Influence of pH on persulfate oxidation of TCE at ambient temperatures

In situ chemical oxidation (ISCO) is a technology used for groundwater remediation. This laboratory study investigated the use of the oxidant sodium persulfate for the chemical oxidation of trichloroethylene (TCE) at near ambient temperatures (10, 20 and 30 C) to determine the influence of pH (pH = 4, 7 and 9) on the reaction rate (i.e., pseudo-first-order rate constants) over the range of temperatures utilized. TCE solutions (60 mg l(-1); 0.46 mM) were prepared in phosphate buffered RO water and a fixed persulfate/TCE molar ratio of 50/1 was employed in all tests. Half-lives of TCE degradation at 10, 20 and 30 degrees C (pH 7) were 115.5, 35.0 and 5.5 h, respectively. Maximum TCE degradation occurred at pH 7. Lowering system pH resulted in a greater decrease in TCE degradation rates than increasing system pH. Radical scavenging tests used to identify predominant radical species suggested that the sulfate radical (SO4.-) predominates under acidic conditions and the hydroxyl radical ((OH)-O-.) predominates under basic conditions. In a side by side comparison of TCE degradation in a groundwater vs. unbuffered RO water it was demonstrated that when the system pH is buffered to near neutral pH conditions due to the presence of natural occurring groundwater constituents that the TCE degradation rate is higher than in unbuffered RO water where the system pH dropped from 5.9 to 2.8. The results of this study suggest that in a field application of ISCO, pH should be monitored and adjusted to near neutral if necessary. (c) 2006 Elsevier Ltd. All rights reserved.