Kinetics of Dimethylated Thioarsenicals and the Formation of Highly Toxic Dimethylmonothioarsinic Acid in Environment

Dimethylmonothioarsinic acid (DMMTA^V) is a highly toxic, thiolated analogue of dimethylarsinic acid (DMA^V). In comparison, a further thiolated analogue, dimethyldithioarsinic acid (DMDTA^V), and DMA^V both exhibit lower toxicity. To understand the environmental conditions responsible for forming DMMTA^V, the kinetics of DMA^V thiolation are examined. The thiolation of DMA^V is pH-dependent and consists of two consecutive first-order reactions under excess sulfide conditions. The first thiolation of DMA^V to form DMMTA^V is faster than the second one to DMDTA^V. DMMTA^V is therefore an intermediate. The first reaction is first-order in H₂S at pH 6.0 and 20 °C; therefore, the overall reaction is second-order and the rate coefficient in this condition is 0.0780 M^-1 s^-1. The rate coefficient significantly decreases at pH 8.0, indicating that H₂S(aq) triggers the thiolation of DMA^V. The second reaction rate is significantly decreased at pH 2.5; therefore, reaction under strongly acidic conditions leads to accumulation of highly toxic DMMTA^V in the early stages of thiolation. The transformation of DMDTA^V to DMMTA^V is catalyzed in the presence of ferric iron. Formation of DMMTA^V should be considered when assessing risk posed by arsenic under sulfidic or sulfate reducing conditions.