A multi-isotope (δD, δO,Sr/Sr,and δB) approach for identifying saltwater intrusion and resolving groundwater evolution along the Western Caprock Escarpment of the Southern High Plains,New Mexico

Declining water levels in arid and semi-arid regions increase an aquifer’s vulnerability to natural and anthropogenic influences. A multi-isotope (δD, δ¹⁸O, ⁸⁷Sr/⁸⁶Sr, and δ¹¹B) approach was used to resolve the geochemical evolution of groundwater in a declining aquifer in a semi-arid region of the southwestern USA as groundwater composition reacts to source-water mixing, cross-formational flow including saltwater intrusion, water–rock interaction, and likely agricultural recharge. Sub-aquifers or local flow systems are present in the Southern High Plains aquifer along the Western Caprock Escarpment in New Mexico, and the study site’s local flow system contains a Na–Cl, high dissolved-solids groundwater that flows from the escarpment until it mixes with a high quality regional aquifer or regional flow system. The local flow system contains water that is similar in composition to the underlying, upper Dockum Group aquifer. Saltwater found in the upper Dockum Group aquifer likely originates in the adjacent Pecos River Basin and crosses beneath or possibly through the hydrologic divide of the Western Caprock Escarpment. Strontium concentrations of 0.9–31 mg/L and a ⁸⁷Sr/⁸⁶Sr range of 0.70845–0.70906 were sufficient to estimate source-water fractions, mixing patterns, and contributions from chemical weathering through mass balance inverse calculations. Boron concentrations (59–1740 mg/L) and δ¹¹B values (+6.0–+46.0‰) were used to confirm source-water mixing, further evaluate water–rock interaction, and examine the influence of possible agricultural recharge. Alteration of B concentrations and δ¹¹B values in an area of likely agricultural recharge indicated the loss of B and decrease in δ¹¹B values likely from plant uptake, adsorption, and weathering contributions in the soil/vadose zone prior to recharge. The effectiveness of ⁸⁷Sr/⁸⁶Sr and δ¹¹B for resolving the geochemical influences in groundwater in the Southern High Plains along the Western Caprock Escarpment allowed for the reinterpretation of the isotopic composition of water that has been shown to be highly variable in the Southern High Plains. This study shows the utility of a multi-isotope approach for resolving the geochemical evolution of groundwater in an aquifer that has a complex relationship with underlying aquifers and the applicability of these isotopes as indicators of the alteration of source waters from natural or anthropogenic influences.     

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.     

Stable isotopic and elemental characteristics of recent tufa from a karstic Krka River (south‐east Slovenia): useful environmental proxies?

Tufa samples from 16 consecutive barrages along a 13 km section of the groundwater‐fed Krka River (Slovenia) were analysed for their petrographical, mineralogical, elemental and stable carbon (δ¹³C) and oxygen (δ¹⁸O) isotope composition, to establish their relation to current climatic and hydrological conditions. Waters constantly oversaturated with calcite and the steep morphology of the Krka riverbed stimulate rapid CO₂ degassing and subsequent tufa precipitation. The carbon isotope fractionation (Δ¹³C) between dissolved inorganic carbon and tufa in the Krka River evolves towards isotopic equilibrium being controlled by continuous CO₂ degassing and tufa precipitation rate downstream. The Δ¹³C increased from 1·9 to 2·5‰ (VPDB); however, since tufa precipitation rates remain similar downstream, the major controlling factor of carbon isotope exchange is most probably related to the continuous ¹²CO₂ degassing downstream leaving the carbon pool enriched in ¹³C. In the case of oxygen, the isotope fractionation (Δ¹⁸O) was found to be from 1·0 to 2·3‰ (VSMOW) smaller than reported in the literature. The observed discrepancies are due to different precipitation rates of calcite deposits because Krka tufas on cascades grow relatively faster compared to slowly precipitated calcite deposits in cave or stream pools. Due to non‐equilibrium oxygen isotope exchange between Krka tufa and water, the δ¹⁸O proxy showed from 1·2 to 8·2°C higher calculated water temperatures compared to measured water temperatures, demonstrating that δ¹⁸O proxy‐based temperature equations are not reliable for water temperature calculations of fast‐growing tufa on cascades. Because Mg is bound to the terrigenous dolomite fraction in the Krka tufa samples, the Mg/Ca was also found to be an unreliable temperature proxy yielding over up to 20°C higher calculated water temperatures.     

Geochemistry and stable isotopic composition of tufa waters and precipitates from the Interlake Region, Manitoba, Canada: Constraints on groundwater origin, calcitization, and tufa formation

New major, trace and isotopic geochemical results from a regional study of springs discharging from the major carbonate rock aquifer in the Interlake Region of Manitoba, Canada, are used to understand water–rock reactions, timing of recharge/discharge, tufa formation processes, and as baseline data. Spring waters are fresh with total dissolved solids (TDS) concentrations ranging from 150 to 880 mg/L. Waters discharging in the northern part of the study area have lower TDS, are dominantly Ca–Mg–HCO₃ waters with low SO₄ concentrations (<< 50 mg/L), and appear to have interacted primarily with Silurian carbonate lithologies. In contrast, waters in the southeastern part of the study area have higher TDS and have elevated SO₄ concentrations (up to 210 mg/L). Spring waters have elevated Mg/Ca_molar (1.23 ± 0.23), typically greater than congruent dissolution of dolomite. Ca and Mg concentrations and Mg/Ca_molar indicate that groundwater residence times were sufficient to allow equilibration with bedrock dolomite lithologies; elevated tritium in northern waters indicates a significant recharge component in the 1960's and 1970's. Tufa precipitates that have formed from many of the spring waters are low-Mg calcite (MgO = 1.70 to 5.80 wt.%). Sr concentrations are variable (57 to 657 ppm) and tufa Sr/Ca_molar ratios appear to be entirely controlled by spring water Sr/Ca_molar. Empirically determined Sr distribution coefficients (D_Sr = 0.389 ± 0.083) indicate rapid crystallization following CO₂ degassing, consistent with heavier δ¹³C_VPDB compared to spring waters. Sulfate concentrations are generally too low for calcitization (dedolomitization) reactions driven by anhydrite dissolution to be the dominant control on the elevated groundwater Mg/Ca_molar, implying either extensive sulfate reduction along the flow paths (however, δ¹³C_DIC suggests the elevated SO₄ is more consistent with Fe-sulfide oxidation), or that other processes are involved. Major ion ratios suggest that the waters in the southern part of the study area are more consistent with interaction with siliciclastic rocks than with anhydrite dissolution. We suggest that calcitization (dedolomitization) reactions driven by anhydrite dissolution may not dominate all carbonate aquifers and that mixing of waters in karst conduits combined with ion exchange reactions are important controls on water chemistry in these systems.     

Laminated tufa sediments formed from overflow karst springs: Controls on their deposition and carbon–oxygen isotope records

Tufa sediments are freshwater carbonates that precipitate in karst regions after degassing of carbon dioxide from groundwater in contact with the atmosphere. When laminated, these carbonates can provide high‐resolution records for the study of climate, hydrological and environmental conditions at the time of their precipitation. The formation of these carbonates directly depends on the hydrological regime, and in karst regions discontinuous discharges are often recorded. This study investigates the record of recent laminated tufa sediments precipitated downstream overflow springs in Trabaque Canyon (central Spain). The hydrological dynamics of the karst system were monitored for over three years and a stable isotope record was obtained from laminated tufa carbonates precipitated from an overflow spring. Additionally, a hydrological model of overflow springs was generated and a tufa δ¹⁸O record under constrained parameters was simulated. Temperature is the dominant control of the variation in tufa δ¹³C and δ¹⁸O values within each lamina, although when comparing different laminae, δ¹³C_DIC and δ¹⁸O of river water are also major controls. The positive correlation between tufa δ¹³C values and water temperature is caused by the fractionation occurred by carbon dioxide degassing due to the thermal dependence of carbon dioxide solubility. Additionally, the system recorded a temperature‐independent degassing process caused by the large gradient between groundwater and atmospheric carbon dioxide that is limited to the proximity of the spring. This study cautions on the risk of assuming continuous deposition when studying laminated tufa sediments and highlights the potential of their stable isotope records to provide hydrological information of their aquifers during the past.     

Using isotopic,hydrogeochemical-tracer and temperature data to characterize recharge and flow paths in a complex karst groundwater flow system in northern China

Isotopic and hydrogeochemical analysis, combined with temperature investigation, was conducted to characterize the flow system in the carbonate aquifer at Taiyuan, northern China. The previous division of karst subsystems in Taiyuan, i.e. the Xishan (XMK), Dongshan (DMK) and Beishan (BMK) mountain systems, were also examined. The measured δD, δ ¹⁸O and ³He/⁴He in water indicate that both thermal and cold groundwaters have a meteoric origin rather than deep crustal origin. Age dating using ³H and ¹⁴C shows that groundwater samples from discharge zones along faults located at the margin of mountains in the XMK and DMK are a mixture of paleometeoric thermal waters and younger cold waters from local flow systems. ¹⁴C data suggest that the average age was about 10,000 years and 4,000 years for thermal and cold groundwater in discharge zones, respectively. Based on the data of temperature, water solute chemical properties, ¹⁴C, δ ³⁴S_SO4, ⁸⁷Sr/⁸⁶Sr and δ ¹⁸O, different flow paths in the XMK and DMK were distinguished. Shallow groundwater passes through the upper Ordovician formations, producing younger waters at the discharge zone (low temperature and ionic concentration and enriched D and ¹⁸O). Deep groundwater flows through the lower Ordovician and Cambrian formations, producing older waters at the discharge zone (high ionic concentration and temperature and depleted D and ¹⁸O). At the margin of mountains, groundwater in deep systems flows vertically up along faults and mixes with groundwater from shallow flow systems. By contrast, only a single flow system through the entire Cambrian to Ordovician formations occurs in the BMK.     

Groundwater recharge in suburban areas of Hanoi,Vietnam: effect of decreasing surface-water bodies and land-use change

Over-exploited groundwater is expected to remain the predominant source of domestic water in suburban areas of Hanoi, Vietnam. In order to evaluate the effect on groundwater recharge, of decreasing surface-water bodies and land-use change caused by urbanization, the relevant groundwater systems and recharge pathways must be characterized in detail. To this end, water levels and water quality were monitored for 3 years regarding groundwater and adjacent surface-water bodies, at two typical suburban sites in Hanoi. Stable isotope (δ¹⁸O, δD of water) analysis and hydrochemical analysis showed that the water from both aquifers and aquitards, including the groundwater obtained from both the monitoring wells and the neighboring household tubewells, was largely derived from evaporation-affected surface-water bodies (e.g., ponds, irrigated farmlands) rather than from rivers. The water-level monitoring results suggested distinct local-scale flow systems for both a Holocene unconfined aquifer (HUA) and Pleistocene confined aquifer (PCA). That is, in the case of the HUA, lateral recharge through the aquifer from neighboring ponds and/or irrigated farmlands appeared to be dominant, rather than recharge by vertical rainwater infiltration. In the case of the PCA, recharge by the above-lying HUA, through areas where the aquitard separating the two aquifers was relatively thin or nonexistent, was suggested. As the decrease in the local surface-water bodies will likely reduce the groundwater recharge, maintaining and enhancing this recharge (through preservation of the surface-water bodies) is considered as essential for the sustainable use of groundwater in the area.

     

Noble gas and isotope geochemistry in western Canadian Arctic watersheds: tracing groundwater recharge in permafrost terrain

In Canada’s western Arctic, perennial discharge from permafrost watersheds is the surface manifestation of active groundwater flow systems with features including the occurrence of year-round open water and the formation of icings, yet understanding the mechanisms of groundwater recharge and flow in periglacial environments remains enigmatic. Stable isotopes (δ¹⁸O, δD, δ¹³C_DIC), and noble gases have proved useful to study groundwater recharge and flow of groundwater which discharges along rivers in Canada’s western Arctic. In these studies of six catchments, groundwater recharge was determined to be a mix of snowmelt and precipitation. All systems investigated show that groundwater has recharged through organic soils with elevated P_CO2, which suggests that recharge occurs largely during summer when biological activity is high. Noble gas concentrations show that the recharge temperature was between 0 and 5 °C, which when considered in the context of discharge temperatures, suggests that there is no significant imbalance of energy flux into the subsurface. Groundwater circulation times were found to be up to 31 years for non-thermal waters using the ³?H-³He method.     

Unusual catchment runoff in a high alpine karst environment influenced by a complex geological setting (Northern Calcareous Alps,Tyrol, Austria)

Garber Schlag (Q-GS) is one of the major springs of the Karwendel Mountains, Tyrol, Austria. This spring has a unique runoff pattern that is mainly controlled by the tectonic setting. The main aquifer is a moderately karstified and jointed limestone of the Wetterstein Formation that is underlain by nonkarstified limestone of the Reifling Formation, which acts as an aquitard. The aquifer and aquitard of the catchment of spring Q-GS form a large anticline that is bound by a major fault (aquitard) to the north. Discharge of this spring shows strong seasonal variations with three recharge origins, based on δ¹⁸O and electrical conductivity values. A clear seasonal trend is observed, caused by the continuously changing portions of water derived from snowmelt, rainfall and groundwater. At the onset of the snowmelt period in May, the discharge is composed mainly of groundwater. During the maximum snowmelt period, the water is dominantly composed of water derived from snowmelt and subordinately from rainfall. During July and August, water derived from snowmelt continuously decreases and water derived from rainfall increases. During September and October, the water released at the spring is mainly derived from groundwater and subordinately from rainfall. The distinct discharge plateau from August to December and the following recession until March is likely related to the large regional groundwater body in the fissured and moderately karstified aquifer of the Wetterstein Formation and the tectonic structures (anticline, major fault). Only a small portion of the water released at spring Q-GS is derived from permafrost.

     

Understanding long-term groundwater flow at Pahute Mesa and vicinity,Nevada National Security Site,USA, from naturally occurring geochemical and isotopic tracers

Recently collected naturally occurring geochemical and isotopic groundwater tracers were combined with historic data from the Pahute Mesa area of the Nevada National Security Site (NNSS), Nevada, USA, to provide insights into long-term regional groundwater flow patterns, mixing and recharge. Pahute Mesa was the site of 85 nuclear detonations between 1965 and 1992, many of them deeply buried devices that introduced radionuclides directly into groundwater. The dataset examined included major ions and field measurements, stable isotopes of hydrogen (δ²H), oxygen (δ¹⁸O), carbon (δ¹³C) and sulfur (δ³⁴S), and radioisotopes of carbon (¹⁴C) and chloride (³⁶Cl). Analysis of the patterns of groundwater ¹⁴C data and the δ²H and δ¹⁸O signatures indicates that groundwater recharge is predominantly of Pleistocene age, except for a few localized areas near major ephemeral drainages. Steep gradients in sulfate (SO₄) and chloride (Cl) define a region near the western edge of the NNSS where high-concentration groundwater flowing south from north of the NNSS merges with dilute groundwater flowing west from eastern Pahute Mesa in a mixing zone that coincides with a groundwater trough associated with major faults. The ³⁶Cl/Cl and δ³⁴S data suggest that the source of the high Cl and SO₄ in the groundwater was a now-dry, pluvial-age playa lake north of the NNSS. Patterns of groundwater flow indicated by the combined data sets show that groundwater is flowing around the northwest margin of the now extinct Timber Mountain Caldera Complex toward regional discharge areas in Oasis Valley.

     

Climatic change recorded by stable isotopes and trace elements in a British Holocene tufa

Combined stable isotope (δ¹⁸O and δ¹³C) and trace element (Mg, Sr) geochemistry from bulk tufa calcite and ostracod shell calcite from an early Holocene British tufa reveal clear records of Holocene palaeoclimatic change. Variation in δ¹⁸O is caused principally by change in the isotopic composition of Holocene rainfall (recharge), itself caused mainly by change in air temperature. The δ¹³C variability through much of the deposit reflects increasing influence of soil‐zone CO₂, owing to progressive woodland soil development. Bulk tufa Mg/Ca and Sr/Ca are controlled by their concentrations in the spring water. Importantly, Mg/Ca ratios are not related to δ¹⁸O values and thus show no temperature dependence. First‐order sympathetic relationships between δ¹³C values and Mg/Ca and Sr/Ca are controlled by aquifer processes (residence times, CO₂ degassing and calcite dissolution/reprecipitation) and probably record intensity of palaeorainfall (recharge) effects. Stable isotope records from ostracod shells show evidence of vital effects relative to bulk tufa data. The ostracod isotopic records are markedly ‘spiky’ because the ostracods record ‘snapshots’ of relatively short duration (years), whereas the bulk tufa samples record averages of longer time periods, probably decades. The δ¹⁸O record appears to show early Holocene warming, a thermal maximum at ca. 8900 cal. yr BP and the global 8200 yr BP cold event. Combined δ¹³C, Mg/Ca and Sr/Ca data suggest that early Holocene warming was accompanied by decreasing rainfall intensity. The Mg/Ca data suggest that the 8200 yr BP cold event was also dry. Warmer and wetter conditions were re‐established after the 8200 yr BP cold event until the top of the preserved tufa sequence at ca. 7100 cal. yr BP. Copyright © 2004 John Wiley & Sons, Ltd.     

Evaluation of the importance of clay confining units on groundwater flow in alluvial basins using solute and isotope tracers: the case of Middle San Pedro Basin in southeastern Arizona (USA)

As groundwater becomes an increasingly important water resource worldwide, it is essential to understand how local geology affects groundwater quality, flowpaths and residence times. This study utilized multiple tracers to improve conceptual and numerical models of groundwater flow in the Middle San Pedro Basin in southeastern Arizona (USA) by determining recharge areas, compartmentalization of water sources, flowpaths and residence times. Ninety-five groundwater and surface-water samples were analyzed for major ion chemistry (water type and Ca/Sr ratios) and stable (¹⁸O, ²H, ¹³C) and radiogenic (³H, ¹⁴C) isotopes, and resulting data were used in conjunction with hydrogeologic information (e.g. hydraulic head and hydrostratigraphy). Results show that recent recharge (<60 years) has occurred within mountain systems along the basin margins and in shallow floodplain aquifers adjacent to the San Pedro River. Groundwater in the lower basin fill aquifer (semi confined) was recharged at high elevation in the fractured bedrock and has been extensively modified by water-rock reactions (increasing F and Sr, decreasing ¹⁴C) over long timescales (up to 35,000 years BP). Distinct solute and isotope geochemistries between the lower and upper basin fill aquifers show the importance of a clay confining unit on groundwater flow in the basin, which minimizes vertical groundwater movement.     

山西太原晋祠—平泉水力联系及对晋祠泉复流的贡献

晋祠泉出露于山西太原西山悬瓮山下,由难老泉、圣母泉、善利泉组成。1954—1958年实测泉水平均流量为l.94 m³/s。与晋祠泉同处山前断裂带的平泉于1978年成为特大岩溶水自流井水源地,自流量最大达到1.56 m³/s。由于这些自流井的开采,使晋祠泉的流量急剧下降,1994年4月30日断流。研究山西太原晋祠泉—平泉水力联系对晋祠泉复流方案制定具有重要意义。本文以晋祠泉、平泉为研究对象,通过样品采集、水质监测,综合运用水化学（离子比例、硫同位素、氢氧同位素）方法。揭示晋祠泉—平泉水文地球化学特征和环境同位素特征,反映地下水流系统的特征、水力联系特征。得出1980—1992年,晋祠泉地下水水位的变化呈稳定下降趋势,主要原因是有太原化学工业公司、开化沟、淸徐县平泉村和梁泉村等水源地大量开采岩溶地下水,导致地下水水位下降。晋祠—平泉一带岩溶地下水氢氧同位素值较接近,说明这一带岩溶地下水补给来源与补给途径相近。水质监测分析得出晋祠泉与平泉各个离子变化趋势基本一致。说明晋祠与平泉存在紧密的水力联系,因此晋祠泉与平泉必然存在一个比较强的导水通道。可以通过在晋祠泉下游导水通道上帷幕灌浆,提高晋祠泉水水位,使晋祠泉出流。     

Delineating volcanic aquifer recharge areas using geochemical and isotopic tools

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

Sources of Sr and implications for weathering of limestone under tallgrass prairie, northeastern Kansas

Grasslands of north-central Kansas are underlain by carbonate aquifers and shale aquitards. Chemical weathering rates in carbonates are poorly known, and, because large areas are underlain by these rocks, solute fluxes are important to estimating global weathering rates. Grasslands exist where the amount of precipitation is extremely variable, both within and between years, so studies in grasslands must account for changes in weathering that accompany changes in precipitation. This study: (1) identifies phases that dominate chemical fluxes at Konza Prairie Biological Station (KPBS) and Long-Term Ecological Research Site, and (2) addresses the impact of variable precipitation on mineral weathering. The study site is a remnant tallgrass prairie in the central USA, representing baseline weathering in a mid-temperate climate grassland.Groundwater chemistry and hydrology in the 1.2 km² watershed used for this study suggest close connections between groundwater and surface water. Water levels fluctuate seasonally. High water levels coincide with periods of precipitation plus low evapotranspiration rather than during precipitation peaks during the growing season. Precipitation is concentrated before recharging aquifers, suggesting an as yet unquantified residence time in the thin soils.Groundwater and surface water are oversaturated with respect to calcite within limitations of available data. Water is more dilute in more permeable aquifers, and water from one aquifer (Morrill) is indistinguishable from surface water. Cations other than Ca co-vary with each other, especially Sr and Mg. Potassium and Si co-vary in all aquifers and surface water, and increases in concentrations of these elements are the best indicators of silicate weathering at this study site. Silicate-weathering indices correlate inversely to aquifer hydraulic conductivity.⁸⁷Sr/⁸⁶Sr in water ranges from 0.70838 to 0.70901, and it decreases with increasing Sr concentration and with increasing silicate-weathering index. Carbonate extracted from aquifer materials, shales, soil, and tufa has Sr ranging from about 240 (soil) to 880 ppm (Paleozoic limestone). ⁸⁷Sr/⁸⁶Sr ranges from 0.70834 ± 0.00006 (limestone) to 0.70904 ± 0.00019 (soil). In all cases, ⁸⁷Sr/⁸⁶Sr of aquifer limestone is lower than ⁸⁷Sr/⁸⁶Sr of groundwater, indicating a phase in addition to aquifer carbonate is contributing solutes to water.Aquifer recharge controls weathering: during periods of reduced recharge, increased residence time increases the total amount of all phases dissolved. Mixing analysis using ⁸⁷Sr/⁸⁶Sr shows that two end members are sufficient to explain sources of dissolved Sr. It is proposed that the less radiogenic end member is a solution derived from dissolving aquifer material; longer residence time increases its contribution. The more radiogenic end member solution probably results from reaction with soil carbonate or eolian dust. This solution dominates solute flux in all but the least permeable aquifer and demonstrates the importance that land-surface and soil-zone reactions have on groundwater chemistry in a carbonate terrain.     

Recharge sources and hydrogeochemical evolution of groundwater in the coal-mining district of Jiaozuo, China

Investigations in the Jiaozuo coal-mining district (China) aim to link water-inrush aquifers with the sources of groundwater recharge. Concentrations of TDS, HCO ₃ ^– , Cl^– and Na⁺ in the groundwater samples gradually decrease with increasing depth; in contrast, the factor 1 value of the Q-mode analysis gradually increases, which indicates that the deep groundwater may upflow, recharging the aquifers near the faulted zone. Some groundwater samples (above the local meteoric water line and ‘evaporation line 1’) may originate from recharge by infiltrating local rainfall. Spring and river samples are symmetrically distributed on the regression line of the Ordovician and Carboniferous limestone aquifer groundwater (δ²H?=?3.76?×?δ¹⁸O?–?31.77) and may, therefore, originate from groundwater recharge in the northern Taihang mountains. This mechanism is supported by the observation that groundwater levels change with rainfall. According to radiocarbon residence-time estimates, two groundwater sample sites may have been recharged during the late glacial stage.     

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.     

Initial assessment of recharge areas for large karst springs: a case study from the central Zagros Mountains,Iran

Sousan Spring emerges from the Keyno Anticline, Zagros Mountains (Iran), and the mean annual discharge is ~24 m³/s. Geological and hydrochemical evaluations suggest that the spring recharge is from the limestone Ilam-Sarvak Formation (Cretaceous) but the Mafaroon Fault, a major thrust feature, influences the regional groundwater flow path by juxtaposing other strata. Geological, geochemical, stable isotope and water balance studies were employed to interpret this behavior. Using the isotope data, the sources and elevations of the recharge area were found. Temporal variations of the isotopic data were compared with variations of electrical conductivity (EC). Unexpectedly, high EC was associated with a relative increase of discharge and depletion of δ¹⁸O. Several hypotheses were investigated and approximate water balance studies employed for validation. It was found that an elongated catchment on the Keyno Anticline plus a lesser catchment on a pair of parallel anticlines recharge the aquifer. While the long groundwater flow path along the Keyno Anticline plus guidance by Mafaroon Fault and the adjacent Garou shaly strata lead to increased EC in the Sousan Spring at the end of the dry season, a flow pulse from two adjoining anticlines (Mahalbakh and Shirgoon) arrives at the same time to increase the discharge and deplete the δ¹⁸O signal. Apparently the spring did not experience true base flow conditions during the recorded hydrological year. Although the spring response to specific precipitation events was similar to typical karst aquifers, standard interpretation of recession curves and related coefficients will not be practical at Sousan.     

A combined geological, hydrochemical, and geophysical approach to understanding a disease contamination hazard in groundwaters at a state fish hatchery

At the Midway, Utah, USA fish hatchery, a groundwater development program was conducted to help transition the facility from surface to groundwater in response to contamination by whirling disease, which is caused by a trout parasite. The unconfined aquifer system that provided the hatchery water became infected through the recharge of infected irrigation water obtained from the Provo River. Whirling disease was first discovered in Utah in 1991 at a private fish farm. Infected fish from the farm quickly infected many of Utah’s waterways and infected the hatchery in 2000. Because the parasite completes its life cycle in multiple organisms and can survive for decades in a variety of harsh environments, a comprehensive study of the hydrostratigraphy and hydrodynamics at the hatchery was critical in order to understand the hazard and avoid further contamination. Drilling revealed the presence of a shallow unconfined (surface to 10 m) and two deeper confined aquifer systems (~20–35 m and >40 m bgs). Confinement is related to tufa layers, detected both by drilling and reflection seismology. The tufa layers are associated with past discharge of the thermal system. Vertical leakage is apparent from upward hydraulic head gradients and incrementally increasing unconfined aquifer discharge into downstream on-site drainage canals. High-resolution seismic profiles reveal small-offset faults that provide pathways for upward flow. Analysis of water quality data demonstrates an inverted geochemical gradient in that apparent ¹⁴C ages, solute concentrations, and temperatures decrease with depth. The origin of the inverted geochemical gradient is related to mixing of upwelling thermal, high-TDS waters with cold, low-TDS systems several kilometers up-gradient from the hatchery. Thermal upwelling appears to be fault controlled. Up-gradient of the hatchery, near-surface groundwater mixes with a larger proportion of thermal groundwater than does deeper groundwater. As these mixed systems flow toward the hatchery, a major locus of groundwater discharge, they are segregated into confined and unconfined compartments. Our study requires integration of hydrological, geochemical, and geophysical strategies in order to understand a complex natural hazard and thus may serve as a model for other similarly complex hydrological environments.     

Sedimentology and geochemistry of fluvio-lacustrine tufa deposits controlled by evaporite solution subsidence in the central Ebro Depression, NE Spain

The Urrea de Jalón tufa deposits constitute the 20‐ to 50‐m‐thick caprock (0·3 km²) of an isolated mesa. They disconformably overlie horizontal strata of the Tertiary Ebro Basin (NE Spain), which contains a thick succession of lacustrine gypsum and marls, followed by limestones, marls and, locally, fluvial sandstones and mudstones. The tufa deposits show a complex, large‐scale framework of basin‐like structures with centripetal dips that decrease progressively from the base to the top of the tufa succession, and beds that thicken towards the centre of the structure (cumulative wedge‐out systems). These geometries reveal that the tufa deposits were affected by differential synsedimentary subsidence. Distinct onlapping depressions reflect time migration of the subsiding areas. The studied carbonates are composed mostly of low‐Mg calcite, with minor quartz. Some samples have anomalously high contents of Fe, Mn and Ba that may exceed 1% (goethite, haematite and barite are present). Carbonate facies are: (a) macrophyte encrustation deposits; (b) bryophyte build‐ups; (c) oncolite and coated grain rudstones; (d) non‐concentric stromatolite‐like structures; (e) massive or bioturbated biomicrites; and (f) green and grey marls. Facies a and c show a great variety of microbial‐related forms. These facies can be arranged in dm‐ to 2‐m‐thick vertical associations representing: (i) fluvial–paludal sequences with bryophyte growths; (ii) pond‐influenced fluvial sequences; and (iii) lacustrine–palustrine sequences. The Urrea de Jalón tufa deposits formed in a fluvio‐lacustrine environment that received little alluvial sediment supply. Isotope compositions (δ¹³C and δ¹⁸O) reveal meteoric signatures and accord with such a hydrologically open system of fresh waters. The Fe, Mn and Ba contents suggest an additional supply of mineralized waters that could be related to springs. These would have been discharge points in the Ebro Depression of a regional aquifer of the Iberian Ranges. Rising groundwater caused the solution of the underlying evaporites and the synsedimentary subsidence of the tufa deposits.