A multi-isotope approach for understanding sources of water,carbon and sulfur in natural springs of the Central Appalachian region

Natural springs have been reliable sources of domestic water and have allowed for the development of recreational facilities and resorts in the Central Appalachians. The structural history of this area is complex and it is unknown whether these natural springs receive significant recharge from modern precipitation or whether they discharge old water recharged over geological times scales. The main objective of this study was to use stable isotopes of water ( $\delta^{18} {\text{O}}_{{{\text{H}}_{2} {\text{O}}}}$ and $\delta^{2} {\text{H}}_{{{\text{H}}_{2} {\text{O}}}}$ ), dissolved inorganic carbon ( $\delta^{13} {\text{C}}_{\text{DIC}}$ ) and dissolved sulfate ( $\delta^{34} {\text{S}}_{{{\text{SO}}_{4} }}$ and $\delta^{18} {\text{O}}_{{{\text{SO}}_{4} }}$ ) to delineate sources of water, carbon and sulfur in several natural springs of the region. Our preliminary isotope data indicate that all springs are being recharged by modern precipitation. The oxygen isotope composition indicates that waters in thermal springs did not encounter the high temperatures required for O isotope exchange between the water and silicate/carbonate minerals, and/or the residence time of water in the aquifers was short due to high flow rates. The carbon isotopic composition of dissolved inorganic carbon and sulfur/oxygen isotopic composition of dissolved sulfate provide evidence of low-temperature water–rock interactions and various biogeochemical transformations these waters have undergone along their flow path.     

Integrated geophysical, geochemical and hydrogeological investigation of shallow groundwater resources in parts of the Ikom-Mamfe Embayment and the adjoining areas in Cross River State, Nigeria

Information generated from geophysical, geochemical and hydrogeological data has been used in assessing the groundwater resource potential, quality and usability and in mapping flow directions within the shallow subsurface of the Mamfe Embayment, Cross River State, Nigeria. The electrical resistivity technique in which the Schlumberger’s vertical electrical sounding field procedure has been adopted was the geophysical method employed; lithology logs from drilling records, discharge rates, static water level information were the hydrogeological information utilized, while the geochemical techniques involve analyses of water samples. Apparent resistances were measured using different resistivity meters including OYO McOhm (model 2115), ABEM terrameter (SAS300B and SAS1000 models) and IGIS (SSP-ATS-MRP model) with maximum current electrode separation reaching 1 km in some communities. Geological information was used as control in the modelling and interpretation of all geophysical data. The physico-chemical parameters of the water samples from the different water sources in the area were determined using different analytical techniques and in some cases, by in situ direct measurement of some parameters. Measured values of electrical conductivity, static water level, available aquifer discharge information and calculated SAR and %Na were integrated into the geophysical and hydrogeological results. The shallow subsurface of the area is segmented into four hydrogeological provinces [crystalline basement province (CBP), Cross River Plain Province (CRPP), Nkporo-Afikpo Shales Province (NASP) and alluvial/buried river province (ABRP) with localized groundwater flow patterns]. Results indicated that the alluvial (discharge rate of 3.83 L/s), fractured sandstone (discharge rate of 2.43 L/s) and basement (discharge rate of 1.80 L/s) aquifers are more yielding than the aquifers in areas covered with deformed shales (discharge rate of 0.62 L/s) and siltstone aquifers (discharge rate of 0.97 L/s). The aquifer horizons are inhomogeneous and anisotropic with topography and lithology exerting significant influence on groundwater flow direction. However, there appears to be some high yielding aquifers at depths greater than 100 m in the CRPP areas although researches on their distribution are still ongoing. Precipitation is the major source of recharge and the water is enriched with Na⁺, K⁺, Ca²⁺, Mg²⁺, ${\text{HCO}}_{ 3}^{ - }$ , Cl^?, ${\text{SO}}_{ 4}^{2 - }$ and ${\text{NO}}_{ 3}^{ - }$ throughout the year. Graphical analyses of hydrochemical data using Piper and Stiff diagrams show that Ca–(Mg)–CO₃–HCO₃ is the dominant water facies. Results from EC, SAR and %Na show that the water is fresh and belongs to the good-to-excellent class and is, therefore, suitable for domestic, agricultural and industrial use.     

Appraisal of groundwater quality in a crystalline aquifer: a chemometric approach

The purpose of this study is to assess the groundwater quality and identify the processes that control the groundwater chemistry in a crystalline aquifer. A total of 72 groundwater samples were collected during pre- and post-monsoon seasons in the year 2014 in a semi-arid region of Gooty Mandal, Anantapur district, Andhra Pradesh, India. The study utilized chemometric analysis like basic statistics, Pearson’s correlation coefficient (r), principal component analysis (PCA), Gibbs ratio, and index of base exchange to understand the mechanism of controlling the groundwater chemistry in the study area. The results reveal that groundwater in the study area is neutral to slightly alkaline in nature. The order of dominance of cations is Na⁺ > Ca²⁺ > Mg²⁺ > K⁺ while for anions, it is \( {\mathrm{HCO}}_3^{-}>{\mathrm{Cl}}^{-} \)>\( {\mathrm{NO}}_3^{-} \)>\( {\mathrm{SO}}_4^{2-} \)>\( {\mathrm{CO}}_3^{2-}>{\mathrm{F}}^{-} \) in both seasons. Based on the Piper classification, most of the groundwater samples are identified as of sodium bicarbonate (\( {\mathrm{Na}}^{+}-{\mathrm{HCO}}_3^{-}\Big) \) type. According to the results of the principal component analysis (PCA), three factors and two factors were identified pre and post monsoon, respectively. The present study indicates that the groundwater chemistry is mostly controlled by geogenic processes (weathering, dissolution, and ion exchange) and some extent of anthropogenic activities.     

Hydrogeochemistry and isotope techniques to determine water interactions in groundwater-dependent shallow lakes,Wet Pampa Plain,Argentina

This paper gives an account of the implementation of hydrochemical and isotopic techniques to identify and explain the processes that govern solute exchange in two groundwater-dependent shallow lakes in the Southeastern Pampa Plain of Argentina. Water samples (lakes, streams, spring water and groundwater) for hydrochemical and stable isotopic determination were collected and the main physical–chemical parameters were measured. The combination of stable isotope data with hydrogeochemical techniques was used for the identification of sources and preferential recharge areas to these aquatic ecosystems which allowed the explanation of the lake water origin. The hydrochemical processes which explain Los Padres Lake water chemistry are evaporation from groundwater, CO₂ input, calcite dissolution, Na⁺ release by Ca²⁺ and Mg²⁺ exchange, and sulfate reduction. The model that best aligns with La Brava Lake hydrochemical constraints includes: mixing, CO₂ and calcite dissolution, cationic exchange with Na⁺ release and Mg²⁺ adsorption, and to a lesser extent, Ca/Na exchange. This model suggests that the fractured aquifer contribution to this water body is greater than 50 %. An isotopic-specific fingerprint for each lake was identified, finding a higher evaporation rate for La Brava Lake compared to Los Padres Lake. Isotopic data demonstrate the importance of these shallow lakes as recharge areas to the regional aquifer, becoming areas of high groundwater vulnerability. The Tandilia Range System, considered in many hydrogeological studies as the impermeable bedrock of the Pampean aquifer, acts as a fissured aquifer in this area, contributing to low salinity waters and with a fingerprint similar to groundwater isotopic composition.     

Hydrochemical and isotopic characteristics of groundwater in the Ndop plain,northwest Cameroon: resilience to seasonal climatic changes

Shallow groundwater (>30 mbgl) is an essential source of drinking water to rural communities in the Ndop plain, northwest Cameroon. As a contribution to water management, the effect of seasonal variation on the groundwater chemistry, hydrochemical controls, drinking quality and recharge were investigated during the peaks of the dry (January) and rainy (September) seasons. Field measurements of physical parameters were preceded by sampling 58 groundwater samples during both seasons for major ions and stable isotope analyses. The groundwater, which was barely acidic (mean pH of 6) and less mineralised (TDS < 272 mg/l), showed no significant seasonal variation in temperature, pH and TDS during the two seasons. The order of cation abundance (meq/l) was Na⁺ > Ca²⁺ > Mg²⁺ > K⁺ and Na⁺ > Mg²⁺ > Ca²⁺ > K⁺ in the dry and rainy seasons, respectively, but that of anions ( \( {\text{HCO}}_{3}^{ - } \)  >  \( {\text{NO}}_{3}^{ - } \)  > Cl^? >  \( {\text{SO}}_{4}^{2 - } \)  > F^?) was similar in both seasons. This suggests a negligible effect of seasonal variations on groundwater chemistry. The groundwater, which was CaMgHCO₃ and NaHCO₃, is chemically evolved rainfall (CaMgSO₄Cl) in the area. Silicate mineral dissolution and cation-exchange were the main controls on groundwater chemistry while there was little anthropogenic influence. The major ions and TDS concentrations classified the water as suitable for human consumption as per WHO guidelines. The narrow cluster of δ¹⁸O and δD of same groundwater from both seasons between the δ¹⁸O and δD values of May–June precipitation along the Ndop Meteoric Water Line indicates meteoric origin, rapid recharge (after precipitation) and timing of recharge between May and June rainfall. Diffuse groundwater recharge mainly occurs at low altitudes (<1,400 m asl) within the plain. Besides major ions and TDS, the similar δ¹⁸O and δD of groundwater from both seasons indicate a consistent groundwater recharge and flow pattern throughout the year and resilience to present day short-term seasonal climatic variations. However, controlled groundwater abstraction is recommended given the increasing demand.     

Hydrochemical characteristics and salinity of groundwater in the Ejina Basin, Northwestern China

A hydrochemical investigation was conducted in the Ejina Basin to identify the hydrochemical characteristics and the salinity of groundwater. The results indicate that groundwater in the area is brackish and are significantly zonation in salinity and water types from the recharge area to the discharge area. The ionic ration plot and saturation index (SI) calculation suggest that the silicate rock weathering and evaporation deposition are the dominant processes that determine the major ionic composition in the study area. Most of the stable isotope δ¹⁸O and δD compositions in the groundwater is a meteoric water feature, indicating that the groundwater mainly sources from meteoric water and most groundwater undergoes a long history of evaporation. Based on radioactive isotope tritium (³H) analysis, the groundwater ages were approximately estimated in different aquifers. The groundwater age ranges from less than 5 years, between 5 years and 50 years, and more than 50 years. Within 1 km of the river water influence zone, the groundwater recharges from recent Heihe river water and the groundwater age is about less than 5 years in shallow aquifer. From 1 km to 10 km of the river water influence zone, the groundwater sources from the mixture waters and the groundwater age is between 5 years and 50 years in shallow aquifer. The groundwater age is more than 50 years in deep confined aquifer.     

Geochemical and isotopic characterization of groundwater from shallow and deep limestone aquifers system of Aleppo basin (north Syria)

Stable isotopes (δ¹⁸O, δ²H and ¹³C) and radioactivity (³H, ¹⁴C) have been used in conjunction with chemical data to evaluate the processes generating the chemical composition, reconstruct the origin of the water and groundwater residence time. The Aleppo basin is comprised of two main limestone aquifers: the first one is unconfined of Paleogene age and the second is confined of Upper Cretaceous age. The chemical data indicate that the dissolution of minerals and evaporation are the main processes controlling groundwater mineralization. The groundwater from the two aquifers is characterized by distinctive stable isotope signatures. This difference in water isotopes is interpreted in terms of difference origin and recharge period. Fresh and brackish shallow groundwater were mostly recharged during the Holocene period. The presence of ³H in several groundwater samples of this aquifer gives evidence that groundwater recharge is going on. Brackish water of the deep confined aquifer has depleted stable isotope composition and very low ¹⁴C activity that indicates recharge during the late Pleistocene cold period.     

Deciphering the interaction between quaternary and continental Sabkhas aquifers in Central Tunisia using hydrochemical and isotopic tools

Climate aridity and intensive exploitation due to uncontrolled pumping for irrigation have caused a drastic decrease in the piezometric level of the shallow aquifer of Chougafiya plain, central Tunisia, and have seriously degraded groundwater quality. According to the hydrochemical data (Cl^?, SO₄ ^2?, NO₃ ^?, HCO₃ ^?, Br^?, Na⁺, Mg²⁺, K⁺, Ca²⁺, Sr²⁺) and the stable isotopes (¹⁸O and ²H content), groundwater salinization in the investigated aquifer is caused by four main processes: (1) evaporite dissolution (2) cation exchange reactions (3) evaporation processes and (4) mixing with Sabkhas salt water causing salinity to increase in the central and southern parts of the basin. The radiogenic (³H) isotope data provided insight into the presence of significant contemporaneous recharge waters in the western part of the shallow aquifer. The movement of the tritiated water may have occurred according to the general flow path (NW–SE). When tritium was used in conjunction with the stable isotopes and chloride, the mixing process could be clearly identified, especially in the central part of the study area.     

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

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

Recharge mode and mineralization of groundwater in a semi-arid region: Sidi Bouzid plain (central Tunisia)

Groundwater is the most important source of water supply in Sidi Bouzid plain located in central Tunisia. Proper understanding of the geochemical evolution of groundwater is important for sustainable development of water resources in this region. A hydrogeochemical survey was conducted on the Mio–Plio–Quaternary aquifer system using stable isotopes, radiocarbon, tritium and major elements, in order to evaluate the groundwater chemistry patterns and the main mineralization processes occurring in this system. The chemical data indicate that dissolution of evaporate minerals and evaporation are the main processes controlling groundwater mineralization. The isotopic data show that groundwater in the study area is a mixture of recent shallow waters located upstream and along Wadi Al Fakka bed and paleowaters located towards plain limits and discharge areas. Low ³H and ¹⁴C contents are observed in major part of the plain indicating that recharge of the aquifer occurs mainly through direct infiltration at Wadi Al Fakka while there is no evidence of significant recharge in major part of the plain and mountains piedmonts.     

The impact of the geologic setting on the Quaternary aquifer,El-Tur area,Southwest Sinai,Egypt

The groundwater extracted from the unconfined Quaternary aquifer is the main source of water supply in El-Tur area. The area is bounded from the east by the elevated basement complex of Southern Sinai and from the west by El-Qabaliyat Ridge. The wadis dissecting these highlands form effective watersheds of the Quaternary aquifer. These wadis form areas of focused recharge. Recharge also occurs directly via the Quaternary sediments covering El-Qaa Plain. Subsurface lateral groundwater flow from the fractured basement contributes significant recharge to the aquifer as well. The aquifer sediment facies affect the type and quality of groundwater. In the eastern part where the aquifer is composed mainly of gravel and coarse sand with fragments of weathered basement, the Na-Cl-SO₄ water dominates. In the west where the facies change is rapid and complex, many water types arise. The base exchange index (BEX) is positive in this part reflecting the role of clay minerals in changing the water types via cation exchange. In the east where clays are insignificant in the aquifer, the BEX is negative. In the western part next to El-Qabaliyat Ridge, the wells discharging from the calcareous sand zone have low groundwater salinities compared to the wells discharging from the alluvium. In general, the groundwater salinity increases in the direction of groundwater flow from the northeast to the southwest which reflects the dissolution of aquifer sediments. The concentration relationships between the major ions on one hand and chloride on the other reflect the dissolution of calcium carbonates, precipitation of K- and Mg-bearing minerals, and cation exchange of Ca for Na on clay minerals. The hydrochemical models support these reactions. In addition, they show that the effect of evaporation on the recharge water in the western catchment is about four times its effect on the eastern recharge water which reflects the rapid recharge through the wadis draining the fractured basement. Moreover, the contribution from the eastern catchment in sample No. 23 is more than four-folds the contribution from the western recharge area. The stable isotopes (²H and ¹⁸O) show that the Quaternary aquifer is recharging from recent rainfall. However, upward leakage of Paleogene groundwater (depleted in ¹⁸O) also occurs. The groundwater level map shows strong overpumping impact especially in the areas close to El-Tur city.     

Effect of diffuse recharge and wastewater on groundwater contamination in Douala,Cameroon

High water demand for domestic use in Douala with over 3 million inhabitants is met mainly by shallow groundwater. Field measurements and water sampling in January 2015 were carried out to examine the major controls on the groundwater composition and spatial view of ions in the water, timing of recharge and link between the recharge process and quality of the water. Fifty-two water samples were analysed for major ions and stable hydrogen and oxygen isotopes. Low pH values (3.61–6.92) in the groundwater indicated an acidic aquifer; thus, prone to acidification. The dominant water type was Na–Cl. Nitrate, which exceeded the WHO guide value of 50 mg/l in 22% of the groundwater, poses a health problem. Mass ratios of Cl^?/Br^? in the water ranged from 54 to 3249 and scattered mostly along the mixing lines between dilute waters, septic-tank effluent and domestic sewage. A majority of the samples, especially the high NO₃ ^? shallow wells, clustered around the septic-tank effluent-end-member indicating high contamination by seepage from pit latrines; hence, vulnerable to pollution. Stable isotopes in the groundwater indicated its meteoric origin and rapid infiltration after rainfall. The δ¹⁸O values showed narrow ranges and overlaps in rivers, springs, open wells and boreholes. These observations depict hydraulic connectivity, good water mixing and a homogeneous aquifer system mainly receiving local direct uniform areal recharge from rainfall. The rapid and diffused recharge favours the leaching of effluent from the pit toilets into the aquifer; hence, the high NO₃ ^? and Cl^? in shallow wells. Silicate weathering, ion exchange and leaching of waste from pit toilets are the dominant controls on the groundwater chemistry. Drilling of deep boreholes is highly recommended for good-quality water supply. However, due the hydraulic connection to the shallow aquifer, geochemical modelling of future effects of such an exploitation of the deeper aquifer should support groundwater management and be ahead of the field actions.     

河套灌区西部浅层地下水咸化机制

浅层地下水水位埋深浅、含盐量高,是导致河套灌区土壤次生盐渍化的重要原因.以河套灌区西部地区为研究区,通过对浅层地下水的水化学和氢氧同位素特征分析以及水文地球化学模拟,探讨了灌区浅层地下水的补给来源和主控水-岩作用过程,并定量估算了蒸发作用对浅层地下水含盐量的影响.研究区内浅层地下水为弱碱性咸水,pH为7.23~8.45,总溶解性固体（total dissolved solids,TDS）变化范围为371~7 599 mg/L;随着地下水咸化程度增大,水化学类型由HCO₃-Na·Mg·Ca型向Cl-Na型过渡.引黄灌溉和大气降水是浅层地下水的主要补给来源,径流过程中浅层地下水受蒸发作用和植物蒸腾作用影响,地下水化学组分主要来源于蒸发盐溶解和硅酸盐风化水解,并受强烈的蒸发作用和离子交换作用影响.水文地球化学模拟和主成分分析结果显示,蒸发作用和岩盐溶解作用对区内浅层地下水咸化贡献最大,石膏和白云石等矿物的溶解、硅酸盐的水解、Na-Ca离子交换以及局部地形起伏对地下水咸化过程也有较大贡献.      

The deep Cretaceous aquifer in the Aleppo and Steppe basins of Syria: assessment of the meteoric origin and geographic source of the groundwater

A drilling project was carried out in Syria to assess the potential of the deep groundwater resources of the Cretaceous aquifer, composed of Cenomanian-Turonian limestones and dolomites. In this context, isotope (¹⁴C, ³H, δ¹³C, δ¹⁸O, δ²H) and hydrochemical analyses were performed on wells in and around the Aleppo and Steppe basins. The interpretation includes complementary results from published and unpublished literature. The results provide evidence that many new wells pump mixed groundwater from the Cretaceous aquifer and the overlying Paleogene aquifer. Radiocarbon measurements confirmed dominating Pleistocene groundwater in the Cretaceous aquifer and mainly Holocene groundwater in the Paleogene aquifer. Most groundwater in the Cretaceous aquifer seems to be recharged in the western limestone ridges, stretching from Jebel az Zawiyah (south of Idlep) via Jebel Samane (south of Afrin and A’zaz) to the region north of Aleppo, and in the Northern Palmyrides mountain belt. Some recharge also occurs around the basalt plateau of the Jebel al Hass, south east of Aleppo. It is concluded that the Taurus Mountains and the Euphrates River do not recharge the Cretaceous aquifer. The sources of recharge seem to be occasionally occurring intensive winter storms that approach from Siberia.     

Isotopes (δD and δ18O) in precipitation, groundwater and surface water in the Ordos Plateau, China: implications with respect to groundwater recharge and circulation

The characteristics of δD and δ¹⁸O in precipitation, groundwater and surface water have been used to understand the groundwater flow system in the Ordos Plateau, north-central China. The slope of the local meteoric water line (LMWL) is smaller than that of the global meteoric water line (GMWL), which signifies secondary evaporation during rainfall. The distribution of stable isotopes of precipitation is influenced by temperature and the amount of precipitation. The lake water is enriched isotopically due to evaporation and its isotopic composition is closely related to the source of recharge and location in the groundwater flow systems. River water is enriched isotopically, indicating that it suffers evaporation. The deep groundwater (more than 150?m) is depleted in heavy isotopes relative to the shallow groundwater (less than 150?m), suggesting that deep groundwater may have been recharged during the late Pleistocene and early Holocene, when the climate was wetter and colder than at present. All groundwater samples plot around the LMWL, implying groundwater is of meteoric origin. Shallow groundwater has undergone evaporation and the average evaporation loss is 53%. There are two recharge mechanisms: preferential flow, and the mixture of evaporated soil moisture and subsequent rain.     

Hydrogeochemistry and pollution assessment of quaternary–tertiary aquifer in the Liwa area,United Arab Emirates

This study presents the data on the hydrochemical characteristics and isotope chemistry of Liwa aquifer, which could be useful to clarify the hydrochemical facies and hydrogeological regime in the study area. Electric conductivity and total dissolved solid values show that the investigated water is slightly brackish, due to the effect of evaporation and the occurrences of evaporite rocks in the adjacent Sabkhas of Abu Dhabi. Major cations and anions arranged according to their decreasing concentrations are: Na⁺ > Ca⁺² > K⁺ > Mg⁺² and Cl⁻ > HCO₃ ⁻ > SO₄⁻², respectively. As sodium is the dominate cation and chloride is the prevailing anion, hydrochemically the groundwater of Liwa can be classified as Na–Cl rich, predominantly chloridic. Ion concentrations increase towards the northeast and presumably coincide with the lithological sources of ions. Factors affecting the hydrochemistry of the groundwater of the investigated area include the effect of weathering of soil and rocks, evaporation and agricultural activities. Stable isotopes of oxygen and hydrogen show that the shallow aquifers contain a single water type that originated in a distinct climatic regime. This water type deviates from the local meteoric water line, as well as from the Eastern Mediterranean Meteoric Water Line, suggesting potential evaporation of recharged water prior to infiltration. The waters are poor in tritium, and thus can be considered generally as indication for recharge prior to 1952. The degradation of groundwater quality can be attributed to evaporation and agricultural practices in most cases.     

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.     

Lithologic controls on mineralization at the Lagunas Norte high-sulfidation epithermal gold deposit, northern Peru

The 13.1-Moz high-sulfidation epithermal gold deposit of Lagunas Norte, Alto Chicama District, northern Peru, is hosted in weakly metamorphosed quartzites of the Upper Jurassic to Lower Cretaceous Chimú Formation and in overlying Miocene volcanic rocks of dacitic to rhyolitic composition. The Dafne and Josefa diatremes crosscut the quartzites and are interpreted to be sources of the pyroclastic volcanic rocks. Hydrothermal activity was centered on the diatremes and four hydrothermal stages have been defined, three of which introduced Au ± Ag mineralization. The first hydrothermal stage is restricted to the quartzites of the Chimú Formation and is characterized by silice parda, a tan-colored aggregate of quartz-auriferous pyrite–rutile ± digenite infilling fractures and faults, partially replacing silty beds and forming cement of small hydraulic breccia bodies. The δ³⁴S values for pyrite (1.7–2.2?‰) and digenite (2.1?‰) indicate a magmatic source for the sulfur. The second hydrothermal stage resulted in the emplacement of diatremes and the related volcanic rocks. The Dafne diatreme features a relatively impermeable core dominated by milled slate from the Chicama Formation, whereas the Josefa diatreme only contains Chimú Formation quartzite clasts. The third hydrothermal stage introduced the bulk of the mineralization and affected the volcanic rocks, the diatremes, and the Chimú Formation. In the volcanic rocks, classic high-sulfidation epithermal alteration zonation exhibiting vuggy quartz surrounded by a quartz–alunite and a quartz–alunite–kaolinite zone is observed. Company data suggest that gold is present in solid solution or micro inclusions in pyrite. In the quartzite, the alteration is subtle and is manifested by the presence of pyrophyllite or kaolinite in the silty beds, the former resulting from relatively high silica activities in the fluid. In the quartzite, gold mineralization is hosted in a fracture network filled with coarse alunite, auriferous pyrite, and enargite. Alteration and mineralization in the breccias were controlled by permeability, which depends on the type and composition of the matrix, cement, and clast abundance. Coarse alunite from the main mineralization stage in textural equilibrium with pyrite and enargite has δ³⁴S values of 24.8–29.4?‰ and $ {\delta^{18 }}{{\mathrm{O}}_{{\mathrm{S}{{\mathrm{O}}_4}}}} $ values of 6.8–13.9?‰, consistent with H₂S as the dominant sulfur species in the mostly magmatic fluid and constraining the fluid composition to low pH (0–2) and logfO₂ of ?28 to ?30. Alunite–pyrite sulfur isotope thermometry records temperatures of 190–260 °C; the highest temperatures corresponding to samples from near the diatremes. Alunite of the third hydrothermal stage has been dated by ⁴⁰Ar/³⁹Ar at 17.0?±?0.22 Ma. The fourth hydrothermal stage introduced only modest amounts of gold and is characterized by the presence of massive alunite–pyrite in fractures, whereas barite, drusy quartz, and native sulfur were deposited in the volcanic rocks. The $ {\delta^{18 }}{{\mathrm{O}}_{{\mathrm{S}{{\mathrm{O}}_4}}}} $ values of stage IV alunite vary between 11.5 and 11.7?‰ and indicate that the fluid was magmatic, an interpretation also supported by the isotopic composition of barite (δ³⁴S?=?27.1 to 33.8?‰ and $ {\delta^{18 }}{{\mathrm{O}}_{{\mathrm{S}{{\mathrm{O}}_4}}}} $ ?=?8.1 to 12.7?‰). The Δ³⁴S_py–alu isotope thermometry records temperatures of 210 to 280 °C with the highest values concentrated around the Josefa diatreme. The Lagunas Norte deposit was oxidized to a depth of about 80 m below the current surface making exploitation by heap leach methods viable.     

A geochemical study of the impact of irrigation and aquifer lithology on groundwater in the Upper Yakima River Basin,Washington, USA

The Yakima River, a major tributary of the Columbia River, is currently overallocated in its surface water usage in part because of large agricultural water use. As a result, groundwater availability and surface water/groundwater interactions have become an important issue in this area. In several sub-basins, the Yakima River water is diverted and applied liberally to fields in the summer creating artificial recharge of shallow groundwater. Major ion, trace element, and stable isotope geochemistry of samples from 26 groundwater wells from a transect across the Yakima River and 24 surface waters in the Kittitas sub-basin were used to delineate waters with similar geochemical signatures and to identify surface water influence on groundwater. Major ion chemistry and stable isotope signatures combined with principal component analysis revealed four major hydrochemical groups. One of these groups, collected from shallow wells within the sedimentary basin fill, displays temporal variations in NO₃ and SO₄ along with high δ¹⁸O and δD values, indicating significant contribution from Yakima River and/or irrigation water. Two other major hydrochemical groups reflect interaction with the main aquifer lithologies in the basin: the Columbia River basalts (high-Na groundwaters), and the volcaniclastic rocks of the Ellensburg Formation (Ca–Mg–HCO₃ type waters). The fourth major group has interacted with the volcaniclastic rocks and is influenced to a lesser degree by surface waters. The geochemical groupings constrain a conceptual model for groundwater flow that includes movement of water between underlying Columbia River basalt and deeper sedimentary basin fill and seasonal input of irrigation water.     

Quantification of the water balance and hydrogeological processes of groundwater–lake interactions in the Pampa Plain, Argentina

This paper gives an account of the assessment and quantification of the water balance and the hydrogeological processes related to lake–groundwater interaction in the Pampa Plain by using hydrogeochemical, isotopic and flow numerical modeling techniques. La Salada is a permanent shallow lake, with an area of 5.8 km², located on the SE of Buenos Aires Province. A total of 29 lake water samples and 15 groundwater samples were collected for both hydrochemical analysis and environmental stable isotope determination. Water table depths were measured in wells closed to the lake. Groundwater samples appear grouped on the Local Meteoric Water Line, suggesting a well-mixed system and that rainfall is the main recharge source to the aquifer. Water evaporation process within La Salada is also corroborated by its isotopic composition. The model that best adjusts to La Salada Lake hydrochemical processes includes evaporation from groundwater, calcite precipitation with CO₂ release and cationic exchange. The annual water balance terms for the lake basin indicates for each hydrological component the following values: 1.16 E⁰⁸ m³ rainfall, 8.15 E⁰⁷ m³ evapotranspiration, 1.90 E⁰⁶ m³ runoff, 1.55 E⁰⁷ m³ groundwater recharge, 6.01 E⁰⁶ m³ groundwater discharge to the lake, 9.54 E⁰⁶ m³ groundwater discharge to the river, 5.00 E⁰⁵ m³ urban extraction and 4.90 E⁰⁶ m³ lake evaporation. Integrated analysis of hydrochemical and isotopic information helped to calibrate the groundwater flow model, to validate the conceptual model and to quantitatively assess the basin water balance.