Sources and controls for the mobility of arsenic in oxidizing groundwaters from loess-type sediments in arid/semi-arid dry climates - evidence from the Chaco-Pampean plain (Argentina).

In oxidizing aquifers, arsenic (As) mobilization from sediments into groundwater is controlled by pH-dependent As desorption from and dissolution of mineral phases. If climate is dry, then the process of evaporative concentration contributes further to the total concentration of dissolved As. In this paper the principal As mobility controls under these conditions have been demonstrated for Salí River alluvial basin in NW Argentina (Tucumán Province; 7000 km(2)), which is representative for other basins or areas of the predominantly semi-arid Chaco-Pampean plain (1,000,000 km(2)) which is one of the world's largest regions affected by high As concentrations in groundwater. Detailed hydrogeochemical studies have been performed in the Salí River basin where 85 groundwater samples from shallow aquifers (42 samples), deep samples (26 samples) and artesian aquifers (17 samples) have been collected. Arsenic concentrations range from 11.4 to 1660 μg L(-1) leaving 100% of the investigated waters above the provisional WHO guideline value of 10 μg L(-1). A strong positive correlation among As, F, and V in shallow groundwaters was found. The correlations among those trace elements and U, B and Mo have less significance. High pH (up to 9.2) and high bicarbonate (HCO(3)) concentrations favour leaching from pyroclastic materials, including volcanic glass which is present to 20-25% in the loess-type aquifer sediments and yield higher trace element concentrations in groundwater from shallow aquifers compared to deep and artesian aquifers. The significant increase in minor and trace element concentrations and salinity in shallow aquifers is related to strong evaporation under semi-arid climatic conditions. Sorption of As and associated minor and trace elements (F, U, B, Mo and V) onto the surface of Fe-, Al- and Mn-oxides and oxi-hydroxides, restricts the mobilization of these elements into groundwater. Nevertheless, this does not hold in the case of the shallow unconfined groundwaters with high pH and high concentrations of potential competitors for adsorption sites (HCO(3), V, P, etc.). Under these geochemical conditions, desorption of the above mentioned anions and oxyanions occurs as a key process for As mobilization, resulting in an increase of minor and trace element concentrations. These geochemical processes that control the concentrations of dissolved As and other trace elements and which determine the groundwater quality especially in the shallow aquifers, are comparable to other areas with high As concentrations in groundwater of oxidizing aquifers and semi-arid or arid climate, which are found in many parts of the world, such as the western sectors of the USA, Mexico, northern Chile, Turkey, Mongolia, central and northern China, and central and northwestern Argentina.