Sorption of selenate on soils and pure phases: kinetic parameters and stabilisation

This study was conducted to identify the principle selenate carrier phases for two selected soils, by comparing their reactivity with selenate to that of pure phases of the solids. Silica, calcium carbonate, aluminium hydroxide, goethite, bentonite and humic acid were selected as the main soil carrier phases. Comparisons were made first on the parameter values obtained with the best fit of a kinetic sorption model which can discriminate instantaneous sorption from kinetically limited sorption. Then comparisons were made of the ability for each solid to stabilise selenate by measuring the ratio of the partition coefficient for sorption (Kdsorption) over that of the desorption (Kddesorption). Kinetics and stabilisation were used to help elucidate the nature of interactions with the test solid phases for a large range of selenate concentrations. The experiments were conducted over 165 h in batch reactors, the solid being isolated from the solution by dialysis tubing, at two pH (5.4 and 8) and three selenate concentrations (1 × 10−3, 1 × 10−6 and 1 × 10−8 mol L−1). The results obtained showed that only aluminium hydroxide can sorb selenate throughout the studied pH range (pH 5.4 to 8.0). The sorption capacity on this mineral was high (Kdsorption > 100 to 1 × 104 L kg−1) and the selenate was mainly stabilized by the formation of inner sphere complexes. The sorption on goethite occurred at pH 5.4 (Kdsorption 52 L kg−1), mainly as outer sphere complexes, and was null at pH 8. On silica, a weak sorption was observed only at pH 5.4 and at 165 h (Kdsorption 4 L kg−1). On bentonite, calcium carbonate and humic acid no significant sorption was observed. Concerning the two soils studied, different behaviours were observed for selenate. For soil Ro (pH 5.4), Kdsorption was low (8 L kg−1) compared to soil Bu (pH 8) (70 L kg−1). The sorption behaviour of selenate on soil Ro was mainly due to outer sphere complexes, as for goethite, whereas for soil Bu the sorption was mainly attributed to inner sphere complexes followed by reduction mechanisms, probably initiated by microorganisms, in which no steady state was reached at the end of the 165 h experiments. The sorption of selenate decreased when concentrations reached 1 × 10−3 mol L−1, due to solid saturation, except for aluminium hydroxide. Reduction of selenate seemed also to occur on goethite and soil Ro, for the same concentration, but without preventing a decrease in sorption. Thus, this work shows that the comparison of selenate behaviour between soil and pure phases helps to elucidate the main carrier phases and sorption mechanisms in soil.

► We model selenate sorption on pure solid phases and on two soils.
► No selenate sorption on calcite, humic acid and silica.
► Selenate sorption as outer sphere complexes on goethite and one soil.
► Selenate sorption as inner sphere complexes on aluminium hydroxide and other soil.
► Data could be modelled with a two sites complexation model (equilibrium and kinetic).