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

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

Groundwater recharge and evolution in the Dunhuang Basin,northwestern China

Groundwater recharge and evolution in the Quaternary aquifer beneath the Dunhuang Basin was investigated using chemical indicators, stable isotopes, and radiocarbon data to provide guidance for regional water management. The quality of groundwater and surface water is generally good with low salinity and it is unpolluted. The dissolution of halite and sylvite from fine-grained sediments controls concentrations of Na⁺ and K⁺ in the groundwater, but Na⁺/Cl⁻ molar ratios >1 in all samples are also indicative of weathering of feldspar contributing to excess Na⁺. The dissolution of carbonate minerals yields Ca²⁺ to the groundwater, thereby exerting a strong influence on groundwater salinity. The δ¹⁸O and δ²H values in unconfined groundwater are enriched along the groundwater flow path from SW to NE. In contrast, confined groundwater was depleted in heavy isotopes, with mean values of −10.4‰ δ¹⁸O and −74.4‰ δ²H. Compared with the precipitation values, all of the groundwater samples were strongly depleted in heavy isotopes, indicating that modern direct recharge to the groundwater aquifers in the plains area is quite limited. The unconfined water is generally young with radiocarbon values of 64.9–79.6 pmc. In the northern basin, radiocarbon content in the confined groundwater is less than 15 pmc and an uncorrected age of ∼15 ka, indicates that this groundwater was recharged during a humid climatic phases of the late Pleistocence or early Holocene. The results have important implications for inter-basin water allocation programmes and groundwater management in the Dunhuang Basin.     

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.     

Controls on δ34S and δ18O of dissolved sulfate in aquifers of the Murray Basin,Australia and their use as indicators of flow processes

The usefulness of stable isotopes of dissolved SO₄ (δ³⁴S and δ¹⁸O) to study recharge processes and to identify areas of significant inter-aquifer mixing was evaluated in a large, semi-arid groundwater basin in south-eastern Australia (the Murray Basin). The distinct isotopic signatures in the oxidizing unconfined Murray Group Aquifer and the deeper reducing Renmark Group confined aquifer may be more sensitive than conventional chemical tracers in establishing aquifer connections. δ³⁴S values in the unconfined Murray Group Aquifer in the south and central part of the study area decrease along the hydraulic gradient from 20.8 to 0.3‰. The concomitant increasing SO₄/Cl ratios, as well as relatively low δ¹⁸O_SO4 values, suggest that vertical input of biogenically derived SO₄ via diffuse recharge is the predominant source of dissolved SO₄ to the aquifer. Further along the hydraulic gradient towards the discharge area near the River Murray, δ³⁴S values in the unconfined Murray Group Aquifer increase, and SO₄/Cl ratios decrease, due to upward leakage of waters from the confined Renmark Group Aquifer which has a distinctly low SO₄/Cl and high δ³⁴S (14.9–56.4‰). Relatively positive δ³⁴S and δ¹⁸O_SO4 values, and low SO₄/Cl in the Renmark Group Aquifer is typical of SO₄ removal by bacterial reduction. The S isotope fractionation between SO₄ and HS⁻ of ∼24‰ estimated for the confined aquifer is similar to the experimentally determined chemical fractionation factor for the reduction process but much lower than the equilibrium fractionation (∼70‰) even though the confined groundwater residence time is >300 Ka years. Mapping the spatial distribution of δ³⁴S and SO₄/Cl of the unconfined Murray Group Aquifer provides an indicative tool for identifying the approximate extent of mixing, however the poorly defined end-member isotopic signatures precludes quantitative estimates of mixing fractions.     

Groundwater recharge and evolution of water quality in China’s Jilantai Basin based on hydrogeochemical and isotopic evidence

We investigated major ions, stable isotopes, and radiocarbon dates in a Quaternary aquifer in semi-arid northwestern China to gain insights into groundwater recharge and evolution. Most deep and shallow groundwater in the Helan Mountains was fresh, with total dissolved solids <1,000 mg L^?1 and Cl^? <250 mg L^?1. The relationships of major ions with Cl^? suggest strong dissolution of evaporites. However, dissolution of carbonates, albite weathering, and ion exchange are also the major groundwater process in Jilantai basin. The shallow desert groundwater is enriched in δ¹⁸O and intercepts the local meteoric water line at δ¹⁸O = ?13.4 ‰, indicating that direct infiltration is a minor recharge source. The isotope compositions in intermediate confined aquifers resemble those of shallow unconfined groundwater, revealing that upward recharge from intermediate formations is a major source of shallow groundwater in the plains and desert. The estimated residence time of 10.0 kyr at one desert site, indicating that some replenishment of desert aquifers occurred in the late Pleistocene and early Holocene with a wetter and colder climate than at present.     

Origin of brine in the Kangan gasfield: isotopic and hydrogeochemical approaches

The Kangan Permo-Triassic brine aquifer and the overlying gas reservoir in the southern Iran are located in Kangan and Dalan Formations, consisting dominantly of limestone, dolomite, and to a lesser extent, shale and anhydrite. The gasfield, 2,900 m in depth and is exploited by 36 wells, some of which produce high salinity water. The produced water gradually changed from fresh to saline, causing severe corrosion in the pipelines and well head facilities. The present research aims to identify the origin of this saline water (brine), as a vital step to manage saline water issues. The major and minor ions, as well as δ²H, δ¹⁸O and δ³⁷Cl isotopes were measured in the Kangan aquifer water and/or the saline produced waters. The potential processes causing salinity can be halite dissolution, membrane filtration, and evaporation of water. The potential sources of water may be meteoric, present or paleo-seawater. The Na/Cl and I/Cl ratios versus Cl^? concentration preclude halite dissolution. Concentrations of Cl, Na, and total dissolved solid were compared with Br concentration, indicating that the evaporated ancient seawater trapped in the structure is the cause of salinization. δ¹⁸O isotope enrichment in the Kangan aquifer water is due to both seawater evaporation and interaction with carbonate rocks. The δ³⁷Cl isotope content also supports the idea of evaporated ancient seawater as the origin of salinity. Membrane filtration is rejected as a possible source of salinity based on the hydrochemistry data, the δ¹⁸O value, and incapability of this process to dramatically enhance salinity up to the observed value of 330,000 mg/L. The overlaying impermeable formations, high pressure in the gas reservoir, and the presence of a cap rock above the Kangan gasfield, all prevent the downward flow of meteoric and Persian Gulf waters into the Kangan aquifer. The evaporated ancient seawater is autochthonous, because the Kangan brine aquifer was formed by entrapment of brine seawater during the deposition of carbonates, gypsum, and minor clastic rocks in a lagoon and sabkha environment. The reliability of determining the source of salinity in a deep complicated inaccessible high-pressure aquifer can be improved by combining various methods of hydrochemistry, isotope, hydrodynamics, hydrogeology and geological settings.     

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

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

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.     

Stable chlorine isotopes in arid non-marine basins: Instances and possible fractionation mechanisms

Stable chlorine isotopes are useful geochemical tracers in processes involving the formation and evolution of evaporitic halite. Halite and dissolved chloride in groundwater that has interacted with halite in arid non-marine basins has a δ³⁷Cl range of 0 ± 3‰, far greater than the range for marine evaporites. Basins characterized by high positive (+1 to +3‰), near-0‰, and negative (−0.3 to −2.6‰) are documented. Halite in weathered crusts of sedimentary rocks has δ³⁷Cl values as high as +5.6‰. Salt-excluding halophyte plants excrete salt with a δ³⁷Cl range of −2.1 to −0.8‰. Differentiated rock chloride sources exist, e.g. in granitoid micas, but cannot provide sufficient chloride to account for the observed data. Single-pass application of known fractionating mechanisms, equilibrium salt-crystal interaction and disequilibrium diffusive transport, cannot account for the large ranges of δ³⁷Cl. Cumulative fractionation as a result of multiple wetting-drying cycles in vadose playas that produce halite crusts can produce observed positive δ³⁷Cl values in hundreds to thousands of cycles. Diffusive isotope fractionation as a result of multiple wetting-drying cycles operating at a spatial scale of 1–10 cm can produce high δ³⁷Cl values in residual halite. Chloride in rainwater is subject to complex fractionation, but develops negative δ³⁷Cl values in certain situations; such may explain halite deposits with bulk negative δ³⁷Cl values. Future field studies will benefit from a better understanding of hydrology and rainwater chemistry, and systematic collection of data for both Cl and Br.     

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.     

Chlorine stable isotope studies of old groundwater,southwestern Great Artesian Basin,Australia

Stable Cl isotope ratios (³⁷Cl/³⁵Cl) were measured in groundwater samples from the southwestern flow system of the Great Artesian Basin, Australia to gain a better understanding of the Cl⁻ sources and transport mechanisms. δ³⁷Cl values range from 0‰ to −2.5‰ (SMOC), and are inversely correlated with Cl⁻ concentration along the inferred flow direction. The Cl isotopic compositions, in conjunction with other geochemical parameters, suggest that Cl⁻ in groundwaters is not derived from salt dissolution. Mixing of the recharge water with saline groundwater cannot explain the relationship between δ³⁷Cl and Cl⁻ concentration measured. Marine aerosols deposited via rainfall and subsequent evapotranspiration appear to be responsible for the Cl⁻ concentrations observed in wells that are close to the recharge area, and in groundwaters sampled along the southern transect. δ³⁷Cl values measured in the leachate of the Bulldog shale suggest that the aquitard is the subsurface source of Cl⁻ for the majority of groundwater samples studied. Diffusion is likely the mechanism through which Cl⁻ is transported from the pore water of the Bulldog shale to the aquifer. However, a more detailed study of the aquitard rocks is required to verify this hypothesis.     

The hydro geochemical characterization of ground waters in Tunisian Chott’s region.

Tunisian Chott’s region is one of the most productive artesian basins in Tunisia. It is located in the southwestern part of the country, and its groundwater resources are developed for water supply and irrigation. The chemical composition of the water is strongly influenced by the interaction with the basinal sediments and by hydrologic characteristics such as the flow pattern and time of residence. The system is composed of an upper unconfined “Plio-Quaternary” aquifer with a varying thickness of 20–200 m, an intermediate confined/unconfined “Complex Terminal” aquifer about 100 m in thickness and a deeper “Continental Intercalaire” aquifer about 150 m in thickness separated by thick clay and marl layers. The dissolution of evaporites and carbonates explains part of the contained Na⁺, Ca²⁺, Mg²⁺, K⁺, SO₄²⁻ and Cl^-, but other processes, such carbonate precipitation, also contributes to the water composition. The stable isotope composition of waters establishes that the deep groundwater (depleted as compared to present corresponding local rainfall) is ancient water recharged probably during the late Pleistocene and the early Holocene periods. The relatively recent water in the Plio-Quaternary aquifer is composed of mixed waters resulting presumably from upward leakage from the deeper groundwater.     

Hydrogeochemical investigation of surface and groundwater composition in an irrigated land in Central Tunisia

Major element concentrations, stable (δ¹⁸O and δ²H) and radiogenic (³H, ¹⁴C) isotopes determined in groundwater provided useful initial tracers for understanding the processes that control groundwater mineralization and identifying recharge sources in semi-arid Cherichira basin (central Tunisia).Chemical data based on the chemistry of several major ions has revealed that the main sources of salinity in the groundwaters are related to the water–rock interaction such as the dissolution of evaporitic and carbonate minerals and some reactions with silicate and feldspar minerals.The stable isotope compositions provide evidence that groundwaters are derived from recent recharge. The δ¹⁸O and δ²H relationships implied rapid infiltration during recharge to both the Oligocene and Quaternary aquifers, with only limited evaporation occurring in the Quaternary aquifer.Chemical and isotopic signatures of the reservoir waters show large seasonal evolution and differ clearly from those of groundwaters.Tritium data support the existence of recent recharge in Quaternary groundwaters. But, the low tritium values in Oligocene groundwaters are justified by the existence of clay lenses which limit the infiltration of meteoric water in the unsaturated zone and prolong the groundwater residence time.Carbon-14 activities confirm that groundwaters are recharged from the surface runoff coming from precipitation.     

Tracing stable isotope values from meteoric water to groundwater in the southwestern part of the Chad basin

The southwestern Chad basin is a semi-arid region with annual rainfall that is generally less than 500 mm and over 2,000 mm of evapotranspiration. Surface water in rivers is seasonal, and therefore groundwater is the perennial source of water supply for domestic and other purposes. Stable isotope has been measured for rainwater, surface water and groundwater samples in this region. The stable isotope data have been used to understand the inter-relationships between the rainwater, surface water, shallow and deep groundwater of this region. This is being used in a qualitative sense to demonstrate present day recharge to the groundwater. Stable isotope in rainwater for the region has an average value of –4‰ δ¹⁸O and –20‰ δ²H. Surface water samples from rivers and Lake Chad fall on the evaporation line of this average value. The Upper Zone aquifer water samples show stable isotope signal with a wide range of values indicating the complex character of the aquifer Zone with three distinguishable units. The wide range of values is attributable to waters from individual unit and/or mixture of waters of different units. The Middle and Lower aquifers Zones’ waters show similar stable isotopes values, probably indicating similarity in timing and/or mechanism of recharge. These are palaeowaters probably recharged under a climate that is different from today. The Upper Zone aquifer is presently being recharged as some of its waters show stable isotope compositions similar to those of average rainfall waters of the region.     

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.     

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.     

Quantification of groundwater–seawater interaction in a coastal sandy aquifer system: a study from Panama,Sri Lanka

The Panama coastal aquifer system is an important water resource in the southeast coast of Sri Lanka that provides adequate supplies of water for agriculture and domestic uses. One of the biggest threats to these fragile aquifers is the sea water intrusion. In this study, recharging mechanism and geochemical evaluation of groundwater in the coastal sandy aquifer of Panama were evaluated using chemical and stable isotope techniques. Thirty groundwater samples were collected and analyzed for their major ion concentrations and stable isotope ratios of oxygen (¹⁸O/¹⁶O) and hydrogen (D/H). All studied samples showed a ranking of major anions in the order Cl^? > HCO ₃ ^?  > SO ₄ ^2?  > N-NO₃ ^? while cations showed a decreasing order of abundance with Na⁺ > Ca²⁺ > Mg²⁺ > K⁺. Dominant groundwater hydrogeochemical types were Na–Cl and mixed Ca–Mg–Cl. Results of saturation index calculations indicate that the investigated groundwater body was mostly saturated with respect to calcite, dolomite and gypsum. In addition, stable isotope and geochemical data suggest that fresh groundwater in the aquifer is recharged mainly by local precipitation with slight modification from evaporation and saline water intrusions. Isotope data suggest that mixing of salt water with freshwater occurs in aquifers which are located towards the lagoon. Since the communities in the study area depend entirely on groundwater, an understanding of the hydrogeochemical characteristics of the aquifer system is extremely important for the better water resource management in the region.     

Groundwater flow patterns in the San Luis Valley,Colorado, USA revisited: an evaluation of solute and isotopic data

Groundwater systems in the San Luis Valley, Colorado, USA have been re-evaluated by an analysis of solute and isotopic data. Existing stream, spring, and groundwater samples have been augmented with 154 solute and isotopic samples. Based on geochemical stratification, three groundwater regimes have been identified within 1,200 m of the surface: unconfined, upper active confined, and lower active confined with maximum TDS concentrations of 35,000, 3,500 and 600 mg/L, respectively. The elevated TDS of northern valley unconfined and upper active confined systems result from mineral dissolution, ion exchange and methanogenesis of organic and evaporate lake sediments deposited in an ancient lake, herein designated as Lake Sipapu. Chemical evolutions along flow paths were modeled with NETPATH. Groundwater ages, and δ¹³C, δ²H and δ¹⁸O compositions and distributions, suggest that mountain front recharge is the principle recharge mechanism for the upper and lower confined aquifers with travel times in the northern valley of more than 20,000 and 30,000 ¹⁴C years, respectively. Southern valley confined aquifer travel times are 5,000 ¹⁴C years or less. The unconfined aquifer contains appreciable modern recharge water and the contribution of confined aquifer water to the unconfined aquifer does not exceed 20%.     

Contributions of boron isotopes to understanding the hydrogeochemistry of the coastal detritic aquifer of Castellón Plain,Spain

The Castellón Plain alluvial aquifer, Spain, is intensively exploited to meet the demand for agricultural irrigation and industrial water supply. The geochemistry of its groundwater shows complex salinization in the northern and southern parts of the aquifer, with significant pollution from human origin in the central portion. Boron content and B isotope geochemistry are useful for distinguishing between various sources of pollution and their relative importance in different parts of this aquifer. Boron concentrations in the groundwater vary between 0.01 and 0.85 mg/L. In the more saline groundwaters, found at the northern and southern ends of the study area, the presence of B is linked to inputs from seawater and water with a calcium-magnesium sulphate facies, which feed the aquifer and clearly influence the chemistry of its waters. Evidence of B adsorption processes in some samples is shown by the low B/Cl ratios and the high values of δ¹¹B. In the central portion of the aquifer, the high B/Cl ratios and the strongly negative δ¹¹B are related to pollution of human origin.     

An experimental determination of chlorine isotope fractionation in acid systems and applications to volcanic fumaroles

The δ³⁷Cl values of volcanic fumarole gases and bubbling springs were measured from the Central American and the Kurile arcs. Low temperature gas samples from the Central American arc have δ³⁷Cl values generally between −2 and 2‰, whereas high-temperature fumaroles (>100 °C) range from 4 to 12‰, with several outliers. This is in contrast to the high-temperature fumaroles from the Kurile island Kudryavy which have slightly positive δ³⁷Cl values, averaging 0.8‰ (±0.6, 1σ), and from our previous work on Izu and Mariana arc samples in which the δ³⁷Cl values of fumarole and ash samples are similar to each other and negative. Assuming that the source for the high-T Central American fumaroles has typical subduction δ³⁷Cl values (−2.5 to 1‰), then there must be a large Cl isotope fractionation in the near-surface fumarolic system. The most likely fractionation mechanism for the high δ³⁷Cl values is between Cl⁻_aq − HCl(g), but published theoretical fractionation for this pair is only ∼1.5‰, insufficient to explain the large range of values observed in the fumaroles. Three experiments were undertaken in order to identify a process that could cause the wide range of δ³⁷Cl values observed in the high-temperature fumaroles. Results are the following: (1) A sub-boiling equilibration experiment between aqueous chloride and HCl gas had , in agreement with the theoretical calculations. (2) Evaporation of HCl(g) from hydrochloric acid at room temperature had fractionation in the opposite sense, with a . (3) A ‘synthetic fumarole’ gave large positive fractionations up to 9‰, with ³⁷Cl strongly partitioned into the vapor phase. The ‘fumarole’ experiments were made by bubbling dry air through boiling hydrochloric acid in an Erlenmeyer flask, and collecting the evolved HCl(g) in a second ‘downstream’ flask filled with distilled water. This extreme enrichment is likely due to a distillation process in which ³⁷Cl-enriched HCl(g) is stripped from the hydrochloric acid followed by a significant fraction of the light HCl(g) redissolving into the constantly condensing water vapor on the walls of the first flask. This distillation experiment creates a Cl isotope fractionation that is the same order of magnitude as observed in the high-temperature fumaroles in Central America. These results suggest that there must be a H₂O liquid-vapor region in the sub-surface fumarole conduit where light Cl is stripped from the HCl gas as it passes through the fumarole. Similar ³⁷Cl enrichments are expected in fossil epithermal boiling systems.