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

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Abstract

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.

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Acknowledgments

This work has been carried out through a Mobility Fellowship for Senior Researchers and Professors Program, and granted by the Education Ministry (Spanish Government). PLS participates with partial funding from the Natural Environment Research Council. We acknowledge the Ministerio de Medio Ambiente, Medio Rural y Marino (MARM) for providing their groundwater chemistry data for boreholes in the Duero Basin. We also acknowledge laboratory staff from IGME and BGS for carrying out chemical analysis of groundwater samples, and from the University of Valladolid for analysis of arsenic species. EGF acknowledges the help of a number of IGME and external colleagues during the course of the conduct of this research. Co-workers from Salamanca Unit of IGME provided useful geological, mineralogical and tectonic information. Finally, sincere thanks go to José Luis Simón Gómez from the University of Zaragoza for advice on tectonic structures, and Javier Sánchez San Román, from the University of Salamanca, for advice on the hydrogeology of the area.

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  1. Instituto Geológico y Minero de España – IGME, Unidad de Salamanca, Calle Azafranal 48, 37001, Salamanca, Spain

    Elena Giménez-Forcada

  2. British Geological Survey – BGS, Keyworth, Nottingham, NG12 5GG, UK

    Pauline L. Smedley

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  1. Elena Giménez-Forcada
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Correspondence to Elena Giménez-Forcada.

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Giménez-Forcada, E., Smedley, P.L. Geological factors controlling occurrence and distribution of arsenic in groundwaters from the southern margin of the Duero Basin, Spain. Environ Geochem Health 36, 1029–1047 (2014). https://doi.org/10.1007/s10653-014-9599-2

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