Mechanism of Base Activation of persulfate.pdfVIP

Mechanism of Base Activation of Persulfate O L H A S . F U R M A N , A M Y L . T E E L , A N D R I C H A R D J . W A T T S * Department of Civil Environmental Engineering, Washington State University, Pullman, Washington 99164-2910 Received April 27, 2010. Revised manuscript received June 24, 2010. Accepted June 28, 2010. Base is the most commonly used activator of persulfate for the treatment of contaminated groundwater by in situ chemical oxidation (ISCO). A mechanism for the base activation of persulfate is proposed involving the base-catalyzed hydrolysis of persulfate to hydroperoxide anion and sulfate followed by the reduction of another persulfate molecule by hydroperoxide. Reduction by hydroperoxide decomposes persulfate into sulfate radical and sulfate anion, and hydroperoxide is oxidized to superoxide. The base-catalyzed hydrolysis of persulfate was supported by kinetic analyses of persulfate decomposition at various base:persulfate molar ratios and an increased rate ofpersulfatedecomposition inD2OvsH2O.Stoichiometricanalyses confirmed that hydroperoxide reacts with persulfate in a 1:1 molar ratio. Addition of hydroperoxide to basic persulfate systems resulted in rapid decomposition of the hydroperoxide and persulfate and decomposition of the superoxide probe hexachloroethane. The presence of superoxide was confirmed with scavenging by Cu(II). Electron spin resonance spectroscopy confirmed the generation of sulfate radical, hydroxyl radical, and superoxide. The results of this research are consistent with the widespread reactivity reported for base-activated persulfate when it is used for ISCO. Introduction In situ chemical oxidation (ISCO) has become a widely used technology for the remediation of contaminated soils and groundwater. The most common ISCO processes are cata- lyzed H2O2 propagations (i.e., modified Fenton’s reag- entsCHP), permanganate, and activated persulfate (1). Each of these ISCO processes has limitations. CHP is often ineffective becau