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.

Complex hydrogeological systems require detailed knowledge of aquifer dynamics to ensure appropriate and sustainable management of the groundwater resource. The Riardo Plain aquifer, southern Italy, is a strategic resource for conjunctive uses; nevertheless, the conceptual model still suffers some uncertainties due to the presence of a deep lateral inflow through the carbonate basement. Therefore, the realisation of a 3D numerical model at catchment scale needs preliminary tests to constrain the possible additional inflow rate, which is at the moment only estimated through the results of the groundwater budget calculation. A 2D section of the mixing area was modelled using FEFLOW in order to test the hypothesis of a combined recharge. Seven versions of the same model were calibrated over an increasing number of adjustable parameters according to their sensitivity. The most efficient model version was identified according to the calculated information criteria and the sum of squared-weighted residuals. In the second phase of the work, nine model scenarios characterised by different deep inflow rates were calibrated and validated according to the same procedure of the first model, in order to identify the range of possible acceptable solutions. The most likely deep inflow rate is 34 ± 4% of the total recharge, corresponding to an estimated deep inflow of 415 ± 50 L/s in the Riardo Plain aquifer through the carbonate basement. This methodological approach will be the basis of following numerical 3D numerical models of the Riardo Plain and can be a valuable tool in conceptualising similar mineral water areas.

Health issues related to aquifer contamination with perchlorate are a growing concern in drinking water management. This study describes perchlorate transport and degradation processes from a contaminated stream toward drinking water pumping wells. Investigations are based on laboratory experiments and field measurements conducted at a well field near Bordeaux (France) in a heterogeneous carbonate aquifer interacting with a stream. Field measurements facilitated the characterization of perchlorate contamination and stream-to-aquifer flow. Experiments on columns of streambed sediments conducted in the laboratory confirmed that perchlorate had been degraded in the hyporheic zone. A one-dimensional reactive transport model was implemented to estimate Monod kinetic rates, which account for the inhibition of perchlorate degradation by nitrate. The estimated half-saturation constant for perchlorate [Formula: see text]) is 6.93 10⁻⁹ mol L⁻¹ and the estimated maximum specific degradation rate ([Formula: see text]) ranges between 10⁻⁵ and 4.0 10⁻³ mol L⁻¹ day⁻¹. Despite degradation in the hyporheic zone, perchlorate-contaminated stream water reaches drinking-water-production units. Such contamination highlights the effects of preferential flow paths between the stream and the pumping wells and significant hydraulic gradients caused by drawdowns. In such contexts, in spite of a good potential for degradation, riverbank filtration may not be effective for the protection of drinking water wells. Lessons from this study also reveal that contamination monitoring can be misleading: low concentrations can be reported in monitoring wells between the contaminant source and the production wells, but the latter may yet be contaminated.

Application of the gravity-driven regional groundwater flow (GDRGF) concept to the hydrogeologically complex thick carbonate system of the Transdanubian Range (TR), Hungary, is justified based on the principle of hydraulic continuity. The GDRGF concept informs about basin hydraulics and groundwater as a geologic agent. It became obvious that the effect of heterogeneity and anisotropy on the flow pattern could be derived from hydraulic reactions of the aquifer system. The topography and heat as driving forces were examined by numerical simulations of flow and heat transport. Evaluation of groups of springs, in terms of related discharge phenomena and regional chloride distribution, reveals the dominance of topography-driven flow when considering flow and related chemical and temperature patterns. Moreover, heat accumulation beneath the confined part of the system also influences these patterns. The presence of cold, lukewarm and thermal springs and related wetlands, creeks, mineral precipitates, and epigenic and hypogenic caves validates the existence of GDRGF in the system. Vice versa, groups of springs reflect rock–water interaction and advective heat transport and inform about basin hydraulics. Based on these findings, a generalized conceptual GDRGF model is proposed for an unconfined and confined carbonate region. An interface was revealed close to the margin of the unconfined and confined carbonates, determined by the GDRGF and freshwater and basinal fluids involved. The application of this model provides a background to interpret manifestations of flowing groundwater in thick carbonates generally, including porosity enlargement and hydrocarbon and heat accumulation.

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.

³H, δ¹³C and hydrochemical data were used to estimate the corrected groundwater age derived from conventional ¹⁴C age of dissolved inorganic carbon (DIC). The Middle-Upper Devonian aquifer system from the Baltic upland recharge area in eastern Lithuania towards the discharge area on the Baltic Sea coast in the west was considered. The concentration of total dissolved solids (TDS) in groundwater changes from 300 to 24,000 mg/L and increases downgradient towards the coast. The other major constituents have the same trend as the TDS. The hydrochemical facies of groundwater vary from an alkali-earth carbonates facies at the eastern upland area to an alkali-earth carbonate-sulfate and chloride facies at transit and discharge areas. Meteoric water percolating through the Quaternary and Devonian aquifers regulate the initial ¹⁴C activities of groundwater involving two main members of DIC: soil CO₂ with modern ¹⁴C activity uptake and dissolution of ¹⁴C-free aquifer carbonates. Other sources of DIC are less common. ¹⁴C activity of DIC in the groundwater ranged from 60 to 108 pMC at the shallow depths. With an increase of the aquifers depth the dolomitization of aqueous solution and leakage of the “old” groundwater from lower aquifers take place, traced by lower activities (7–30 pMC).

Groundwater flow and the geochemical evolution of a freshwater lens in an aquifer on a Pacific atoll were investigated by hydrogeochemical surveys. Sulfur hexafluoride measurements showed that deeper groundwater and groundwater at the periphery of the lens are older, consistent with a downward and outward groundwater flow scheme. This is the typical flow scheme on Pacific atolls where a Holocene–Pleistocene unconformity restricts the shape of the freshwater lens. Enrichment of Mg/Ca in the groundwater is another indicator of a longer residence time, because contact between the groundwater and the carbonate sediments composing the aquifer leads to the release of Mg from high-Mg calcite and the precipitation of Ca as low-Mg calcite. Groundwater quality was also affected by anthropogenic nitrogen loading and aboveground organic matter, which were altered by denitrification and sulfate reduction in the aquifer, especially in the older groundwater. The chemical composition of the groundwater in the center of the island, where saline water is up-coning, implies that freshwater recharge dilutes the older saline water, which as time passes will eventually be replaced by newly recharged freshwater.

Shallow groundwater is the main source for drinking water in Kabul, Afghanistan. It comes from a multitude of shallow hand-pumped wells spread over the whole city area. The groundwater is characterised by slightly oxic redox conditions. Interactions with aquifer carbonates lead to near-neutral pH and high degrees of hardness. The mostly negative water budget of the Kabul Basin is the result of strong evaporation which leads to an increase in salt and also of some undesirable constituents, e.g. borate. Several years of drought have aggravated this problem. The shallow groundwater in the city has received tremendous amounts of pollution due to a lack of proper waste disposal and sewage treatment. Common indicators are elevated concentrations of nutrients such as nitrate and faecal bacteria. The high infant mortality can at least partially be attributed to the insufficient water hygiene. Acid generated during the mineralisation of the wastewater is hidden due to the strong pH buffering capacity of the groundwater system. Redox and pH conditions preclude significant mobilisation of trace metals and metalloids.

Stable hydrogen and oxygen isotope signatures of waters within Church and Inkwell blue holes are measured on San Salvador Island (Bahamas) to identify the origin of their fresh and saline waters. Stable isotope data, paired with a suite of physicochemical water parameters measured throughout the blue holes, as a function of both time and depth, provide a detailed understanding of the tidally influenced groundwater interactions on the island. Blue holes are prominent karst features in carbonate environments which serve as windows into subterranean hydrologic processes. Carbonate island hydrology is often complicated by complex interactions between the marine and meteoric water systems, as tidal pumping and water mixing result in diagenetic alteration of the bedrock, that in turn influence dissolution rates and preferential flow paths. Although the blue holes on the island are physically influenced by tidal forcing, the stable isotope data indicate that both their fresh and saline waters are of a meteoric origin rather than seawater, where the meteoric water is likely becoming saline through enrichment by aerosol-derived sea salts. Additionally, the physical profiles of each blue hole indicate differences in mixing processes driven by wind and tidal forcing, where stronger mixing can result in a disruption of the freshwater lens. The implications of this study are important for assessing mixing corrosion processes and dissolution effects, but more research and longer data sets are needed to show whether these results are applicable to other coastal carbonate environments.

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.