Abstract: The oxidation of As(III) to As(V) by K-birnessite was examined at different temperatures, pHs, and birnessite/As(III) ratios. Experiments ranged in duration from 5 to 64 hr, and solution and solid products were determined at several intervals. All experiments showed that the reaction produced large amounts of K+ to solution and very little Mn2+. As(V) was released to solution and incorporated into the K-birnessite. The oxidation was initially rapid and then slowed. The oxidation of As(III) was probably facilitated initially by autocatalytic Mn-As(V) reactions occurring mostly in the interlayer, in which large amounts of As(V) and K+ could be easily released to solution. The reaction also slowed when interlayer Mn was exhausted by forming Mn-As(V) complexes. Mn(IV) could only be acquired from the octahedral sheets of the birnessite. The two-stage reaction process proposed here depended on the layered structure of birnessite, the specific surface, and presence of exchangeable cations in K-birnessite.