Iron Plaque at Rice Roots: No Barrier for Methylated Thioarsenates

Iron (hydr)oxide coating at rice roots, so-called iron plaque (IP), is often an important barrier for uptake of inorganic oxyarsenic species and their accumulation in rice grains. Sorption of methylated thioarsenates, which can co-exist with inorganic and methylated oxyarsenates in paddy soils, was not studied yet, even though these toxic species were detected in xylem and grains of rice plants before. Hydroponic experiments at pH 6.5 with 20 day-old rice plants showed lower net arsenic enrichment in IP for plants exposed to monomethylthioarsenate (MMMTA) compared to monomethylarsenate (MMA) and no enrichment for dimethylmonothioarsenate (DMMTA). Goethite was the dominant mineral phase in our IP. Sorption experiments with synthesized goethite and ferrihydrite revealed a 30-times-higher sorption capacity for MMMTA to amorphous ferrihydrite than to crystalline goethite, comparable to methylated oxyarsenates. No evidence for direct MMMTA binding was found. Instead, we postulate that MMMTA transformation to MMA is a prerequisite for removal. DMMTA showed very little sorption, even to amorphous ferrihydrite, which is in line with a lack of direct binding and reported slow transformation to dimethylarsenate. Our study implies that IP is no effective barrier for methylated thioarsenates and that especially DMMTA is very mobile with a high risk of uptake in rice plants.