Natural and anthropogenic sources of solutes in the wet precipitation of a densely populated city of Southern South America.

The chemistry of rainwater is controlled by the interaction among water, airborne particles and gas sources, whether natural or human-made. This article analyzes the chemical composition dynamics of individual rainfall events collected over a three-year period in the densely populated city of Córdoba (Argentina). The main purpose is to identify the natural and/or anthropogenic sources, and the extent to which they determine the seasonal chemical signature exhibited by wet precipitation in the heart of the South Eastern South America. The results reveal that, despite geogenic components are only minor constituents of the airborne particles in downtown Córdoba, they appear to be the main source of solutes in rainwaters, also responsible for the alkaline water pH that predominates most of the year. This fraction mostly corresponds to wind-blown soil particles transported either from local or distant sources, with rare earth elements (REE) patterns similar to those of rainwaters produced during the dry season. Anthropogenic contributions are only evident during the wet season, when rainwater shows REE patterns similar to those of industrial emissions and exhibits moderate enrichment of heavy metals such as Cu and Zn, derived from soluble compounds used in agricultural activities (e.g, sowing, fertilizing). With the exception of these two metals, the remaining heavy metals are depleted in rainwater suggesting that the airborne conveying compounds (mostly anthropogenic) are barely soluble.

Rare earth elements mobility processes in an AMD-affected estuary: Huelva Estuary (SW Spain).

Huelva Estuary is a transition zone where REE-rich acidic waters interact with saline-alkaline seawater. This mixing process influences the geochemical and mineralogical characteristics of particulate and dissolved fractions. The Tinto River has >11,000µgL-1 dissolved REE (pH=1.66), whereas seawater only reaches 8.75·10-2µgL-1 dissolved REE (pH=7.87). REE-normalized patterns in "pH<6 solutions" are parallel and show similarities, diminishing their concentration as pH increases. Sequential extraction performed on the generated precipitates of mixed solutions indicates that most REE are associated to the residual phase. In a second order, REE are associated with soluble salts at pH3 and 3.5 whereas in sediments generated at pH4 and 5, they are distributed in salts (1° extraction), poorly crystallized Fe-bearing minerals (schwertmannite, 3° extraction) and well crystallized Fe-bearing minerals (goethite - hematite, 4° extraction). Finally, precipitated REE are highest at pH6 newly formed minerals with a release to solution in higher pH.

Geochemical behavior of an acid drainage system: the case of the Amarillo River, Famatina (La Rioja, Argentina).

The Amarillo River (Famatina range, Argentina, ~29° S and ~67° W) is unusual because acid mine drainage (AMD) is superimposed on the previously existing acid rock drainage (ARD) scenario, as a Holocene paleolake sedimentary sequence shows. In a markedly oxidizing environment, its water is currently ferrous and of the sulfate-magnesium type with high electrical conductivity (>10 mS cm-1 in uppermost catchments). At the time of sampling, the interaction of the mineralized zone with the remnants of mining labors determined an increase in some elements (e.g., Cu ~3 to ~45 mg L-1; As ~0.2 to ~0.5 mg L-1). Dissolved concentrations were controlled by pH, decreasing significantly by precipitation of neoformed minerals (jarosite and schwertmannite) and subsequent metal sorption (~700 mg kg-1 As, 320 mg kg-1 Zn). Dilution also played a significant role (i.e., by the mixing with circumneutral waters which reduces the dissolved concentration and also enhances mineral precipitation). Downstream, most metals exhibited a significant attenuation (As 100 %, Fe 100 %, Zn 99 %). PHREEQC-calculated saturation indices (SI) indicated that Fe-bearing minerals, especially schwertmannite, were supersaturated throughout the basin. All positive SI increased through the input of circumneutral water. PHREEQC inverse geochemical models showed throughout the upper and middle basin, that about 1.5 mmol L-1 of Fe-bearing minerals were precipitated. The modeling exercise of mixing different waters yielded results with a >99 % of correlation between observed and modeled data.