Validation of chemical speciation model of inorganic arsenic in river waters with mobilisation processes

Abstract

The thermodynamic model of inorganic arsenic (acid–base, complexation, precipitation and redox equilibria) was validated with results obtained in arsenic mobilisation processes taking place in several river sediment samples of the Basque Country (North of Spain). Natural waters in contact with the sediment were collected at each sampling point, together with the sediment samples. These waters were analysed and then used as the extractant in the mobilisation studies. Considering pH, redox potential and total concentration values of the main cations and anions, the stoichiometric equilibrium constant were computed for each river water situation. The activity coefficient values of the inorganic arsenic species were estimated by means of the Modified Bromley Methodology (MBM). Both water and sediment for each sampling site were used in the mobility experiments, and the results were compared with the theoretical predictions of the thermodynamic model extrapolated to the chemical conditions of the sampling point. Moreover, a correlation analysis was also performed taking into account all the data and sampling sites; these results were also discussed and compared with the theoretical speciation obtained from the basic model of inorganic arsenic.