Elevated concentrations of arsenic (As) have been detected in soils of former railway corridors in South Australia, Australia. Elevated As concentrations resulted from the long-term application of As-based herbicides to control grass growth along former railway corridors. A study of former railway corridors revealed considerable surface (0-10 cm) contamination with As (<20 to >1000 mg As kg-1). The distribution of As in soils was related with particle size fraction and iron (Fe) oxide content. Total As increased markedly with decreasing particle size; sand<<silt<clay, with increasing As concentration generally correlated with increasing Fe concentrations (R2=0.57). A sequential fractionation of soils collected from selected sites showed that As was primarily associated with the amorphous and crystalline Fe and Al oxide materials. Solid phase speciation of As-contaminated soil indicated that arsenate (AsV) was the dominant As species present in the soil. However, in some soils, arsenite (AsIII) composed up to 40% of the total As present. The reasons for the presence of AsIII under alkaline and aerobic conditions are unclear.