Competitive Sorption of Arsenate and Phosphate on Different Clay Minerals and Soils

Sorption and desorption of AsO 4 on or from different soil components may have a dominant role in regulating As mobility in soils. The objectives of this work were to provide information on the factors that influence the competitive sorption of AsO 4 and PO 4 in soil. We studied the competitive sorption of PO 4 and AsO 4 on selected phyllosilicates, metal oxides, synthetic organo‐mineral complexes, and soil samples as affected by pH (4.0–8.0), ligands concentration, surface coverage of the oxyanions on the samples and the residence time. We found that Mn, Fe, and Ti oxides and phyllosilicates particularly rich in Fe (nontronite, ferruginous smectites) were more effective in sorbing AsO 4 than PO 4 In fact, by adding AsO 4 and PO 4 as a mixture (AsO 4 /PO 4 molar ratio of 1) more AsO 4 than PO 4 was usually sorbed on birnessite, pyrolusite, goethite, nontronite, and ferruginous smectite, but more PO 4 than AsO 4 was sorbed on noncrystalline Al precipitation products, gibbsite, boehmite, allophane, and kaolinite. For example, at pH 5.0 the sorbed AsO 4 /sorbed PO 4 molar ratio (rf) was 1.81 for birnessite, 1.05 for nontronite, but was only 0.45 for kaolinite and 0.14 for allophane. For montmorillonite, illite, and vermiculite the rf values were slightly <1. For soil samples, particularly rich in kaolinite, halloysite, allophane, and containing relatively large amounts of organic C, the rf values were usually much <1. For all the samples, the rf values increased by decreasing the pH and with the residence time of the oxyanions. The sorption of AsO 4 (or PO 4 ) on goethite and gibbsite decreased by increasing the initial PO 4 /AsO 4 (or AsO 4 /PO 4 molar ratio) up to 2.0. However, PO 4 inhibited AsO 4 sorption more on gibbsite than on goethite, whereas AsO 4 prevented PO 4 sorption more on goethite than on gibbsite. The data reported in this paper suggest that the mobility, the bioavailability, and the toxicity of As in soil environments may be greatly affected by the nature of soil components, pH, presence of anions (PO 4 ), and residence time.