Oxidation process of dissolvable sulfide by synthesized todorokite in aqueous systems

Abstract

Todorokite, formed from Mn(II) in supergene environments, can affect the transformation and migration of dissolvable sulfides in soils and water. In this work, todorokite was synthesized with different degrees of crystallinity, and the redox mechanism of dissolvable sulfide and todorokite was studied in both closed and open aqueous systems. The influences of pH, temperature, crystallinity, the amount of manganese oxides, and oxygen gas on S(2-) oxidation process were investigated. It is found that S(2-) was oxidized to S(0), SO3(2-), S2O3(2-) and SO4(2-), and about 90% of S(2-) was converted into S(0) in closed systems. The participation of oxygen facilitated the further oxidation of S(0) to S2O3(2-). S(0) and S2O3(2-) were formed with the conversion rates of S(2-) about 45.3% and 38.4% after 1h of reaction, respectively, and the conversion rate for S2O3(2-) increased as reaction prolonged for a longer period. In addition, todorokite was reduced to Mn(OH)2 in the presence of nitrogen gas, and its chemical stability increased when oxygen gas was admitted into the reaction system during the process. The oxidation rate of dissolvable sulfide followed a pseudo-first-order kinetic law in the initial stage (within 10 min), and the initial oxidation rate constant of S(2-) increased with elevating temperature, increasing the quantity and decreasing crystallinity of todorokite. The initial oxidation rate of dissolvable sulfide decreased with continuous feeding of O2 into the test solution, possibly due to a decrease in active Mn(III) content in todorokite. The present work demonstrates the redox behaviors and kinetics of dissolvable sulfide and todorokite in aquatic environments.

Keywords: Dissolvable sulfide; Environmental chemistry; Mn(III); Redox reaction; Soil; Todorokite.