Naturally occurring arsenic in groundwater and identification of the geochemical sources in the Duero Cenozoic Basin, Spain

Arsenic concentrations surpassing potability limit of 10 μg/L in the groundwater supplies of an extensive area in the Duero Cenozoic Basin (central Spain) have been detected and the main sources of arsenic identified. Arsenic in 514 samples of groundwater, having mean values of 40.8 μg/L, is natural in origin. Geochemical analysis of 553 rock samples, assaying arsenic mean values of 23 mg/kg, was performed. Spatial coincidence between the arsenic anomaly in groundwater and the arsenic lithogeochemical distribution recorded in the Middle Miocene clayey organic-rich Zaratan facies illustrates that the rocks of this unit are the main source of arsenic in groundwater. The ferricretes associated to the Late Cretaceous–Middle Miocene siliciclastics also constitute a potential arsenic source. Mineralogical study has identified the presence of arsenic in iron oxides, authigenic pyrite, manganese oxides, inherited titanium–iron oxides, phyllosilicates and organomineral compounds. Arsenic mobilization to groundwater corresponds to arsenic desorption from iron and manganese oxides and from organic matter.