Elevated Arsenic (As) and Fluoride (F) concentrations in groundwater have been studied in the shallow aquifers of northeastern of La Pampa province, in the Chaco-Pampean plain, Argentina. The source of As and co-contaminants is mainly geogenic, from the weathering of volcanic ash and loess (rhyolitic glass) that erupted from the Andean volcanic range. In this study we have assessed the groundwater quality in two semi-arid areas of La Pampa. We have also identified the spatial distribution of As and co-contaminants in groundwater and determined the major factors controlling the mobilization of As in the shallow aquifers. The groundwater samples were circum-neutral to alkaline (7.4 to 92), oxidizing (Eh similar to 0.24 V) and characterized by high salinity (EC = 456-11,400 mu S/cm) and Na+-HCO3- water types in recharge areas. Carbonate concretions ("tosca") were abundant in the upper layers of the shallow aquifer. The concentration of total As (5.6 to 535 mu g/L) and F (0.5 to 14.2 mg/L) were heterogeneous and exceeded the recommended WHO Guidelines and the Argentine Standards for drinking water. The predominant As species were arsenate As(V) oxyanions, determined by thermodynamic calculations. Arsenic was positively correlated with bicarbonate (HCO3-), fluoride (F), boron (B) and vanadium (V), but negatively correlated with iron (Fe), aluminium (Al), and manganese (Mn), which were present in low concentrations. The highest amount of As in sediments was from the surface of the dry lake. The mechanisms for As mobilization are associated with multiple factors: geochemical reactions, hydrogeological characteristics of the local aquifer and climatic factors. Desorption of As(V) at high pH, and ion competition for adsorption sites are considered the principal mechanisms for As mobilization in the shallow aquifers. In addition, the long-term consumption of the groundwater could pose a threat for the health of the local community and low cost remediation techniques are required to improve the drinking water quality.