Defining hydrochemical evolution of streamflow through flowpath dynamics in Kawakami headwater catchment,Central Japan

The hydrochemical behaviour of catchments is often investigated by inferring stream chemistry through identification of source areas involved in hydrograph separation analysis, yet its dynamic evolution of hydrologic pathways has received little attention. Intensive hydrometric and hydrochemical measurements were performed during two different storms on March 29, 2001 and August 21–22, 2001 to define hydrochemical evolution under the dynamic of flow pathways in a 5·2 ha first‐order drainage of the Kawakami experimental basin (KEB), Central Japan, a forested headwater catchment with various soil depths (1·8 to 5 m) overlying late Neogene of volcanic bedrocks. The hydraulic potential distribution and flow lines data showed that the change in flow direction, which was controlled by rainfall amount and antecedent wetness of the soil profile, agreed well with the hydrochemical change across the slope segment during the storm. Hydrograph separation predicted by end‐member mixing analysis (EMMA) using Ca²⁺ and SiO₂ showed that near surface riparian, hillslope soil water and deep riparian groundwater were important in stream flow generation. The evidence of decrease in solutes concentration at a depth of 1 m in the hillslope and 0·6 m in the near surface riparian during peak storm suggested a flushing of high solutes concentration. Most of the solutes accumulated in the deep riparian groundwater zone, which was due to prominent downward flow and agreed well with the residence time. The distinct flow pathways and chemistry between the near surface riparian and deep riparian groundwater zones and the linkage hillslope aquifer and near surface riparian reservoir, which controls rapid flow and solutes flushing during the storm event, are in conflict with the typical assumption that the whole riparian zone resets flow pathways and chemical signature of hillslope soil water, as has been reported in a previous study. Copyright © 2005 John Wiley & Sons, Ltd.     

Controls on Ground Water Chemistry in the Central Couloir Sud Rifain,Morocco

Irrigation, urbanization, and drought pose challenges for the sustainable use of ground water in the central Couloir sud rifain, a major agricultural region in north-central Morocco, which includes the cities of Fès and Meknès. The central Couloir is underlain by unconfined and confined carbonate aquifers that have suffered declines in hydraulic head and reductions in spring flow in recent decades. Previous studies have surveyed ground water flow and water quality in wells and springs but have not comprehensively addressed the chemistry of the regional aquifer system. Using graphical techniques and saturation index calculations, we infer that major ion chemistry is controlled (1) in the surficial aquifer by cation exchange, calcite dissolution, mixing with deep ground water, and possibly calcite precipitation and (2) in the confined aquifer and warm springs by calcite dissolution, dolomite dissolution, mixing with water that has dissolved gypsum and halite, and calcite precipitation. Analyses of ²H and ¹⁸O indicate that shallow ground water is affected by evaporation during recharge (either of infiltrating precipitation or return flow), whereas deep ground water is sustained by meteoric recharge with little evaporation. Mechanisms of recharge and hydrochemical evolution are broadly consistent with those delineated for similar regional aquifer systems elsewhere in Morocco and in southern Spain.     

Water source characterization through spatiotemporal patterns of major,minor and trace element stream concentrations in a complex,mesoscale German catchment

The link between spatiotemporal patterns of stream water chemistry and catchment characteristics for the mesoscale Dill catchment (692 km²) in Germany is explored to assess the catchment scale controls on water quality and to characterize water sources. In order to record the spatiotemporal pattern, ‘snapshot sampling’ was applied during low, mean and high flow, including 73 nested sites throughout the catchment. Water samples were analysed for the elements Li, B, Na, Mg, Al, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr, Mo, Ba, Pb and U using inductively‐coupled‐plasma mass spectrometry, and for electric conductivity and pH. Principle component analysis and hierarchical cluster analysis were used to find typical element associations and to group water samples according to their hydrochemical fingerprints. This revealed regional hydrochemical patterns of water quality which were subsequently related to catchment attributes to draw conclusions about the controls on stream chemistry. It was found that various lithologic signals and anthropogenic point source inputs controlled the base flow hydrochemistry. During increased flows, stream waters were diluted causing additional hydrochemical variability in response to heterogeneous precipitation inputs and differences in aquifer storage capacities. The hydrochemical patterns further displayed in‐stream mixing of waters. This implied, that stream waters could be apportioned to the identified water sources throughout the catchment. The basin‐wide hydrochemical variability has the potential to outrange the tracer signatures typically inferred in studies at the hillslope scale and is able to strongly influence the complexity of the catchment output. Both have to be considered for further catchment scale tracer and modelling work. Despite the likelihood of non‐conservative behaviour, the minor and trace elements enhanced the rather qualitative discrimination of the various groundwater types, as the major cations were strongly masked by point source inputs. Copyright © 2007 John Wiley & Sons, Ltd.     

Using Hydrochemical Fades to Delineate Ground Water Flowpaths in Fractured Shale

Large differences in chemistry between sampling points separated In short vertical intervals are often observed in contaminant plumes in both granular and fractured aquifers. However, most regional models assume that such differences will be reduced by dispersive mixing during transport. At a field site located in a discharge area on the Oak Ridge Reservation, Tennessee, ground water flows along discrete flowpaths, as evidenced by the presence of four distinct water types—Ca-HCO₃, Ca-Na-HCO₃, and Na-Ca-HCO₃, and Na-Ca-HCO₃-S0₄—in samples collected from shallow (< 3D in) multilevel wells. The preservation of distinct chemical signatures suggests that ground water must he contained in discrete flow zones during much of its transport time. The chemical composition of the water types can be explained primarily by strata-bound flow over varying flowpath lengths and secondarily by mixing of waters during cross-formational flow in a discharge zone. The hydrochemical facies identified by correlation of water types between the boreholes indicate the general orientation of ground water How paths. These inferred flowpaths are oblique to the orientation of the measured hydraulic gradient and are more closely aligned with bedding and the calculated flow direction. Results of this study indicate that discrete multilevel sampling for analysis of major ions, in addition to information gathered from tracer tests, borehole flow tests. and visual core observations, can provide valuable information on flow directions and preferential flowpaths for contaminant transport.     

STUDY ON RECHARGE OF GROUNDWATERS AND INTERRELATIONS BETWEEN VARIOUS WATERS BY MEANS OF ENVIRONMENTAL ISOTOPES

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Multivariate analyses of water chemistry: surface and ground water interactions

Multivariate statistical methods (MSMs) applied to ground water chemistry provide valuable insight into the main hydrochemical species, hydrochemical processes, and water flowpaths important to ground water evolution. The MSMs of principal component factor analysis (FA) and k-means cluster analysis (CA) were sequentially applied to major ion chemistry from 211 different ground water-sampling locations in the Amargosa Desert. The FA reduces the number of variables describing the system and finds relationships between major ions. The CA of the reduced system produced objective hydrochemical facies, which are independent of, but in good agreement with, lithological data. The derived factors and hydrochemical facies are innovatively presented on biplots, revealing composition of hydrochemical processes and facies, and overlaid on a digital elevation model, displaying flowpaths and interactions with geologic and topographic features in the region. In particular, a distinct ground water chemical signature is observed beneath and surrounding the extended flowpath of Fortymile Wash, presenting some contradiction to contemporary water levels along with potential interaction with a fault line. The signature surrounding the ephemeral Fortymile Wash is believed to represent the relic of water that infiltrated during past pluvial periods when the amount of runoff in the wash was significantly larger than during the current drier period. This hypothesis and aforementioned analyses are supported by the examination of available chloride, oxygen-18, hydrogen-2, and carbon-14 data from the region.     

Combination of CFCs and stable isotopes to characterize the mechanism of groundwater–surface water interactions in a headwater basin of the North China Plain

Mountainous areas are characterized by steep slopes and rocky landforms, with hydrological conditions varying rapidly from upstream to downstream, creating variable interactions between groundwater and surface water. In this study, mechanisms of groundwater–surface water interactions within a headwater catchment of the North China Plain were assessed along the stream length and during different seasons, using hydrochemical and stable isotope data, and groundwater residence times estimated using chlorofluorocarbons. These tracers indicate that the river is gaining, due to groundwater discharge in the headwater catchment both in the dry and rainy seasons. Residence time estimation of groundwater using chlorofluorocarbons data reveals that groundwater flow in the shallow sedimentary aquifer is dominated by the binary mixing of water approximating a piston flow model along 2 flow paths: old water, carried by a regional flow system along the direction of river flow, along with young water, which enters the river through local flow systems from hilly areas adjacent to the river valley (particularly during the rainy season). The larger mixing ratio of young water from lateral groundwater recharge and return flow of irrigation during the rainy season result in higher ion concentrations in groundwater than in the dry season. The binary mixing model showed that the ratio of young water versus total groundwater ranged from 0.88 to 0.22 and 1.0 to 0.74 in the upper and lower reaches, respectively. In the middle reach, meandering stream morphology allows some loss of river water back into the aquifer, leading to increasing estimates of the ratio of young water (from 0.22 to 1). This is also explained by declining groundwater levels near the river, due to groundwater extraction for agricultural irrigation. The switch from a greater predominance of regional flow in the dry season, to more localized groundwater flow paths in the wet season is an important groundwater–surface water interactions mechanism, with important catchment management implications.     

Environmental isotopes and hydrochemical study applied to surface water and groundwater interaction in the Awash River basin

An environmental isotope and hydrochemical study was carried out to conceptualize the surface water and groundwater interaction and to explore the groundwater flow pattern in relation to the geological setting. More emphasis is given to the Afar Depression where groundwater is a vital source of water supply. Conventional field hydrogeological study and river discharge records support the isotope and hydrochemical analysis. The region is tectonically active, comprising rift volcanic terrain bordered by highlands. The result revealed that recent meteoric water is the major source of recharge. Three distinct groundwater zones were identified associated with the highlands, transitional escarpment and the rift. Towards the rift, the ionic concentration and isotopic enrichment (δ²H and δ^18degO) increases following the groundwater flow paths, which is strongly controlled by axial rift faults. The groundwater flow converges to the seismically active volcano–tectonic depressions with internal drainage and to the Awash River. Within the Afar Depression, at least four groundwater regimen are identified: (1) fresh and shallow groundwater associated with alluvial deposits ultimately recharged by isotopically depleted recent highland rainfall and the evaporated Awash River; (2) cold and relatively younger groundwater within localized fractured volcanics showing mixed origin in axial fault zones; (3) old groundwater with very high ionic concentration and low isotopic signature localized in deep volcanic aquifers; and (4) old and hot saline groundwaters connected to geothermal systems. The study demonstrated that dependable groundwater can only be obtained from the first two aquifer types in aerially restricted zones in flat plains following river courses, local wadis and volcano–tectonic depressions. The conventional hydrogeological survey and discharge records indicate substantial channel losses from the Awash River, which becomes a more dominant source of recharge in central and lower Awash valleys. Copyright © 2007 John Wiley & Sons, Ltd.     

The seasonal variation of streamwater chemistry in three forested Mediterranean catchments

Streamwater chemistry is described for three streams draining undisturbed, evergreen broad-leaved forested catchments on phyllites in NE Spain: two streams with no or negligible flow in summer are located in the Prades massif, and one perennial stream is in the wetter Montseny mountains. Weekly data for a study period of 2–4 years are provided to (1) describe the seasonal variations in streamwater chemistry, (2) analyse the relationship between stream discharge and solute concentrations using a two-component mixing model and (3) search for patterns of temporal variation in stream solute concentrations after discounting the effects of discharge. At Prades, concentrations of all analysed ions, except NO⁻₃, showed marked seasonal variations in stream water, whereas at Montseny only ions related to mineral weathering (HCO⁻₃, Na⁺, Ca²⁺ and Mg²⁺) showed strong seasonality. Ion concentrations were more closely dependent on instantaneous discharge at Montseny than at Prades. The residuals of the relationship between solute concentrations and discharge retained a strong seasonality at Prades, but not at Montseny. These differences are related to the major hydrochemical processes that determine the streamwater chemistry at each site. The same processes are probably operative in the three catchments, but are of varying relative importance. At Montseny, the mixing of waters of different chemical composition seems to be the major process controlling streamwater chemistry, although the soilwater end-member composition predicted by the mixing model applied did not match the measured soilwater chemistry. In the drier Prades catchments, the two major hydrochemical processes determining the seasonal variation of streamwater chemistry are (1) the restart of flow after the summer drought, which flushes out the solutes accumulated during the dry period, and (2) the seasonal changes in groundwater chemistry that result from the interplay of water residence time, temperature and CO₂ partial pressure. In Mediterranean catchments with relatively high precipitation, such as Montseny, the seasonal variation in the streamwater chemistry is largely determined by the same processes as at humid-temperate sites, whereas in drier Mediterranean catchments, such as Prades, the major hydrochemical processes are clearly distinct.     

Fracture control of ground water flow and water chemistry in a rock aquitard

There are few studies on the hydrogeology of sedimentary rock aquitards although they are important controls in regional ground water flow systems. We formulate and test a three-dimensional (3D) conceptual model of ground water flow and hydrochemistry in a fractured sedimentary rock aquitard to show that flow dynamics within the aquitard are more complex than previously believed. Similar conceptual models, based on regional observations and recently emerging principles of mechanical stratigraphy in heterogeneous sedimentary rocks, have previously been applied only to aquifers, but we show that they are potentially applicable to aquitards. The major elements of this conceptual model, which is based on detailed information from two sites in the Maquoketa Formation in southeastern Wisconsin, include orders of magnitude contrast between hydraulic diffusivity (K/S(s)) of fractured zones and relatively intact aquitard rock matrix, laterally extensive bedding-plane fracture zones extending over distances of over 10 km, very low vertical hydraulic conductivity of thick shale-rich intervals of the aquitard, and a vertical hydraulic head profile controlled by a lateral boundary at the aquitard subcrop, where numerous surface water bodies dominate the shallow aquifer system. Results from a 3D numerical flow model based on this conceptual model are consistent with field observations, which did not fit the typical conceptual model of strictly vertical flow through an aquitard. The 3D flow through an aquitard has implications for predicting ground water flow and for planning and protecting water supplies.     

Constraining a Flow Model with Field Measurements to Assess Water Transit Time Through a Vadose Zone

The modeling of thick vadose zones is particularly challenging because of difficulties in collecting a variety of measured sediment properties, which are required for parameterizing the model. Some models rely on synthetic data, whereas others are simplified by running as homogeneous sediment domains and relying on a single set of sediment properties. Few studies have simulated flow processes through a thick vadose zone using real and comprehensive data sets comprising multiple measurements. Here, we develop a flow model for a 7-m-thick vadose zone. This model, combining the numerical codes CTRAN/W with SEEP/W, includes the measured sediment hydraulic properties of the investigated vadose zone and incorporates the actual climate and subsurface conditions of the study site (precipitations, water-table elevations, and stable isotope data). The model is calibrated by fitting the simulated and measured vertical profiles of water content. Our flow model calculates a transit time of 1 year for the travel of water through the 7-m vadose zone; this estimate matches stable isotope-based results obtained previously for this site. A homogeneous sediment domain flow model, which considers only a single set of sediment properties, produces a transit time that is approximately half the duration of that of the heterogeneous flow model. This difference highlights the importance of assuming heterogeneous material within models of thick vadose zones and testifies to the advantage gained when using real sediment hydraulic properties to parametrize a flow model.     

Hydrochemical Relation Between Shallow Groundwater with Elevated Fluoride and Groundwater in Underlying Carbonates

In the arid to semi-arid district of Chengcheng, Weinan City, in central Shaanxi Province, diminishing groundwater reserves in the shallow Quaternary (QLB) aquifer and elevated fluoride in the similarly shallow Permo-Triassic (PTF) aquifer, have promoted interest in the development of groundwater resources in the deep but poorly understood Cambrian-Ordovician carbonate aquifer system (COC). To investigate the origin of the COC groundwaters and the relationship between the deep and shallower systems, a hydrochemical study was undertaken involving 179 major and minor ion analyses, 39 stable isotope analyses (δD and δ¹⁸O), and 14 carbon isotope analyses (¹⁴C and δ¹³C). PHREEQC 3.0 was used to investigate mixing. Hydrochemical data support the presence of a well-connected regional flow system extending southwards from the more mountainous north. Stable isotope data indicate that the COC groundwaters originate as soil zone infiltration, under a much cooler regime than is found locally today. This is confirmed by ¹⁴C, which indicates the groundwater to be palaeowater recharged during the late Pleistocene (∼10–12 ka B.P.). The presence of nitrate in the COC groundwaters suggests leakage from overlying shallow aquifers currently provides an additional source of COC recharge, with major faults possibly providing the primary pathways for downward vertical flow.     

Sequential analysis of hydrochemical data for watershed characterization

A methodology for characterizing the hydrogeology of watersheds using hydrochemical data that combine statistical, geochemical, and spatial techniques is presented. Surface water and ground water base flow and spring runoff samples (180 total) from a single watershed are first classified using hierarchical cluster analysis. The statistical clusters are analyzed for spatial coherence confirming that the clusters have a geological basis corresponding to topographic flowpaths and showing that the fractured rock aquifer behaves as an equivalent porous medium on the watershed scale. Then principal component analysis (PCA) is used to determine the sources of variation between parameters. PCA analysis shows that the variations within the dataset are related to variations in calcium, magnesium, SO4, and HCO3, which are derived from natural weathering reactions, and pH, NO3, and chlorine, which indicate anthropogenic impact. PHREEQC modeling is used to quantitatively describe the natural hydrochemical evolution for the watershed and aid in discrimination of samples that have an anthropogenic component. Finally, the seasonal changes in the water chemistry of individual sites were analyzed to better characterize the spatial variability of vertical hydraulic conductivity. The integrated result provides a method to characterize the hydrogeology of the watershed that fully utilizes traditional data.     

A simulation of large‐scale groundwater flow and travel time in a fractured rock environment for waste disposal purposes

Two‐dimensional regional groundwater flow was simulated based on a conceptual model of low‐permeability crystalline rocks of the Whiteshell Research Area (WRA) in south‐eastern Manitoba. The conceptual model consists of fracture zones that strike in different directions and dip at various angles in the background rock mass. The thickness and hydraulic properties of the fracture zones in the conceptual model were varied as were the fluid properties and the boundary conditions of the groundwater flow system. The effects of these variations on the groundwater flow pattern and on the convective travel time along pathways from a hypothetical disposal vault at 500 m depth to discharge locations at the ground surface were evaluated. The vault was located in the regional discharge area of the groundwater system. A homogeneous conceptual model of the WRA, having only freshwater flow, formed a groundwater flow pattern with a regional flow system. Local flow systems developed increasingly with the introduction of fracture zones 20 m and 3 m thick, and depth‐dependent fluid density. This indicates a reduction in groundwater residence time by fracture zones and fluid density. Flow pathways were analysed using both a stream‐function and a particle‐tracking technique. The pathways and their lengths from the location of the vault to the surface varied spatially according to the flow patterns. The minimum travel time along these pathways was less than 150 000 and greater than 4 000 000 years in models with and without fracture zones, respectively, indicating that the presence of fracture zones was the major controlling factor. A precise knowledge and refinement of conceptual model parameters is necessary during site selection for waste disposal purposes. Copyright © 2004 John Wiley & Sons, Ltd.     

Regional changes in groundwater flow patterns and effects on groundwater composition

Wetlands on the Vecht river plain in the Netherlands are threatened by pollution of ground water on the adjacent ridge ‘Het Gooi’. To assess the impact of this pollution, information is needed on the present groundwater flow pattern and hydrochemical processes occurring during flow. In the determination of hydrochemical processes past changes in flow patterns must be taken into consideration.

Over the past 600 years impoldering and groundwater extraction have induced important hydrological changes in the study area. Exercises with a two-dimensional finite difference groundwater model were used to study the effects of these changes on regional groundwater flow patterns. Steady-state simulations along a vertical section were carried out for four different points in time, namely, the 14th century, 1885, 1941 and 1985. Changes in flow patterns are inferred from a comparison of the steady-state simulations. The results indicate that groundwater flow changed from a simple pattern under natural conditions to a complex flow pattern dominated by artificially man-controlled hydraulic heads at present.

The computer simulations are used to estimate the effect of changes in flow patterns on regional groundwater composition. Data on the distribution of chloride and oxygen-18 in ground water provide a verification of the estimated effects and information on the present position of the fresh-brackish groundwater interface in the study area. Isochrones calculated by the model are used to estimate the position of this front where data on water composition are absent. The future displacement of the fresh-brackish groundwater front is inferred from the position of successive isochrones, assuming that the present flow pattern will remain in steady state.

The computer simulations provide a general framework for the determination of hydrochemical processes in future studies addressing the impact of groundwater pollution on wetlands in the river plain.     

Effect of overpumping and irrigation stress on hydrochemistry and hydrodynamics of a Saharan oasis groundwater system

Stepwise hydrochemical and isotope-based methodology was adopted to identify mineralization processes, assess the impact of resources overexploitation and flood irrigation, and conceptualize groundwater hydrodynamics in the Djérid aquifer system, Tunisia. The study demonstrates that the main processes controlling groundwater geochemistry are dissolution of evaporates and phosphate-bearing rocks, cation exchange, mixing between high and low TDS end-members, and irrigation return flow. Interpretation of isotope data demonstrates that the deep aquifer was mostly recharged by late Pleistocene palaeowater, while the shallow aquifer is entirely recharged by return flow. The intermediate aquifer groundwater is actually a mixing of early to middle Holocene palaeowater, late Pleistocene deep aquifer palaeowater and return flow waters. The established conceptual model shows that deep and shallow groundwater leakages into the intermediate aquifer are enhanced by the presence of deep faults, the high hydraulic head of the deep aquifer, the overexploitation of the intermediate aquifer, and the long-term flood irrigation.     

Analysis of induced seismicity for stress field determination and pore pressure mapping

The focal mechanisms of some one hundred microseismic events induced by various water injections have been determined. Within the same depth interval, numerous stress measurements have been conducted with the HTPF method. When inverted simultaneously, the HTPF data and the focal plane solutions help determine the complete stress field in a fairly large volume of rock (about 15×10⁶ m³). These results demonstrate that hydraulically conductive fault zones are associated with local stress heterogeneities. Some of these stress heterogeneities correspond to local stress concentrations with principal stress magnitudes much larger than those of the regional stress field. They preclude the determination of the regional stress field from the sole inversion of focal mechanisms. In addition to determining the regional stress field, the integrated inversion of focal mechanisms and HTPF data help identify the fault plane for each for each of the focal mechanisms. These slip motions have been demonstrated to be consistent with Terzaghi's effective stress principle and a Coulomb friction law with a friction coefficient ranging from 0.65 to 0.9. This has been used for mapping the pore pressure in the rock mass. This mapping shows that induced seismicity does not outline zones of high flow rate but only zones of high pore pressure. For one fault zone where no significant flow has been observed, the local pore pressure has been found to be larger than the regional minimum principal stress but no hydraulic fracturing has been detected there.     

A hydrochemical approach to quantify the role of return flow in a surface flow‐dominated catchment

Stormflow generation in headwater catchments dominated by subsurface flow has been studied extensively, yet catchments dominated by surface flow have received less attention. We addressed this by testing whether stormflow chemistry is controlled by either (a) the event‐water signature of overland flow, or (b) the pre‐event water signature of return flow. We used a high‐resolution hydrochemical data set of stormflow and end‐members of multiple storms in an end‐member mixing analysis to determine the number of end‐members needed to explain stormflow, characterize and identify potential end‐members, calculate their contributions to stormflow, and develop a conceptual model of stormflow. The arrangement and relative positioning of end‐members in stormflow mixing space suggest that saturation excess overland flow (26–48%) and return flow from two different subsurface storage pools (17–53%) are both similarly important for stormflow. These results suggest that pipes and fractures are important flow paths to rapidly release stored water and highlight the value of within‐event resolution hydrochemical data to assess the full range and dynamics of flow paths.     

The use of isotopes in evolving groundwater circulation models of regional continental aquifers: The case of the Guarani Aquifer System

The Guarani Aquifer System (GAS) has been studied since the 1970s, a time frame that coincides with the advent of isotopic techniques in Brazil. The GAS isotope data from many studies are organized in different phases: (a) the advent of isotope techniques, (b) consolidation and new applications, (c) isotope assessments and hydrochemistry evolution, and (d) a roadmap to a new conceptual model. The reasons behind the phases, their methodological approaches, and impacts on the regional flow conceptual models are examined. Starting with local δ²H and δ¹⁸O assessments of values for water fingerprinting and estimates of recharge palaeoclimate scenarios, studies evolved to more integrated approaches based on multiple tracers. Stable isotope application techniques were consolidated during the 1980s, when new dating approaches dealing with radiogenic and heavy isotopes were introduced. Through the execution of an international transboundary project, the GAS was studied and extensively sampled for isotopes. These results have triggered wider application of isotope techniques, reflecting also world research trends. Presently, hydrochemical evolution models along flow lines from recharge to discharge areas, across large‐scale tectonic features within the entire sedimentary basin, are being combined with residence time estimates at GAS outcrop areas and deep confined units. In a complex system, it is normal that many, and even contradictory hypotheses are proposed, but isotope techniques provide a unique chance to test them. Stable isotope assessments are still needed near recharge areas, and they can be combined with groundwater classical dating procedures, complemented by newer techniques (³H‐³He, CFCs, and SF₆)_. Recent noble gas sampling and world pioneer analytical efforts focused on the confined units in the GAS will certainly led to new findings on the overall GAS circulation. The objective of this article is to discuss how isotope information can contribute to the evolution of conceptual groundwater flow models for regional continental aquifers, such as the GAS.     

Hydrogeochemical Evolution of Interaction Between Surface Water and Groundwater Affected by Exploitation

Hydrogeochemical evolution of interactions between surface water and groundwater is crucial for guaranteeing water supply quality in a riverside water source area. This study focuses on the seasonal and spatial characteristics of hydrogeochemical evolution affected by groundwater exploitation in the Hulan water source area using hydrochemical analyses and stable isotope tracers. Results show that the concentrations of major ions and total dissolved solids (TDS) increase considerably during the dry season. A bicarbonate water type is primarily produced by the dissolution of calcite, dolomite and gypsum, as well as the cation exchange and human activities. Along the typical infiltration path, the proportions of surface water increase with proximity to the river from 8%-63% during the wet season to 11%-84% during the dry season, which are attributed to an increased hydraulic gradient by exploitation. The typical path is classified into two zones. The first is the intensive mixing zone (within 1 km) with increasing concentrations of major ions and TDS due to mixing effect. The second is the exploitation influence zone (1-3.3 km) with increased concentrations of Ca²⁺, Mg²⁺, SO₄²⁻, and HCO₃⁻ during the dry season due to two reasons of seasonal variations in evaporation, stronger water-rock interactions and mixing effects with increased surface water by exploitation.