The Agua Negra drainage system (30 12'S, 69 50' W), in the Argentine Andes holds several ice- and rock-glaciers, which are distributed from 4200 up to 6300 m a.s.l. The geochemical study of meltwaters reveals that ice-glaciers deliver a HCO₃⁻----Ca²⁺ solution and rock-glaciers a SO₄²⁻----HCO₃⁻----Ca²⁺ solution. The site is presumably strongly influenced by sublimation and dry deposition. The main processes supplying solutes to meltwater are sulphide oxidation (i.e. abundant hydrothermal manifestations), and hydrolysis and dissolution of carbonates and silicates. Marine aerosols are the main source of NaCl. The fine-grained products of glacial comminution play a significant role in the control of dissolved minor and trace elements: transition metals (e.g. Mn, Zr, Cu, and Co) appear to be selectively removed from solution, whereas some LIL (large ion lithophile) elements, such as Sr, Cs, and major cations, are more concentrated in the lowermost reach. Daily concentration variation of dissolved rare earth elements (REE) tends to increase with discharge. Through PHREEQC inverse modelling, it is shown that gypsum dissolution (i.e. sulphide oxidation) is the most important geochemical mechanism delivering solutes to the Agua Negra drainage system, particularly in rock-glaciers. At the lowermost reach, the chemical signature appears to change depending on the relative significance of different meltwater sources: silicate weathering seems to be more important when meltwater has a longer residence time, and calcite and gypsum dissolution is more conspicuous in recently melted waters. A comparison with a non-glacierized semiarid drainage of comparable size shows that the glacierized basin has a higher specific denudation, but it is mostly accounted for by relatively soluble phases (i.e. gypsum and calcite). Meltwater chemistry in glacierized arid areas appears strongly influenced by sublimation/evaporation, in contrast with its humid counterparts.

What is the source of geogenic (natural or native) solutes in groundwater? The orthodox explanation suggests it is largely a function of water–rock interaction (weathering of the soil zone and aquifer mineral framework). It is proposed herein that atmospheric deposition (combination of wet and dry aerosols from ocean spray, smoke, volcanoes, continental dust, and lightning) is a significant source, and in many cases the dominant source, of the major and minor geogenic solutes in groundwater. Solute mass-balance analyses suggest that much of the mass of major and minor ions must be transported into the aquifer from an external source. Example case studies are presented: analysis of groundwater in a coastal marine aquifer located in an arid area (United Arab Emirates) suggests that over 50% of several major ions potentially originate from atmospheric deposition; in an alluvial fan in a semi-arid system (High Plains, USA), 100% of most solutes potentially originate from atmospheric deposition; and in a humid glacial aquifer system (Michigan, USA), 20–30% of many major ions are potentially from atmospheric deposition. These observations contrast with many hydrogeologic textbooks, which still propose the origin to be water–rock interaction—hence, the myth.

Lake water, river water, and groundwater from the Lake Qinghai catchment in the northeastern Tibetan Plateau, China have been analyzed and the results demonstrate that the chemical components and ⁸⁷Sr/⁸⁶Sr ratios of the waters are strictly constrained by the age and rock types of the tributaries, especially for groundwater. Dissolved ions in the Lake Qinghai catchment are derived from carbonate weathering and part from silicate sources. The chemistry of Buha River water, the largest tributary within the catchment, underlain by the late Paleozoic marine limestone and sandstones, constrains carbonate-dominated compositions of the lake water, being buffered by the waters from the other tributaries and probably by groundwater. The variation of ⁸⁷Sr/⁸⁶Sr ratios with cation concentrations places constraint on the Sr-isotopic compositions of the main subcatchments surrounding Lake Qinghai. The relative significance of river-water sources from different tributaries (possibly groundwater as well) in controlling the Sr distribution in Lake Qinghai provides the potential to link the influence of hydrological processes to past biological and physical parameters in the lake. The potential role of groundwater input in the water budget and chemistry of the lake emphasizes the need to further understand hydrogeological processes within the Lake Qinghai system.

Hydrogeochemical analysis and multivariate statistics were applied to identify flow patterns and major processes controlling the hydrogeochemistry of groundwater in the Jianghan Plain, which is located in central Yangtze River Basin (central China) and characterized by intensive surface-water/groundwater interaction. Although HCO₃-Ca-(Mg) type water predominated in the study area, the 457 (21 surface water and 436 groundwater) samples were effectively classified into five clusters by hierarchical cluster analysis. The hydrochemical variations among these clusters were governed by three factors from factor analysis. Major components (e.g., Ca, Mg and HCO₃) in surface water and groundwater originated from carbonate and silicate weathering (factor 1). Redox conditions (factor 2) influenced the geogenic Fe and As contamination in shallow confined groundwater. Anthropogenic activities (factor 3) primarily caused high levels of Cl and SO₄ in surface water and phreatic groundwater. Furthermore, the factor score 1 of samples in the shallow confined aquifer gradually increased along the flow paths. This study demonstrates that enhanced information on hydrochemistry in complex groundwater flow systems, by multivariate statistical methods, improves the understanding of groundwater flow and hydrogeochemical evolution due to natural and anthropogenic impacts.

Influences of hydraulic conductivity (K) heterogeneities on bedrock groundwater (BG) flow systems in mountainous topography are investigated using a conceptual 2D numerical modelling approach. A conceptual model for K heterogeneity in crystalline bedrock mountainous environments is developed based on a review of previous research, and represents heterogeneities due to weathering profile, bedrock fracture characteristics, and catchment-scale (∼0.1–1 km) structural features. Numerical groundwater modelling of K scenarios for hypothetical mountain catchment topography indicates that general characteristics of the BG flow directions are dominated by prominent topographic features. Within the modelled saturated BG flow system, ∼90 % or more of total BG flux is focussed within a fractured bedrock zone, extending to depths of ∼100–200 m below the ground surface, overlying lower-K bedrock. Structural features and heterogeneities, represented as discrete zones of higher or lower K relative to surrounding bedrock, locally influence BG flow, but do not influence general BG flow patterns or general positions of BG flow divides. This result is supported by similar BG transit-time distribution shapes and statistics for systems with and without structural features. The results support the development of topography-based methods for predicting general locations of BG flow-system boundaries in mountain regions.

Geochemical and isotopic characterization of groundwater and lake-water samples were combined with water and total dissolved solids balances to evaluate sources of groundwater quality deterioration in eastern Hetao Basin, Inner Mongolia, China. Groundwater quality is poor; 11 of 13 wells exceed drinking-water guidelines for at least one health-based parameter and all wells exceed aesthetic guidelines. The well water is largely derived from Yellow River irrigation water. Notably high uranium concentrations in the Yellow River, relative to world rivers, suggest groundwater uranium and other trace elements may originate in the river-derived irrigation water. Complex hydrostratigraphy and spatial variation in groundwater recharge result in spatially complex groundwater flow and geochemistry. Evapotranspiration of irrigation water causes chloride concentration increases of up to two orders of magnitude in the basin, notably in shallow groundwater around Wuliangsuhai Lake. In addition to evapotranspiration, groundwater quality is affected by mineral precipitation and dissolution, silicate weathering, and redox processes. The lake-water and TDS balances suggest that a small amount of discharge to groundwater (but associated with very high solute concentrations) contributes to groundwater salinization in this region. Increasing salinity in the groundwater and Wuliangsuhai Lake will continue to deteriorate water quality unless irrigation management practices improve.

Hydrogeochemistry and environmental isotopes were used to gain insight into the recharge processes, water–rock interactions, and groundwater residence time, and to identify groundwater flow systems (GFSs) in an interfluve between the Han River and Yangtze River in the eastern Jianghan Plain (China), an alluvial-lacustrine plain in the middle reaches of the Yangtze River. Because of carbonate mineral weathering, groundwater in the plain is predominantly HCO₃-Ca or HCO₃-Ca-Mg type. The decrease in typical ions and isotopic depletion with increasing depth indicates that the GFSs were divided into local and regional GFSs with an approximate depth limitation of 20 m. The consistent variations are attributable to complex anthropogenic activities, water–rock interactions and groundwater flow patterns. The multiple independent local GFSs exhibited a pattern in which groundwater was discharged into surface waters during the non-flood season. Groundwater age of local GFSs is modern according to the ³H concentrations, so the hydrodynamic circulation is active. Furthermore, the regional GFS pattern is controlled by slow lateral flow from west or northwest to east, eventually discharging into the Yangtze and Han rivers. The distribution of δ¹⁸O indicated three zones in regional GFSs that are likely dominated by the altitude effect of recharge areas. The groundwater age of regional GFSs varied from hundreds of years to 5000 years, estimated by ¹⁴C isotope data, revealing that the hydrodynamic circulation of regional GFSs is slow to relatively stagnant. The hydrodynamic characteristics and hydrochemical distributions corroborated the mixing zones of differently hierarchical GFSs in the discharge area of the Jianghan Plain.

A preliminary conceptual model of groundwater flow was developed for the Serra Geral fractured basalt aquifer in order to assess the recharge to the underlying sandstone Guarani Aquifer System, one of the main aquifer systems in Brazil, which supplies water to millions of people. Detailed geological investigations included macroscopic description of the basalt flow units and the underlying sandstone. Petrographic and chemical analyzes were conducted on rock samples from outcrops and from five drilled boreholes. Detailed fracture surveys were accomplished at outcrops to characterize fracture sets and their potential to transmit water in the current tectonic context. Four basalt flows were identified in the Ribeirao Preto area and were named B1, B2, B3 and B4 (from oldest to youngest). The cooling process in flow B3 led to the generation of large sub-horizontal fractures at the contacts B2/B3 and B3-C/B3-E, which are the most transmissive structures. Groundwater flow in the basalt appears to be of the stratabound type because fractures, in general, do not propagate through the basalt vesicular layers, which behave as a regional hydraulic barrier for the vertical groundwater flow. However, it is proposed that the localized, continuous and closely spaced subvertical tectonic fractures, the only features that have the potential to crosscut the vesicular layers and the intertrappe sediments, can vertically connect the sub-horizontal transmissive fractures. Weathering and water seepage, observed in rock exposures, indicate that subvertical NE-trending fractures would be the most transmissive in the Ribeirao Preto area.

A numerical groundwater model of the weathered crystalline aquifer of Ursuya (a major water source for the north-western Pyrenees region, south-western France) has been computed based on monitoring of hydrological, hydrodynamic and meteorological parameters over 3 years. The equivalent porous media model was used to simulate groundwater flow in the different layers of the weathered profile: from surface to depth, the weathered layer (5 · 10⁻⁸ ≤ K ≤ 5 · 10⁻⁷ m s⁻¹), the transition layer (7 · 10⁻⁸ ≤ K ≤ 1 · 10⁻⁵ m s⁻¹, the highest values being along major discontinuities), two fissured layers (3.5 · 10⁻⁸ ≤ K ≤ 5 · 10⁻⁴ m s⁻¹, depending on weathering profile conditions and on the existence of active fractures), and the hard-rock basement simulated with a negligible hydraulic conductivity (K = 1 10 ⁻⁹). Hydrodynamic properties of these five calculation layers demonstrate both the impact of the weathering degree and of the discontinuities on the groundwater flow. The great agreement between simulated and observed hydraulic conditions allowed for validation of the methodology and its proposed use for application on analogous aquifers. With the aim of long-term management of this strategic aquifer, the model was then used to evaluate the impact of climate change on the groundwater resource. The simulations performed according to the most pessimistic climatic scenario until 2050 show a low sensitivity of the aquifer. The decreasing trend of the natural discharge is estimated at about −360 m³ y⁻¹ for recharge decreasing at about −5.6 mm y⁻¹ (0.8 % of annual recharge).