Hugo Nicolli

Hydrogeochemistry of arsenic and other inorganic constituents in groundwaters from La Pampa, Argentina

Groundwaters from Quaternary loess aquifers in northern La Pampa Province of central Argentina have significant quality problems due to high concentrations of potentially harmful elements such as As, F, NO3-N, B, Mo, Se and U and high salinity. The extent of the problems is not well-defined, but is believed to cover large parts of the Argentine Chaco-Pampean Plain, over an area of perhaps 106 km2. Groundwaters from La Pampa have a very large range of chemical compositions and spatial variability is considerable over distances of a few km. Dissolved As spans over 4 orders of magnitude (<4–5300 μg l−1) and concentrations of F have a range of 0.03–29 mg l−1, B of 0.5–14 mg l−l, V of 0.02–5.4 mg l−1, NO3–N of <0.2–140 mg l−1, Mo of 2.7–990 μg l−1 and U of 6.2–250 μg l−1. Of the groundwaters investigated, 95% exceed 10 μg As l−1 (the WHO guideline value) and 73% exceed 50 μg As l−1 (the Argentine national standard). In addition, 83% exceed the WHO guideline value for F (1.5 mg l−1), 99% for B (0.5 mg l−1), 47% for NO3-N (11.3 mg l−1), 39% for Mo (70 μg l−1), 32% for Se (10 μg l−1) and 100% for U (2 μg l−1). Total dissolved solids range between 730 and 11400 mg l−1, the high values resulting mainly from evaporation under ambient semi-arid climatic conditions. The groundwaters are universally oxidising with high dissolved-O2 concentrations. Groundwater pHs are neutral to alkaline (7.0–8.7). Arsenic is present in solution predominantly as As(V). Groundwater As correlates positively with pH, alkalinity (HCO3), F and V. Weaker correlations are also observed with B, Mo, U and Be. Desorption of these elements from metal oxides, especially Fe and Mn oxides under the high-pH conditions is considered an important control on their mobilisation. Mutual competition between these elements for sorption sites on oxide minerals may also have enhanced their mobility. Weathering of primary silicate minerals and accessory minerals such as apatite in the loess and incorporated volcanic ash may also have contributed a proportion of the dissolved As and other trace elements. Concentrations of As and other anions and oxyanions appear to be particularly high in groundwaters close to low-lying depressions which act as localised groundwater-discharge zones. Concentrations up to 7500 μg l−1 were found in saturated-zone porewaters extracted from a cored borehole adjacent to one such depression. Concentrations are also relatively high where groundwater is abstracted from close to the water table, presumably because this zone is a location of more active weathering reactions. The development of groundwaters with high pH and alkalinity results from silicate and carbonate reactions, facilitated by the arid climatic conditions. These factors, together with the young age of the loess sediments and slow groundwater flow have enabled the accumulation of the high concentrations of As and other elements in solution without significant opportunity for flushing of the aquifer to enable their removal.

One century of arsenic exposure in Latin America: a review of history and occurrence from 14 countries.

The global impact on public health of elevated arsenic (As) in water supplies is highlighted by an increasing number of countries worldwide reporting high As concentrations in drinking water. In Latin America, the problem of As contamination in water is known in 14 out of 20 countries: Argentina, Bolivia, Brazil, Chile, Colombia, Cuba, Ecuador, El Salvador, Guatemala, Honduras, Mexico, Nicaragua, Peru and Uruguay. Considering the 10 μg/L limit for As in drinking water established by international and several national agencies, the number of exposed people is estimated to be about 14 million. Health effects of As exposure were identified for the first time already in the 1910s in Bellville (Córdoba province, Argentina). Nevertheless, contamination of As in waters has been detected in 10 Latin American countries only within the last 10 to 15 years. Arsenic is mobilized predominantly from young volcanic rocks and their weathering products. In alluvial aquifers, which are water sources frequently used for water supply, desorption of As from metal oxyhydroxides at high pH (>8) is the predominant mobility control; redox conditions are moderate reducing to oxidizing and As(V) is the predominant species. In the Andes, the Middle American cordillera and the Transmexican Volcanic Belt, oxidation of sulfide minerals is the primary As mobilization process. Rivers that originate in the Andean mountains, transport As to more densely populated areas in the lowlands (e.g. Rímac river in Peru, Pilcomayo river in Bolivia/Argentina/Paraguay). In many parts of Latin America, As often occurs together with F and B; in the Chaco-Pampean plain As is found additionally with V, Mo and U whereas in areas with sulfide ore deposits As often occurs together with heavy metals. These co-occurrences and the anthropogenic activities in mining areas that enhance the mobilization of As and other pollutants make more dramatic the environmental problem.

Co-occurrence of arsenic and fluoride in groundwater of semi-arid regions in Latin America: Genesis, mobility and remediation

Several million people around the world are currently exposed to excessive amounts of arsenic (As) and fluoride (F) in their drinking water. Although the individual toxic effects of As and F have been analyzed, there are few studies addressing their co-occurrences and water treatment options. Several studies conducted in arid and semi-arid regions of Latin America show that the co-occurrences of As and F in drinking water are linked to the volcaniclastic particles in the loess or alluvium, alkaline pH, and limited recharge. The As and F contamination results from water-rock interactions and may be accelerated by geothermal and mining activities, as well as by aquifer over-exploitation. These types of contamination are particularly pronounced in arid and semi-arid regions, where high As concentrations often show a direct relationship with high F concentrations. Enrichment of F is generally related to fluorite dissolution and it is also associated with high Cl, Br, and V concentrations. The methods of As and F removal, such as chemical precipitation followed by filtration and reverse osmosis, are currently being used at different scales and scenarios in Latin America. Although such technologies are available in Latin America, it is still urgent to develop technologies and methods capable of monitoring and removing both of these contaminants simultaneously from drinking water, with a particular focus towards small-scale rural operations.

Arsenic and associated trace-elements in groundwater from the Chaco-Pampean plain, Argentina: results from 100 years of research.

The Chaco-Pampean plain, Argentina, is a vast geographical unit (1,000,000 km²) affected by high arsenic (As) concentrations in universal oxidizing groundwater. The socio-economic development of the region is restricted by water availability and its low quality caused by high salinity and hardness. In addition, high As and associated trace-elements (F, U, V, B, Se, Sb, Mo) concentrations of geogenic origin turn waters unsuitable for human consumption. Shallow groundwater with high As and F concentrations (ranges: <10-5300 μg As/L; 51-7,340 μg F/L) exceeding the WHO guideline values (As: 10 μg/L; F: 1,500 μg/L) introduces a potential risk of hydroarsenicism disease in the entire region and fluorosis in some areas. The rural population is affected (2-8 million inhabitants). Calcareous loess-type sediments and/or intercalated volcanic ash layers in pedosedimentary sequences hosting the aquifers are the sources of contaminant trace-elements. Large intra and interbasin variabilities of trace-element concentrations, especially between shallow and deep aquifers have been observed. All areas of the Chaco-Pampean plain were affected in different grades: the Chaco-Salteña plain (in the NNE of the region) and the northern La Pampa plain (in the center-south) have been shown the highest concentrations. The ranges of As and F contents in loess-sediments are 6-25 and 534-3340 mg/kg, respectively in the Salí River basin. Three key processes render high As concentrations in shallow aquifers: i) volcanic glass dissolution and/or hydrolysis and leaching of silicates minerals hosted in loess; ii) desorption processes from the surface of Al-, Fe- and Mn-oxi-hydroxides (coating lithic fragments) at high pH and mobilization as complex oxyanions (As and trace elements)in Na-bicarbonate type groundwaters; and iii) evaporative concentration in areas with semiarid and arid climates. Local factors play also an important role in the control of high As concentrations, highly influenced by lithology-mineralogy, soils-geomorphology, actual climate and paleoclimates, hydraulic parameters, and residence time of groundwaters.

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 worlds 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.