Redox-dependent effects of phosphate on arsenic speciation in paddy soils.

Evaluating speciation of arsenic (As) is essential to assess its risk in paddy soils. In this study, effects of phosphate on speciation of As in six paddy soils differing in redox status were studied over a range of pH (pH 3-9) and different background calcium (Ca) levels by batch adsorption experiments and speciation modeling. Contrasting effects of phosphate on As speciation were observed in suboxic and anoxic soils. Under suboxic conditions, phosphate inhibited Fe and As reduction probably due to stabilization of Fe-(hydr)oxides, but increased soluble As(V) concentration as a result of competitive adsorption between As(V) and phosphate. In anoxic soils, phosphate stimulated Fe and As reduction and caused increases of As(III) in soil solution under both acidic and neutral/alkaline pH. The LCD (Ligand and Charge Distribution) and NOM-CD (Natural Organic Matter-Charge Distribution) model can describe effects of pH, calcium and phosphate on As speciation in these paddy soils. The results suggest that phosphate fertilization may decrease (at low pH) or increase (at neutral/alkaline pH) As mobility in paddy soils under (sub)oxic conditions, but under anoxic conditions and in phosphorus deficient soils phosphate fertilization may strongly mobilize As by promoting microbial activities.