemistry—to analyse C–Q relations in the Manitou Experimental Forest in the Colorado Front Range, USA, a site where chemostasis is observed. We combine field data with laboratory analyses of whole rock and clay x-ray diffraction and soil cation-extraction experiments to investigate the role that clays play in influencing stream chemistry. We use Geochemist's Workbench to identify geochemical reactions driving stream chemistry and subsequently suggest how climate change will impact stream C–Q trends. We show that as groundwater age increases, C–Q slope and stream solute response are not impacted. Instead, primary mineral dissolution and subsequent clay precipitation drive strong chemostasis for silica and aluminium and enable cation exchange that buffers calcium and magnesium concentrations, leading to weak chemostatic behaviour for divalent cations. The influence of clays on stream C–Q highlights the importance of delineating geochemical controls along flowpaths, as upgradient mineral dissolution and clay precipitation enable downgradient cation exchange. Our results suggest that geochemical reactions will not be impacted by future decreasing flows, and thus where chemostasis currently exists, it will continue to persist despite changes in recharge.     

Quasi-Saturated Layer: Implications for Estimating Recharge and Groundwater Modeling

This study presents an extension of the concept of “quasi-saturation” to a quasi-saturated layer, defined as the uppermost dynamic portion of the saturated zone subject to water table fluctuations. Entrapped air here may cause substantial reductions in the hydraulic conductivity (K) and fillable pore water. Air entrapment is caused by a rising water table, usually as a result of groundwater recharge. The most significant effects of entrapped air are recharge overestimation based on methods that use specific yield (S_y), such as the water table fluctuation method (WTF), and reductions in K values. These effects impact estimation of fluid flow velocities and contaminant migration rates in groundwater. In order to quantify actual groundwater recharge rates and the effects of entrapped air, numerical simulations with the FEFLOW (Version 7.0) groundwater flow model were carried out using a quasi-saturated layer for a pilot area in Rio Claro, Brazil. The calculated recharge rate represented 16% of the average precipitation over an 8-year period, approximately half of estimates using the WTF method. Air entrapment amounted to a fillable porosity of 0.07, significant lower that the value of 0.17 obtained experimentally for S_y. Numerical results showed that the entrapped air volume in the quasi-saturated layer can be very significant (0.58 of the air fraction) and hence can significantly affect estimates of groundwater recharge and groundwater flow rates near the water table.     

Field investigation of the groundwater contribution to baseflow in an urban stream from a Quaternary aquifer with a leaky base

Groundwater contributions to baseflow in Minnehaha Creek, a creek located in a highly developed watershed in the Minneapolis-St. Paul metropolitan area, from the watershed's Quaternary aquifer were quantified as part of an effort to manage low flow conditions in the creek. Considerable uncertainty exists with any single method used to quantify groundwater contributions to baseflow; therefore, a “weight of evidence” approach in which methods spanning multiple spatial scales was utilized. Analyses conducted at the watershed-scale (streamflow separation and stable isotope analyses) were corroborated with site-scale measurements (piezometer, seepage meter, and streambed temperature profiles) over a multi-year period to understand processes and conditions controlling connectivity between the stream, its shallow aquifer system and other flow sources. In the case of Minnehaha Creek, groundwater discharge was found to range from 6.2 to 23 mm year⁻¹, which represented only 5 to 11% of annual streamflow during the study period. From the weight of evidence, it is conjectured that regional-scale hydrogeological conditions control groundwater discharge in Minnehaha Creek. Implications of these results with regard to possible augmentation of baseflow by increasing groundwater recharge with infiltration of stormwater are discussed.     

Hydrochemical and isotopic characterization of groundwater in the southeastern part of the Plateaux Region,Togo

Hydrochemical, inverse geochemical modelling and isotopic approaches are used to assess the hydrogeochemical evolution of groundwater from the basement aquifers in the southeastern part of the Plateaux Region, Togo. Groundwater originates from present-day rainwater infiltration and is mostly fresh and slightly acidic to neutral. Hydrochemical facies are predominantly mixed cations-HCO₃ associated with Ca/Mg-Cl, Na-HCO₃ and Na-Cl water types in equilibrium with kaolinite and Ca/Mg-smectites. They are related to silicates hydrolysis, anthropogenic contamination, nitrification/denitrification, mixing along flowpaths and dissolution/precipitation of secondary minerals. The pattern of flow paths is in accordance with an increasing trend in total dissolved solids (TDS) toward the potentiometric depression located in the central and southern parts of the aquifer system. Inverse geochemical modelling using the NETPATH-WIN model showed the relative importance of biotite, plagioclase and amphibole weathering and dissolution of secondary carbonate minerals along the flowpath, suggesting that an abundance of minerals is not necessarily the main factor controlling the groundwater chemistry evolution.     

Geochemistry and Provenance of Springs in a Baja California Sur Mountain Catchment

Fractured rock aquifers cover much of Earth's surface and are important mountain sites for groundwater recharge but are poorly understood. To investigate groundwater systematics of a fractured-dominated aquifer in Baja California Sur, Mexico, we examined the spatial patterns of aquifer recharge and connectivity using the geochemistry of springs. We evaluate a range of geochemical data within the context of two endmember hypotheses describing spatial recharge patterns and fracture connectivity. Hypothesis 1 is that the aquifer system is segmented, and springs are fed by local recharge. Hypothesis 2 is that the aquifer system is well connected, with dominant recharge occurring in the higher elevations. The study site is a small <15 km² catchment. Thirty-four distinct springs and two wells were identified in the study area, and 24 of these sites were sampled for geochemical analyses along an elevation gradient and canyon transect. These analyses included major ion composition, trace element and strontium isotopes, δ¹⁸O and δ²H isotopes, radiocarbon, and tritium. δ¹⁸O and δ²H isotopes suggest that the precipitation feeding the groundwater system has at least two distinct sources. Carbon isotopes showed a change along the canyon transect, suggesting that shorter flowpaths feed springs in the top of the transect, and longer flowpaths discharge near the bottom. Geochemical interpretations support a combination of the two proposed hypotheses. Understanding of the connectivity and provenance of these springs is significant as they are the primary source of water for the communities that inhabit this region and may be impacted by changes in recharge and use.     

Patterns of groundwater hydrochemistry in Apan-Tochac sub-basin,Mexico

Abstract

On the basis of the degree of mineralization, the groundwater of Apan-Tochac sub-basin may be considered as fresh (TDS < 500 ppm). However, chlorination is necessary to make it fit for human consumption. Major ion analyses of over 235 water samples reveal a striking relationship between hydrochemical evolution and the groundwater flow system. A high content of total dissolved solids, and low values of the Ca:Mg ratio are present in wells located on the plain (discharge zone), whereas opposite conditions are associated with wells located in higher regions (recharge zone). Statistical data analysis using the method of principal components allowed to differentiation of two hydrochemical families: (a) low mineralization corresponding to the recharge zone, and (b) high mineralization corresponding to the discharge zone. Waters of the Ca + Mg + HCO₃, and Na + Mg + HCO₃ hydrochemical fades are present and the former is dominant. The water is slightly alkaline, having slight problems of salinity during the year owing mainly to Ca²⁺HCO₃ ^? and Na⁺Cl^? salts. The hydrochemistry of the groundwater reflects the pattern of local groundwater flow for this sub-basin.     

Groundwater recharge in the Akaki catchment,central Ethiopia: evidence from environmental isotopes (δ18O, δ2H and 3H) and chloride mass balance

Recharge patterns, possible flow paths and the relative age of groundwater in the Akaki catchment in central Ethiopia have been investigated using stable environmental isotopes δ¹⁸O and δ²H and radioactive tritium (³H) coupled with conservative chloride measurements. Stable isotopic signatures are encoded in the groundwater solely from summer rainfall. Thus, groundwater recharge occurs predominantly in the summer months from late June to early September during the major Ethiopian rainy season. Winter recharge is lost through high evaporation–evapotranspiration within the unsaturated zone after relatively long dry periods of high accumulated soil moisture deficits. Chloride mass balance coupled with the isotope results demonstrates the presence of both preferential and piston flow groundwater recharge mechanisms. The stable and radioactive isotope measurements further revealed that groundwater in the Akaki catchment is found to be compartmentalized into zones. Groundwater mixing following the flow paths and topography is complicated by the lithologic complexity. An uncommon, highly depleted stable isotope and zero‐³H groundwater, observed in a nearly east–west stretch through the central sector of the catchment, is coincident with the Filwoha Fault zone. Here, deep circulating meteoric water has lost its isotopic content through exchange reactions with CO₂ originating at deeper sources or it has been recharged with precipitation from a different rainfall regime with a depleted isotopic content. Copyright © 2006 John Wiley & Sons, Ltd.     

A Geochemical Approach to Determine Sources and Movement of Saline Groundwater in a Coastal Aquifer

Geochemical evaluation of the sources and movement of saline groundwater in coastal aquifers can aid in the initial mapping of the subsurface when geological information is unavailable. Chloride concentrations of groundwater in a coastal aquifer near San Diego, California, range from about 57 to 39,400 mg/L. On the basis of relative proportions of major‐ions, the chemical composition is classified as Na‐Ca‐Cl‐SO₄, Na‐Cl, or Na‐Ca‐Cl type water. δ²H and δ¹⁸O values range from ?47.7‰ to ?12.8‰ and from ?7.0‰ to ?1.2‰, respectively. The isotopically depleted groundwater occurs in the deeper part of the coastal aquifer, and the isotopically enriched groundwater occurs in zones of sea water intrusion. ⁸⁷Sr/⁸⁶Sr ratios range from about 0.7050 to 0.7090, and differ between shallower and deeper flow paths in the coastal aquifer. ³H and ¹⁴C analyses indicate that most of the groundwater was recharged many thousands of years ago. The analysis of multiple chemical and isotopic tracers indicates that the sources and movement of saline groundwater in the San Diego coastal aquifer are dominated by: (1) recharge of local precipitation in relatively shallow parts of the flow system; (2) regional flow of recharge of higher‐elevation precipitation along deep flow paths that freshen a previously saline aquifer; and (3) intrusion of sea water that entered the aquifer primarily during premodern times. Two northwest‐to‐southeast trending sections show the spatial distribution of the different geochemical groups and suggest the subsurface in the coastal aquifer can be separated into two predominant hydrostratigraphic layers.     

Hydro-geochemical simulation for the evolution of groundwater quality in Yinchuan Plain,China

ABSTRACT

Water quality in the arid regions has long been an issue of great concern in the world. In this study, quantitative research was carried out to create new knowledge to understand the processes that determine the variation in the groundwater chemical composition of the Yinchuan Plain, China. In this context, the distribution and zonation characteristics of groundwater in this area were assessed using geochemical modelling of groundwater quality evolution. The results show the existence of an obvious zonation from the recharge area to the discharge area in the study area. Dominant anions transform from HCO₃ in the inclined pluvial area to HCO₃·SO₄·Cl in the discharge region, while the main cations vary from Ca and Mg to Na and Mg. The simulation results indicate that the evaporation process triggers 2–35% of groundwater loss, leading to an increase in the total dissolved solids. The irrigation leakage mixes with the groundwater at about 8:2, suggesting that the irrigation leakage dilutes the groundwater.     

Origin of sulphate in the unsaturated zone and groundwater of a loess aquifer

The use of the sulphate mass balance (SMB) between precipitation and soil water as a supplementary method to estimate the diffuse recharge rate assumes that the sulphate in soil water originated entirely from atmospheric deposition; however, the origin of sulphate in soil and groundwater is often unclear, especially in loess aquifers. This study analysed the sulphur (δ³⁴S-SO₄) and oxygen (δ¹⁸O-SO₄) isotopes of sulphate in precipitation, water-extractable soil water, and shallow groundwater samples and used these data along with hydrochemical data to determine the sources of sulphate in the thick unsaturated zone and groundwater of a loess aquifer. The results suggest that sulphate in groundwater mainly originated from old precipitation. When precipitation percolates through the unsaturated zone to recharge groundwater, sulphates were rarely dissolved due to the formation of CaCO₃ film on the surface of sulphate minerals. The water-extractable sulphate in the deep unsaturated zone (>10 m) was mainly derived from the dissolution of evaporite minerals and there was no oxidation of sulphide minerals during the extraction of soil water by elutriating soil samples with deionized water. The water-extractable concentration of SO₄ was not representative of the actual SO₄ concentration in mobile soil water. Therefore, the recharge rate cannot be estimated by the SMB method using the water-extractable concentration of SO₄ in the loess areas. This study is important for identifying sulphate sources and clarifying the proper method for estimating the recharge rate in loess aquifers.     

Characteristics of chemistry and stable isotopes in groundwater of Chaobai and Yongding River basin,North China Plain

To identify the groundwater flow system in the North China Plain, the chemical and stable isotopes of the groundwater and surface water were analysed along the Chaobai River and Yongding River basin. According to the field survey, the study area in the North China Plain was classified hydrogeologically into three parts: mountain, piedmont alluvial fan and lowland areas. The change of electrical conductance and pH values coincided with groundwater flow from mountain to lowland areas. The following groundwater types are recognized: Ca? HCO₃ and Ca? Mg? HCO₃ in mountain areas, Ca? Mg? HCO₃ and Na? K? HCO₃ in piedmont alluvial fan areas, and HCO₃? Na in lowland areas. The stable isotope distribution of groundwater in the study area also has a good corresponding relation with other chemical characteristics. Stable isotope signatures reveal a major recharge from precipitation and surface water in the mountain areas. Chemical and stable isotope analysis data suggest that mountain and piedmont alluvial fan areas were the major recharge zones and the lowland areas belong to the main discharge zone. Precipitation and surface water were the major sources for groundwater in the North China Plain. Stable isotopic enrichment of groundwater near the dam area in front of the piedmont alluvial fan areas shows that the dam water infiltrated to the ground after evaporation. As a result, from the stable isotope analysis, isotope value of groundwater tends to deplete from sea level (horizontal ground surface) to both top of the mountain and the bottom of the lowland areas in symmetrically. This suggests that groundwater in the study area is controlled by the altitude effect. Shallow groundwater in the study area belongs to the local flow system and deep groundwater part of the regional flow system. Copyright © 2007 John Wiley & Sons, Ltd.     

Application of geochemical tracers for the investigations of groundwater resources in semi-arid region (Central-East Tunisia)

Groundwater resources in Mahdia-Ksour Essef region, located in the central-eastern part of Tunisia, suffer from intensive exploitation and degradation of water quality. The assessment of groundwater vulnerability, the well-understanding of geochemical processes and the investigation of groundwater quality variations are of particular importance for water resources management in this semi-arid region. The results of this multi-disciplinary investigation show that groundwaters of Mahdia-Ksour Essef region are flowing from El Jem and Boumerdes regions in the South, towards the Mediterranean Sea and the sebkha of Moknine in the North. The groundwaters are classified as either Na-Cl or Ca-SO₄. Stable oxygen and hydrogen isotope compositions (δ¹⁸O and δ²H) confirm a recharge by rapid water infiltration, evaporate surface water and water-rock interaction processes in the salinity increase. The rock-water interaction processes of the mineralization of groundwaters include the cation-exchange reactions and the dissolution of carbonates and evaporate. The high values of the water quality index (WQI) and of the total dissolved solids (TDS) (3.7–11 g/L) of these groundwaters indicate their unsuitability for drinking purpose. Moreover, the combination of the WQI, TDS and nitrate results prove the vulnerability of the studied groundwater to the anthropogenic pollution linked to agriculture and domestic activities and to the salt water contamination.     

Hydrological and isotopic characterization of river water,groundwater, and groundwater recharge in the Heihe River basin,northwestern China

We used hydrochemistry and environmental isotope data (δ¹⁸O, δD, tritium, and ¹⁴C) to investigate the characteristics of river water, groundwater, and groundwater recharge in China's Heihe River basin. The river water and groundwater could be characterized as Ca²⁺? Mg²⁺? HCO₃^?? SO₄^2? and Na⁺? Mg²⁺? SO₄^2?? Cl^? types, respectively. Hydrogeochemical modelling using PHREEQC software revealed that the main hydrogeochemical processes are dissolution (except for gypsum and anhydrite) along groundwater flow paths from the upper to middle Heihe reaches. Towards the lower reaches, dolomite and calcite tend to precipitate. The isotopic data for most of the river water and groundwater lie on the global meteoric water line (GMWL) or between the GMWL and the meteoric water line in northwestern China, indicating weak evaporation. No direct relationship existed between recharge and discharge of groundwater in the middle and lower reaches based on the isotope ratios, d‐excess, and ¹⁴C values. On the basis of tritium in precipitation and by adopting an exponential piston‐flow model, we evaluated the mean residence time of shallow groundwater with high tritium activities, which was around 50 years (a). Furthermore, based on the several popular models, it is calculated that the deep groundwaters in piedmont alluvial fan zone of the middle reaches and in southern part of the lower reaches are modern water, whereas the deep groundwaters in the edge of the middle reaches and around Juyan Lake in the lower reaches of Heihe river basin are old water. Copyright © 2010 John Wiley & Sons, Ltd.     

Using multivariate statistical techniques and geochemical modelling to identify factors controlling the evolution of groundwater chemistry in a typical transitional area between Taihang Mountains and North China Plain

Identifying the key factors controlling groundwater chemical evolution in mountain-plain transitional areas is crucial for the security of groundwater resources in both headwater basins and downstream plains. In this study, multivariate statistical techniques and geochemical modelling were used to analyse the groundwater chemical data from a typical headwater basin of the North China Plain. Groundwater samples were divided into three groups, which evolved from Group A with low mineralized Ca-HCO₃ water, through Group B with moderate mineralized Ca-SO₄-HCO₃ water, to Group C with highly saline Ca-SO₄ and Ca-Cl water. Water-rock interaction and nitrate contamination were mainly responsible for the variation in groundwater chemistry. Groundwater chemical compositions in Group A were mainly influenced by dissolution of carbonates and cation exchange, and suffered less nitrate contamination, closely relating to their locations in woodland and grassland with less pronounced human interference. Chemical evolution of groundwater in Groups B and C was gradually predominated by the dissolution of evaporites, reverse ion exchange, and anthropogenic factors. Additionally, the results of the inverse geochemical model showed that dedolomitization caused by gypsum dissolution, played a key role in the geochemical evolution from Group A to Group B. Heavy nitrate enrichment in most groundwater samples of Groups B and C was closely associated with the land-use patterns of farmland and residential areas. Apart from the high loads of chemical fertilizers in irrigation return flow as the main source for nitrate contamination, the stagnant zones, flood irrigation pattern, mine drainage, and groundwater-exploitation reduction program were also important contributors for such high mineralization and heavy NO₃⁻ contents in Group C. The important findings of this work not only provide the conceptual framework for the headwater basin but also have important implications for sustainable management of groundwater resources in other headwater basins of the North China Plain.     

Application of geochemical and stable isotopic tracers to investigate groundwater salinity in the Ochi-Narkwa Basin,Ghana

Rainwater, groundwater and soil-water samples were analysed to assess groundwater geochemistry and the origin of salinity in the Ochi-Narkwa basin of the Central Region of Ghana. The samples were measured for major ions and stable isotopes (δ¹⁸O, δ²H and δ¹³C). The Cl^? content in rainwater decreased with distance from the coast. The major hydrochemical facies were Na-Cl for the shallow groundwaters and Ca-Mg-HCO₃, Na-Cl and Ca-Mg-Cl-SO₄ for the deep groundwaters. Groundwater salinization is caused largely by halite dissolution and to a minor extent by silicate weathering and seawater intrusion. Stable isotope composition of the groundwaters followed a slope of 3.44, suggesting a mixing line. Chloride profiles in the soil zone revealed the existence of salt crusts, which support halite dissolution in the study area. A conceptual flow model developed to explain the mechanism of salinization showed principal groundwater flow in the NW–SE direction.

EDITOR D. Koutsoyiannis

ASSOCIATE EDITOR K. Heal