Carbonate and carbon isotopic evolution of groundwater contaminated by produced water brine with hydrocarbons

The major ionic and dissolved inorganic carbon (DIC) concentrations and the stable carbon isotope composition of DIC (δ¹³C_DIC) were measured in a freshwater aquifer contaminated by produced water brine with petroleum hydrocarbons. Our aim was to determine the effects of produced water brine contamination on the carbonate evolution of groundwater. The groundwater was characterized by three distinct anion facies: HCO₃⁻-rich, SO₄²⁻-rich and Cl⁻-rich. The HCO₃⁻-rich groundwater is undergoing closed system carbonate evolution from soil CO_2(g) and weathering of aquifer carbonates. The SO₄²⁻-rich groundwater evolves from gypsum induced dedolomitization and pyrite oxidation. The Cl⁻-rich groundwater is contaminated by produced water brine and undergoes common ion induced carbonate precipitation. The δ¹³C_DIC of the HCO₃⁻-rich groundwater was controlled by nearly equal contribution of carbon from soil CO_2(g) and the aquifer carbonates, such that the δ¹³C of carbon added to the groundwater was −11.6‰. In the SO₄²⁻-rich groundwater, gypsum induced dedolomitization increased the ¹³C such that the δ¹³C of carbon added to the groundwater was −9.4‰. In the produced water brine contaminated Cl⁻-rich groundwater, common ion induced precipitation of calcite depleted the ¹³C such that the δ¹³C of carbon added to the groundwater was −12.7‰. The results of this study demonstrate that produced water brine contamination of fresh groundwater in carbonate aquifers alters the carbonate and carbon isotopic evolution.     

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

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

Assessing groundwater availability and the response of the groundwater system to intensive exploitation in the North China Plain by analysis of long-term isotopic tracer data

The use of isotope tracers as a tool for assessing aquifer responses to intensive exploitation is demonstrated and used to attain a better understanding of the sustainability of intensively exploited aquifers in the North China Plain. Eleven well sites were selected that have long-term (years 1985–2014) analysis data of isotopic tracers. The stable isotopes δ¹⁸O and δ²H and hydrochemistry were used to understand the hydrodynamic responses of the aquifer system, including unconfined and confined aquifers, to groundwater abstraction. The time series data of ¹⁴C activity were also used to assess groundwater age, thereby contributing to an understanding of groundwater sustainability and aquifer depletion. Enrichment of the heavy oxygen isotope (¹⁸O) and elevated concentrations of chloride, sulfate, and nitrate were found in groundwater abstracted from the unconfined aquifer, which suggests that intensive exploitation might induce the potential for aquifer contamination. The time series data of ¹⁴C activity showed an increase of groundwater age with exploitation of the confined parts of the aquifer system, which indicates that a larger fraction of old water has been exploited over time, and that the groundwater from the deep aquifer has been mined. The current water demand exceeds the sustainable production capabilities of the aquifer system in the North China Plain. Some measures must be taken to ensure major cuts in groundwater withdrawals from the aquifers after a long period of depletion.     

Different isotopic evolutionary trends of δ34S and δ18O compositions of dissolved sulfate in an anaerobic deltaic aquifer system

Concentration and isotope ratios (δ³⁴S_SO4 and δ¹⁸O_SO4) of dissolved sulfate of groundwater were analyzed in a very large anaerobic aquifer system under the Lower Central Plain (LCP) (25,000 km²) in Thailand. Groundwater samples were collected in two different kinds of aquifers; type 1 with a saline water contribution and type 2 lateritic aquifers with no saline water contribution. Two different isotopic compositional trends were observed: in type 1 aquifers sulfate isotope ratios range from low values (+2.2‰ for δ³⁴S_SO4 and +8.0‰ for δ¹⁸O_SO4) to high values (+49.9‰ for δ³⁴S_SO4 and +17.9‰ for δ¹⁸O_SO4); in type 2 aquifers sulfate isotope ratios range from low values (−0.1‰ for δ³⁴S_SO4 and +12.2‰ for δ¹⁸O_SO4) to high δ¹⁸O_SO4 ratios (+18.4‰) but with low δ³⁴S_SO4 ratios (<+12.9‰). Isotopic comparison with possible source materials and theoretical geochemical models suggests that the sulfate isotope variation for type 1 aquifer groundwater can be explained by two main processes. One is the contribution of remnant seawater, which has experienced dissimilatory sulfate reduction in the marine clay, into recharge water of freshwater origin. This process accounts for the high salinity groundwater. The other process, explaining for the modest salinity groundwater, is the bacterial sulfate reduction of the mixture water between high salinity water and fresh groundwater. Isotopic variation of type 2 aquifer groundwater may also be explained by bacterial sulfate reduction, with slower reduction rate than that of the groundwater with saline water effect. The origin of groundwater sulfate with low δ³⁴S_SO4 but high δ¹⁸O_SO4 is recognized as an important topic to be examined in a future investigation.     

Isotope Geochemistry of Groundwater from Fractured Dolomite Aquifers in Central Slovenia

The hydrogeochemistry and isotope geochemistry of groundwater from 85 wells in fractured dolomite aquifers of Central Slovenia were investigated. This groundwater represents waters strongly influenced by chemical weathering of dolomite with an average of δ¹³C_CARB value of +2.2 ‰. The major groundwater geochemical composition is HCO₃ ^? > Ca²⁺ > Mg²⁺. Several differences in hydrogeochemical properties among the classes of dolomites were observed when they were divided based on their age and sedimentological properties, with a clear distinction of pure dolomites exhibiting high Mg²⁺/Ca²⁺ ratios and low Na⁺, K⁺ and Si values. Trace element and nutrient concentrations (SO₄ ^2?, NO₃ ^?) were low, implying that karstic and fractured dolomite aquifers are of good quality to be used as tap water. Groundwater was generally slightly oversaturated with respect to calcite and dolomite, and dissolved CO₂ was up to 46 times supersaturated relative to the atmosphere. The isotopic composition of oxygen (δ¹⁸O_H2O), hydrogen (δD_H2O) and tritium ranged from ?10.3 to ?8.4 ‰, from ?68.5 to ?52.7 ‰ and from 3.5 TU to 10.5 TU, respectively. δ¹⁸O and δD values fell between the GMWL (Global Meteoric Water Line) and the MMWL (Mediterranean Meteoric Water Line) and indicate recharge from precipitation with little evaporation. The tritium activity in groundwater suggests that groundwater is generally younger than 50 years. δ¹³C_DIC values ranged from ?14.6 to ?9.3 ‰ and indicated groundwater with a contribution of degraded organic matter/dissolved inorganic carbon in the aquifer. The mass balances for groundwater interacting with carbonate rocks suggested that carbonate dissolution contributes from 43.7 to 65.4 % and degradation of organic matter from 34.6 to 56.3 %.     

Distribution of δ~(34)S and δ~(18)O in SO_4~(2-) in Groundwater from the Ordos Cretaceous Groundwater Basin and Geological Implications

<正>The Ordos Cretaceous Groundwater Basin,located in an arid-semiarid area in northwestern China,is a large-style groundwater basin.SO_4~(2-) is one of the major harmful components in groundwater.Dissolved SO_4~(2-) concentrations,andδ~(34)S-SO_4~(2-) andδ~(18)O-SO_4~(2-) in groundwater from 14 boreholes and in gypsum from aquifer were analyzed.Results show that SO_4~(2-) in shallow groundwaters originates from precipitation,sulfide oxidation,and dissolution of stratum sulphate,with a big range ofδ~(34)S values,from-10.7‰to 9.2‰,and addition of SO_4~(2-) in deep groundwater results from dissolution of stratum sulphate,with biggerδ~(34)S values,from 7.8‰to 18.5‰,compared with those in shallow groundwater.This research also indicates that three types of sulphate are present in the strata,and characterized by highδ~(34)S values and highδ~(18)O values-style,highδ~(34)S values and middleδ~(18)O valuesstyle, middleδ~(34)S values and lowδ~(18)O values-style,respectively.Theδ~(34)S-SO_4~(2-) andδ~(18)O-SO_4~(2-) in groundwater have a good perspective for application in distinguishing different groundwater systems and determining groundwater circulation and evolution in this area.     

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.     

Hydrogeochemistry and groundwater quality assessment of the multilayered aquifer in Lower Kelantan Basin,Kelantan, Malaysia

Continual expansion of population density, urbanization, agriculture, and industry in most parts of the world has increased the generation of pollution, which contributes to the deterioration of surface water quality. This causes the dependence on groundwater sources for their daily needs to accumulate day by day, which raises concerns about their quality and hydrogeochemistry. This study was carried out to increase understanding of the geological setup and assess the groundwater hydrogeochemical characteristics of the multilayered aquifers in Lower Kelantan Basin. Based on lithological data correlation of exploration wells, the study area can be divided into three main aquifers: shallow, intermediate and deep aquifers. From these three aquifers, 101 groundwater samples were collected and analyzed for various parameters. The results showed that pH values in the shallow, intermediate and deep aquifers were generally acidic to slightly alkaline. The sequences of major cations and anions were Na⁺ > Ca²⁺ > Mg²⁺ > K⁺ and HCO₃^? > Cl^? > SO₄^2? > CO₃^2?, respectively. In the intermediate aquifer, the influence of ancient seawater was the primary factor that contributed to the elevated values of electrical conductivity (EC), Cl^? and total dissolved solids (TDS). The main facies in the shallow aquifer were Ca–HCO₃ and Na–HCO₃ water types. The water types were dominated by Na–Cl and Na–HCO₃ in the intermediate aquifer and by Na–HCO₃ in the deep aquifer. The Gibbs diagram reveals that the majority of groundwater samples belonged to the deep aquifer and fell in the rock dominance zone. Shallow aquifer samples mostly fell in the rainfall zone, suggesting that this aquifer is affected by anthropogenic activities. In contrast, the results suggest that the deep aquifer is heavily influenced by natural processes.     

Redox processes in the Oderbruch polder groundwater flow system in Germany

Large scale redox processes were investigated in a river recharged aquifer in the Oderbruch polder alongside the river Oder in north-eastern Germany. Major hydraulic and hydrochemical processes were identified qualitatively. As a result of intensive drainage activities in the past 250 a, the groundwater level within the polder is situated below the river water level and a levee prevents flooding of the lowland. As a consequence, river water permanently infiltrates into the shallow confined aquifer. A sequence of redox reactions, driven by organic matter degradation, can be observed during infiltration of oxic river water into the groundwater. Up to 3 km from the river, reduction processes from O₂ respiration to SO²⁻₄ reduction dominate the groundwater chemistry. While reduction of Fe- and Mn(hydr)oxides is the source of the high amounts of dissolved Fe²⁺ and Mn²⁺, carbonate dissolution/precipitation reactions control the actual groundwater concentration of Mn²⁺. The first order rate constant for SO²⁻₄ reduction was found to be −0.0169 a⁻¹. Fe²⁺ is released into the groundwater at a rate of 0.0033 mmol l⁻¹ a⁻¹. The groundwater chemistry is strongly linked to the hydraulic conditions. Near the river, the groundwater is confined and recharged by bank-filtration only. In contrast, in the central polder the groundwater is unconfined and percolation of rainwater through the dried loam is possible because of texture changes such as shrinkage fissures. Geogenic pyrite present within the alluvial loam is oxidised and large amounts of SO²⁻₄ are released into the groundwater.     

Nitrate distribution and potential attenuation mechanisms of a municipal water supply bedrock aquifer

The Silurian bedrock aquifer constitutes a major aquifer system for groundwater supply across the Ontario province in Canada. The application of natural and industrial fertilizers near urban centers has led to groundwater NO₃⁻-N concentrations that sometimes have exceeded the drinking water limit, posing a threat to the usage of groundwater for the human consumption. Therefore, there is a growing interest and concern about how nitrate is being leached, transported and potentially attenuated in bedrock aquifers. This study assesses the local distribution of groundwater NO₃⁻ in the up-gradient area of two historically impacted municipal wells, called Carter Wells, in the City of Guelph, Canada, in order to evaluate the potential nitrate attenuation mechanisms, using both groundwater geochemical and isotopic analysis (³H, δ¹⁵N-NO₃, δ¹⁸O-NO₃, δ¹⁸O-SO₄, δ³⁴S-SO₄) and a detailed vertical hydrogeological and geochemical bedrock characterization. The results indicate that probably the main source of nitrate to the Carter Wells is the up-gradient Arkell Research Station (ARS), an agricultural research facility where manure has been historically applied. The overburden and bedrock groundwater with high NO₃ concentrations at the ARS exhibits a manure-related δ¹⁵N and δ¹⁸O signature, isotopically similar to the high nitrate in the down-gradient groundwater from domestic wells and from the Carter Wells. The nitrate spatial distribution appears to be influenced and controlled by the geology, in which more permeable rock is found in the Guelph Formation which in turn is related to most of the high NO₃⁻ groundwater. The presence of an underlying low permeability Eramosa Formation favors the development of oxygen-depleted conditions, a key factor for the occurrence of denitrification. Groundwater with low NO₃⁻-N concentrations associated with more oxygen-limited conditions and coincident with high SO₄²⁻ concentrations are related to more enriched δ¹⁵N and δ¹⁸O values in NO₃⁻ and to more depleted δ³⁴S and δ¹⁸O values in SO₄²⁻, suggesting that denitrification coupled with pyrite oxidation is taking place. The presence of macro crystalized and disseminated pyrite especially in the Eramosa Formation, can support the occurrence of this attenuation process. Moreover, based on tritium analysis, some denitrification can occur in shallow bedrock and within relatively short residence times, associated with less permeable conditions in depth which facilitates oxygen consumption through sulfide oxidation. The role of denitrification mediated by organic carbon cannot be discarded at the study site. This study suggests that the geological configuration and particularly the presence of low permeability Eramosa Formation can play an important role on nitrate natural attenuation, which may serve as a decision factor on defining the bedrock water supply system for both domestic and municipal purposes.     

Hydrogeochemical evaluation of fractured Limestone aquifer by applying a geochemical model in eastern Nile Valley,Egypt

Rock water interactions play an important role in the flow of groundwater. Groundwater samples were collected from deep production wells with depths ranging from 120 to 230 m. Complete chemical analysis of 40 groundwater samples was collected from the fractured limestone aquifer including major cations (Na⁺, K⁺, Ca²⁺, Mg²⁺) and major anions (Cl^?, SO₄ ^2?, HCO₃ ^?, CO₃ ^2?). A geochemical modeling (NETPATH Software) was applied for environmental simulate net geochemical mass-balance reactions between initial and final waters along a hydrologic flow path. This program simulates selected evolutionary waters for every possible combination of the plausible phases that account for the composition of a selected set of chemical constraints in the system. The groundwater of the Eocene aquifer mainly belongs to fairly fresh water with salinity contents ranging from 228 to 3595 ppm. The measured groundwater levels range between 8 and 25 m near the river Nile to the limestone plateau (eastwards). Consequently, groundwater flows from east to westward toward the river Nile. Groundwater aquifer in the study area is mainly composed of fractured limestone; the saturated states of the PCO₂, calcite, aragonite, dolomite, siderite, gypsum, anhydrite, hematite, and goethite in addition to H₂ gas were estimated. The undersaturated state of carbon dioxide reflects closed conditions and very low probability of recent recharge, and it reveals also the high tendency of water to precipitates carbonate species. Undersaturation by carbonate minerals is only restricted to some pockets distributed on the different places of the aquifer in the study area. The majority of groundwater samples of Eocene aquifer in the study area indicated that groundwater is not suitable for irrigation with treatment and requires good drainage.     

Origin of groundwater salinity in the Fasa Plain,southern Iran,hydrogeochemical and isotopic approaches

The study area, the Fasa Plain, is situated in the semiarid region of Fars Province in the south of Iran. The Salloo diapir is a salt dome that crops out in the northwest of the study area. Isotopic and hydrochemical analyses were used to examine the water and how the origin of salinity and the diapir affect the quality of the groundwater quality in the study area. Groundwater was sampled from 31 representative pumping wells in alluvial aquifer and five springs in order to measure their stable isotope compositions, bromide ion concentration, and physical and chemical parameters. The alluvial aquifer was organized into two main groups based on the chemistry, with Group 1 consisting of low-salinity well samples (544–1744 µS/cm) with water type Ca–Mg–HCO₃–SO₄ which were taken in the center and north of the area, and Group 2 consisting of high-salinity samples (2550–4620 µS/cm) with water type Ca–Mg–Cl–SO₄ which were taken from the wells in the south and southwest of the area. A saline spring near the salt dome with an EC of 10,280 µS/cm has water type Na–Cl, while the compositions of the water in the other karstic springs is comparable to the fresh groundwater samples. All groundwater samples are undersaturated with respect to gypsum, anhydrite, and halite and are supersaturated with respect to calcite and dolomite. Stable isotopes (δ¹⁸O and δ²H) differentiated four water types: saline springs, freshwater spring, fresh groundwater, and saline groundwater. The results indicate that meteoric water is the main origin of these water resources. Halite dissolution from the salt dome was identified as the origin of salinity. The Na/Cl and Cl/Br ratios confirmed the results. Groundwater compositions in the southwestern part of the area are affected by the intrusion of saltwater from the salt dome. The average saltwater fraction in the some water wells is about 0.2%. In the south and southwestern part of the area, the saltwater fraction is positive in mixed freshwater/saltwater (Group 2). Different processes interact together to change the hydrochemical properties of Fasa’s alluvial aquifer. The main processes that occur in the aquifer are mixing, gypsum dissolution, and calcite precipitation.     

Multivariate statistical analysis of chemical and stable isotopic data as indicative of groundwater evolution with reduced exploitation

Groundwater resources in the North China Plain (NCP) are undergoing tremendous changes in response to the operation of groundwater exploitation reduction (GWER) project. To identify groundwater evolution in this complex context, hierarchical cluster analysis (HCA) and principal component analysis (PCA) were combined to interpret an integrated dataset of stable isotopes and chemical data from four sampling campaigns in a pilot area of groundwater control. We proposed a novel HCA approach integrating stable isotopes and chemical signals, which successfully partitioned the groundwater samples into the unconfined and the confined water samples. Stable isotopic evidence showed that the lateral inflow and the surface water may contribute more to groundwater recharge in this region than local modern precipitation. The unconfined water’s main hydrochemical types were Na type with mixed anions, and Na–Cl–SO₄ type, while the confined water was mainly Na–Cl and Na–SO₄ types. Geochemical processes mainly involved the dissolution/precipitation of halite, gypsum, Glauber's salt, feldspar, calcite and dolomite, as well as the cation exchange. PCA results showed that water–rock interaction (i.e., salinity-based and alkalinity-based processes) predominated the hydrochemical evolution, along with local nitrate contamination resulting from fertilizers and domestic sewage. The GWER project regulated the natural evolution of unconfined water chemistry, and significantly reduced the unconfined water’s salinity (mainly Na⁺, Mg²⁺, SO₄^2?). This may be attributed to upward leakage from low-salinity confined water at some parts of the aquifer. Additionally, insignificant changes in the confined water’s salinity reflected that the impact of GWER on the confined aquifer was negligible. This study facilitates the groundwater classification effectively in the areas lack of geological data, and enhances the knowledge of groundwater chemical evolution in such a region where groundwater restoration is in progress, with important implications for groundwater sustainable management in similar basins worldwide.     

Identifying the recharge sources and age of groundwater in the Songnen Plain (Northeast China) using environmental isotopes

The recharge sources and groundwater age in the Songnen Plain, Northeast China, were confirmed using environmental isotopes. The isotopic signatures of the unconfined aquifers in the southeast elevated plain and the north and west piedmont, cluster along local meteoric water lines (LMWLs) with a slope of about 5. The signature of source water was obtained by the intersection of these LMWLs with the regional meteoric water line (RMWL). This finding provides evidence that the recharge water for these areas originate from the Changbai Mountains and the Low and High Hingan Mountains, respectively. Groundwater in the unconfined aquifer in the low plain yields a LMWL with a slope of 4.4; its nitrate concentration indicates the admixture of irrigation return flow. The δ-values of the unconfined aquifer in the east elevated plain plot along the RMWL, reflecting recharge by local precipitation. The mean residence time of groundwater in these aquifers is less than 50?years. However, the ¹⁴C age of the groundwater in the confined Quaternary aquifer ranges from modern to 19,500?years, and in the Tertiary confined aquifer from 3,100 to 24,900?years. Modern groundwater is mainly recharged to the Quaternary confined aquifer on the piedmont by local precipitation and lateral subsurface flow.     

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.     

Hydrogeochemical and isotopic evidences of the groundwater regime in Datong Basin, Northern China

Datong Basin is one of the Cenozoic faulted basins in Northern China’s Shanxi province, where groundwater is the major source of water supply. The results of hydrochemical investigation show that along the groundwater flow path, from the margins to the lower-lying central parts of the basin, groundwater generally shows increases in concentrations of TDS, HCO₃ ^?, SO₄ ^2?, Cl^?, Na⁺ and Mg²⁺ (except for Ca²⁺ content). Along the basin margin, groundwater is dominantly of Ca–HCO₃ type; however, in the central parts of the basin it becomes more saline with Na–HCO₃-dominant or mixed-ion type. The medium-deep groundwater has chemical compositions similar to those of shallow groundwater, except for the local area affected by human activity. From the mountain front to the basin area, shallow groundwater concentrations of major ions increase and are commonly higher than those in medium-deep aquifers, due to intense evapotranspiration and anthropogenic contamination. Hydrolysis of aluminosilicate and silicate minerals, cation exchange and evaporation are prevailing geochemical processes occurring in the aquifers at Datong Basin. The isotopic compositions indicate that meteoric water is the main source of groundwater recharge. Evaporation is the major way of discharge of shallow groundwater. The groundwater in medium-deep aquifers may be related to regional recharges of rainwater by infiltrating along the mountain front faults, and of groundwater permeating laterally from bedrocks of the mountain range. However, in areas of groundwater depression cones, groundwater in the deep confined aquifers may be recharged by groundwater from the upper unconfined aquifer through aquitards.     

Hydrochemical indications of human impact on karst groundwater in a subtropical karst area,Chongqing, China

The application of combined isotopic and hydrochemical compositions may be useful for evaluating water quality problems in karst aquifers in which it is difficult to distinguish the sources of solutes from the natural background of those due to human activities. Multiple isotopes (δ¹³C–DIC, δ³⁴S–SO₄ ^2?) and chemical parameters were measured in rainwater, groundwater and sewage in order to elucidate the solute sources and impacts from human activities and natural background in the Laolongdong karst catchment in Chongqing Municipality, SW China. Overall, the dissolution of carbonate rock controls Ca²⁺, Mg²⁺ and HCO₃ ^? content in rainwater and karst groundwater. SO₄ ^2? originated mainly from gypsum dissolution in karst groundwater. Carbonate rocks in the studied site could be dissolved jointly by H₂CO₃ from the natural CO₂–H₂O reaction and other acids (organic acids and HNO₃) from sewage and soils. Sewage discharge from urban areas and agriculture activities lead to the increase of NO₃ ^?, PO₄ ^3? and Cl^? in karst groundwater. To protect and sustainably utilize the karst aquifer, sewage originating from urban areas must be controlled and treated and the use of fertilizer should be limited.     

Distribution of terminal electron-accepting processes in an aquifer having multiple contaminant sources

Concentrations of electron acceptors, electron donors, and H₂ in groundwater were measured to determine the distribution of terminal electron-accepting processes (TEAPs) in an alluvial aquifer having multiple contaminant sources. Upgradient contaminant sources included two separate hydrocarbon point sources, one of which contained the fuel oxygenate methyl tertbutyl ether (MTBE). Infiltrating river water was a source of dissolved NO₃, SO₄ and organic carbon (DOC) to the downgradient part of the aquifer. Groundwater downgradient from the MTBE source had larger concentrations of electron acceptors (dissolved O₂ and SO₄) and smaller concentrations of TEAP end products (dissolved inorganic C, Fe²⁺ and CH₄) than groundwater downgradient from the other hydrocarbon source, suggesting that MTBE was not as suitable for supporting TEAPs as the other hydrocarbons. Measurements of dissolved H₂ indicated that SO₄ reduction predominated in the aquifer during a period of high water levels in the aquifer and river. The predominant TEAP shifted to Fe³⁺ reduction in upgradient areas after water levels receded but remained SO₄ reducing downgradient near the river. This distribution of TEAPs is the opposite of what is commonly observed in aquifers having a single contaminant point source and probably reflects the input of DOC and SO₄ to the aquifer from the river. Results of this study indicate that the distribution of TEAPs in aquifers having multiple contaminant sources depends on the composition and location of the contaminants and on the availability of electron acceptors.     

Hydrogeochemical Analysis of Processes Through Modeling of Seawater Intrusion Impacts in Biscayne Aquifer Water Quality,USA

Hydrogeochemical processes that accompany seawater intrusion in coastal aquifers can alter the resulting water quality and are important ingredients in coastal aquifer management. The presence of dissolution–precipitation reactions and ion exchange in the mixing zone of the Biscayne aquifer (FL, USA) are suggested based on changes in major ion concentrations and mineral saturation indices (SI). Major ion concentrations from 11 groundwater samples are compared with theoretical mixing between freshwater and seawater. PHREEQC code was used to calculate saturation indices of the samples with respect to common phases in the Biscayne aquifer. High Ca²⁺ and HCO₃ ^? content of the samples is typical of waters in contact with carbonate aquifers. Water quality of the samples is mainly attributed to mixing and precipitation–dissolution reactions with calcite and dolomite. The samples were saturated with calcite (SI ~ 0) and undersaturated for dolomite (SI < 0), while a few samples showed dolomite saturation. Because gypsum and halite SI could be predicted by theoretical mixing, reactions with those minerals, if present, are thought to be insignificant. In the active intrusion areas, cation exchange also appears to modify water quality leading to excess Ca²⁺, but depleted Na⁺, Mg²⁺ and K⁺ concentrations. On the other hand, samples from previous intrusion areas plotted very close to the theoretical mixing line and approached equilibrium with the seawater.     

Degradation of groundwater quality in coastal aquifer of Sabratah area,NW Libya

Overextraction of groundwater is widely occurring along the coast where good quality groundwater is at risk, due to urbanization, tourist development and intensive agriculture. The Sabratah area at the northern central part of Jifarah Plain, Northwest Libya, is a typical area where the contamination of the aquifer in the form of saltwater intrusion, gypsum/anhydrite dissolution and high nitrate concentrations is very developed. Fifty groundwater samples were collected from the study area and analysed for certain parameters that indicate salinization and pollution of the aquifer. The results demonstrate high values of the parameters electrical conductivity, sodium, potassium, magnesium, chloride and sulphate which can be attributed to seawater intrusion. The intensive extraction of groundwater from the aquifer reduces freshwater outflow to the sea, creates drawdown cones and lowering of the water table to as much as 30 m below mean sea level. Irrigation with nitrogen fertilizers and domestic sewage and movement of contaminants in areas of high hydraulic gradients within the drawdown cones probably are responsible for the high nitrate concentration towards the south of the region. Seawater intrusion and deep salt water upconing result in general high SO₄ ^2? concentrations in groundwater near the shoreline, where localized SO₄ ^2? anomalies are also due to the dissolution of sebkha deposits for few wells in the nearby sebkhas. Upstream, the increase in SO₄ ^2? concentrations in the south is ascribed to the dissolution of gypsum at depth in the upper aquifer.