Analysis of the geological control on the spatial distribution of potentially toxic concentrations of As and F- in groundwater on a Pan-European scale.

The distribution of the high concentrations of arsenic (As) and fluoride (F-) in groundwater on a Pan-European scale could be explained by the geological European context (lithology and structural faults). To test this hypothesis, seventeen countries and eighteen geological survey organizations (GSOs) have participated in the dataset. The methodology has used the HydroGeoToxicity (HGT) and the Baseline Concentration (BLC) index. The results prove that most of the waters considered in this study are in good conditions for drinking water consumption, in terms of As and/or F- content. A low proportion of the analysed samples present HGT≥ 1 levels (4% and 7% for As and F-, respectively). The spatial distribution of the highest As and/or F- concentrations (via BLC values) has been analysed using GIS tools. The highest values are identified associated with fissured hard rock outcrops (crystalline rocks) or Cenozoic sedimentary zones, where basement fractures seems to have an obvious control on the distribution of maximum concentrations of these elements in groundwaters.

Characterization of regional cold-hydrothermal inflows enriched in arsenic and associated trace-elements in the southern part of the Duero Basin (Spain), by multivariate statistical analysis.

Naturally occurring arsenic in groundwater exceeding the limit for potability has been reported along the southern edge of the Cenozoic Duero Basin (CDB) near its contact with the Spanish Central System (SCS). In this area, spatial variability of arsenic is high, peaking at 241µg/L. Forty-seven percent of samples collected contained arsenic above the maximum allowable concentration for drinking water (10µg/L). Correlations of As with other hydrochemical variables were investigated using multivariate statistical analysis (Hierarchical Cluster Analysis, HCA and Principal Component Analysis, PCA). It was found that As, V, Cr and pH are closely related and that there were also close correlations with temperature and Na+. The highest concentrations of arsenic and other associated Potentially Toxic Geogenic Trace Elements (PTGTE) are linked to alkaline NaHCO3 waters (pH≈9), moderate oxic conditions and temperatures of around 18°C-19°C. The most plausible hypothesis to explain the high arsenic concentrations is the contribution of deeper regional flows with a significant hydrothermal component (cold-hydrothermal waters), flowing through faults in the basement rock. Water mixing and water-rock interactions occur both in the fissured aquifer media (igneous and metasedimentary bedrock) and in the sedimentary environment of the CDB, where agricultural pollution phenomena are also active. A combination of multivariate statistical tools and hydrochemical analysis enabled the distribution pattern of dissolved As and other PTGTE in groundwaters in the study area to be interpreted, and their most likely origin to be established. This methodology could be applied to other sedimentary areas with similar characteristics and problems.

Algae metabolism and organic carbon in sediments determining arsenic mobilisation in ground- and surface water. A field study in Doñana National Park, Spain.

A study has been performed to explore the origin, spatiotemporal behaviour and mobilisation mechanism of the elevated arsenic (As) concentrations found in ground water and drinking ponds of the Doñana National Park, Southern Spain. At a larger scale, 13 piezometers and surface water samples of about 50 artificial drinking ponds and freshwater lagoons throughout the National Park were collected and analysed for major ions, metals and trace elements. At a smaller scale, 5 locations were equipped with piezometers and groundwater was sampled up to 4 times for ambient parameters, major ions, metals, trace elements and iron (Fe) speciation. As was analysed for inorganic and organic speciation. Undisturbed sediment samples were analysed for physical parameters, mineralogy, geochemistry as well as As species. Sediment analyses yielded total As between 0.1 and 18 mg/kg and are not correlated with As concentration in water. Results of the surface- and groundwater sampling revealed elevated concentration of As up to 302 µg/L within a restricted area of the National Park. Results of groundwater sampling reveals strong correlation of As with Fe(2+) pointing to As mobilisation due to reductive dissolution of hydroferric oxides (HFO) in areas of locally elevated amounts of organic matter within the sediments. High As concentrations in surface water ponds are correlated with elevated alkalinity and pH attributed to algae metabolism, leading to As desorption from HFO. The algae metabolism is responsible for the presence of methylated arsenic species in surface water, in contrast to ground water in which only inorganic As species was found. Temporal variations in surface water and groundwater are also related to changes in pH and alkalinity as a result of enhanced algae metabolism in surface water or related to changes in the redox level in the case of groundwater.

Arsenic, barium, strontium and uranium geochemistry and their utility as tracers to characterize groundwaters from the Espadán-Calderona Triassic Domain, Spain.

A set of analytical data from the Espadán-Calderona Triassic Domain aquifers was processed using hierarchical agglomerative cluster analysis (HCA) and principal component analysis (PCA), to achieve a quantitative and independent approach to investigate the characteristics of groundwater composition and possible differences between groundwater flows from Triassic aquifers from the Espadán-Calderona Triassic Domain (Spain). Mineralization in the Triassic series has led to the presence of several metals and metalloids in groundwater, including As, Mn, Fe and U. These are associated with fresher bicarbonate groundwaters, characterized by lower Sr/Ba ratios. Levels containing sulfate evaporitic salt, which are interbedded through the Triassic series, seem to exert a strong influence on the chemistry of several groundwaters, characterized by calcium sulfate facies with high Sr concentration and high Sr/Ba ratios. The application of multivariate statistical techniques to the interpretation of analytical results allows the differentiation of groundwater types occurring in the Triassic aquifers and identification of the role of a number of minor or trace elements and their ratios that can be treated as hydrogeochemical tracers. With them it was possible to correlate the different recharge waters with the tectonic morphology of the Espadán-Calderona Triassic Domain.

An Excel Macro to Plot the HFE-Diagram to Identify Sea Water Intrusion Phases.

A hydrochemical facies evolution diagram (HFE-D) is a multirectangular diagram, which is a useful tool in the interpretation of sea water intrusion processes. This method note describes a simple method for generating an HFE-D plot using the spreadsheet software package, Microsoft Excel. The code was applied to groundwater from the alluvial coastal plain of Grosseto (Tuscany, Italy), which is characterized by a complex salinization process in which sea water mixes with sulfate or bicarbonate recharge water.

Geological factors controlling occurrence and distribution of arsenic in groundwaters from the southern margin of the Duero Basin, Spain.

Groundwater from springs and boreholes on the southern edge of the Cenozoic Duero Basin (DB) of Spain has concentrations of arsenic (As) which are commonly above the EC drinking-water limit of 10 µg/L and reach observed values up to 241 µg/L. Groundwater compositions within the sedimentary aquifer vary from Ca-HCO3 type, variably affected by evaporation and agricultural pollution at shallow levels, to Na-HCO3 compositions in deeper boreholes of the basin. Groundwater conditions are mainly oxidising, but reducing groundwaters exist in sub-basins within the aquifer, localised flow paths likely being influenced by basement structure. Arsenic concentrations are spatially variable, reaching up to 38 µg/L in springs of the Spanish Central System (SCS) basement aquifer and up to 62 µg/L in springs from the DB. Highest As concentrations are associated with the Na-HCO3 compositions in deep boreholes (200-450 m depth) within the DB. These have high pH values (up to 9.6) which can give rise to associated elevated concentrations of V and U (up to 64 and 30 µg/L, respectively). In the deep borehole waters of the DB, oxidising flows derived from the mineralised igneous-metamorphic basement and discharging via major faults, and are considered the origin of the higher concentrations. Compositions are consistent with desorption of As and other anionic species from metal oxyhydroxides in an oxic environment. Under locally reducing conditions prevalent in some low-flow parts of the DB, an absence of detectable dissolved As is coincident with low or undetectable SO4 concentrations, and consistent with loss via formation of authigenic sulphide minerals. Mitigation measures are needed urgently in this semi-arid region where provision of alternative sources of safe drinking water is logistically difficult and expensive.

Dynamic of sea water interface using hydrochemical facies evolution diagram.

assignment of hydrochemical facies identifies whether the aquifer is in the phase of sea water intrusion or freshening, indicating the status of the aquifer in terms of the advance or regression of the saline front. A new multi-rectangular diagram is proposed that aids interpretation of these important processes through the representation and evolution of hydrochemical facies (hydrochemical facies evolution diagram, HFE-D). As an example, the HEF-D is applied to an alluvial aquifer in the Vinaroz-Peñíscola Plain (Spain), where Ca-Cl facies characterize the sea water intrusion phase, while Na-MixHCO(3)/MixSO(4) facies characterize a freshening stage.

Hydrogeochemical considerations about the origin of groundwater salinization in some coastal plains of Elba Island (Tuscany, Italy).

Several coastal plains of the Elba Island (Marina di Campo, Portoferraio, Schiopparello, Mola, Porto Azzurro and Barbarossa plains) in Tuscany (Italy) were studied to determine the causes of decline in groundwater quality, using major ion chemistry to establish the causes of groundwater salinization. The study demonstrates that salinization of coastal plain alluvial aquifers is not simply linked to seawater intrusion but is also intimately related to inflows from adjacent aquifers. Ionic ratios, correlation graphs and distribution value maps were employed as the means to understand the hydrochemistry of the study areas. The Mg/Cl ratio in particular can be considered a good tracer to distinguish the main salinization processes that control groundwater chemistry. Seawater intrusion only partly determines the chemistry of some groundwaters, which generally belong to a chloride facies where the salinity is derived principally from freshwater-seawater mixing and the participation of cation exchange. Proceeding inland groundwater quality seems to be principally determined by the inflow of Mg, Ca-HCO(3) or Ca, Na-HCO(3) waters formed from the weathering of silicate minerals in adjoining aquifers. Hydrolysis of these minerals is of prime importance in controlling groundwater chemistry in adjacent alluvial plains. The lateral recharge flows introduce water with a different chemical composition and this variable of freshwater recharge changes the hydrochemistry as a result of mixing between two or more waters types. This situation is further complicated when seawater and base exchange reactions participate, due to seawater intrusion.