Soil properties affecting solid–liquid distribution of As(V) in soils

The prediction of the mobility of arsenic (As) is crucial for predicting risks in soils contaminated with As. The objective of this study is to predict the distribution of As between solid and solution in soils based on soil properties and the fraction of As in soil that is reversibly adsorbed. We studied adsorption of As(V) in suspensions at radiotrace concentrations for 30 uncontaminated soils (pH 4.4–6.6). The solid–liquid distribution coefficient of As (K_d) varied from 14 to 4430 l kg^?1. The logarithm of the concentration of oxalate‐extractable Fe explained 63% of the variation in log K_d; by introducing the logarithm of the concentration of oxalate‐extractable P in the regression model, 85% of the variation in log K_d is explained. Double labelling experiments with ⁷³As(V) and ³²P(V) showed that the As to P adsorption selectivity coefficient decreased from 3.1 to 0.2 with increasing degree of P saturation of the amorphous oxides. The addition of As(V) (0–6 mmol kg^?1) reduced the K_d of ⁷³As up to 17‐fold, whereas corresponding additions of P(V) had smaller effects. These studies suggest that As(V) is adsorbed to amorphous oxides in soils and that sites of adsorption vary in their selectivity in respect of As and P. The concentration of isotopically exchangeable As in 27 contaminated soils (total As 13–1080 mg kg^?1) was between 1.2 and 19% (mean 8.2%) of its total concentration, illustrating that a major fraction of As is fixed. We propose a two‐site model of competitive As(V)–P(V) sorption in which amorphous Fe and Al oxides represent the site capacity and the isotopically exchangeable As represents the adsorbed phase. This model is fitted to ⁷³As adsorption data of uncontaminated soils and explains 69% of the variation of log K_d in these soils. The log K_d in contaminated soils predicted using this two‐site model correlated well with the observed log K_d (r = 0.75). We conclude that solubility of As is related to the available binding sites on amorphous oxides and to the fraction of As that is fixed.