Evolution of As speciation with depth in a soil profile with a geothermal As origin

High contents of arsenic were detected in soils in Guandu plain, northwest Taiwan. To determine the sources and speciation of As in the soils, the depth profiles of soil properties, elemental composition and As speciation were investigated. The As concentrations in the soil profile ranged from 152 to 1222 mg kg^-1, with the highest concentration at the depth of 70-80 cm. The As distribution was found to be positively correlated to Fe, Pb, and Ba. The As(V)-adsorbed ferrihydrite and scorodite were the predominant phases in the top layers (<50 cm), while beudantite was the predominant phase below 50 cm along with As(III)- and As(V)-adsorbed ferrihydrite as the minor components. The results of sequential extraction showed that As-associated with noncrystalline and crystalline Fe/Al hydrous oxides and residual phases were predominant at the depths of 0-60, 60-100 and 100-140 cm, respectively, indicating an increasing As recalcitrance with soil depth. Based on the soil properties, and elemental and mineral compositions at different soil depths, the origin of beudantite in the soils was likely allogenic rather than authigenic or anthropogenic. The formation of scorodite in the surface soils was suggested to be transformed from beudantite. As-associated Fe hydrous oxides may be contributed by the progressive dissolution of beudantite and scorodite, and the continuous influxes of As and Fe. While Fe hydrous oxides were able to immobilize As during the dissolution of As-bearing minerals, the increase of As mobility in soils may imply an increase in the environmental risk of As over time.