Mobilization of arsenic and other trace elements of health concern in groundwater from the Salí River Basin, Tucumán Province, Argentina.

The Salí River Basin in north-west Argentina (7,000 km(2)) is composed of a sequence of Tertiary and Quaternary loess deposits, which have been substantially reworked by fluvial and aeolian processes. As with other areas of the Chaco-Pampean Plain, groundwater in the basin suffers a range of chemical quality problems, including arsenic (concentrations in the range of 12.2-1,660 µg L(-1)), fluoride (50-8,740 µg L(-1)), boron (34.0-9,550 µg L(-1)), vanadium (30.7-300 µg L(-1)) and uranium (0.03-125 µg L(-1)). Shallow groundwater (depths up to 15 m) has particularly high concentrations of these elements. Exceedances above WHO (2011) guideline values are 100% for As, 35% for B, 21% for U and 17% for F. Concentrations in deep (>200 m) and artesian groundwater in the basin are also often high, though less extreme than at shallow depths. The waters are oxidizing, with often high bicarbonate concentrations (50.0-1,260 mg L(-1)) and pH (6.28-9.24). The ultimate sources of these trace elements are the volcanic components of the loess deposits, although sorption reactions involving secondary Al and Fe oxides also regulate the distribution and mobility of trace elements in the aquifers. In addition, concentrations of chromium lie in range of 79.4-232 µg L(-1) in shallow groundwater, 129-250 µg L(-1) in deep groundwater and 110-218 µg L(-1) in artesian groundwater. All exceed the WHO guideline value of 50 µg L(-1). Their origin is likely to be predominantly geogenic, present as chromate in the ambient oxic and alkaline aquifer conditions.

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.