title: Persulfate oxidation for in situ remediation of TCE. II. Activated by chelated ferrous ion.
abstract: In situ chemical oxidation (ISCO) is a technique used to remediate contaminated soil and groundwater systems. It has been postulated that sodium persulfate (Na2S2O8) can be activated by transition metal ions such as ferrous ion (Fe2+) to produce a powerful oxidant known as the sulfate free radical (SO4-*) with a redox potential of 2.6 V, which can potentially destroy organic contaminants. In this laboratory study persulfate oxidation of dissolved trichloroethylene (TCE) was investigated in aqueous and soil slurry systems under a variety of experimental conditions. A chelating agent (i.e., citric acid) was used in attempt to manipulate the quantity of ferrous ion in solution by providing an appropriate chelate/Fe2+ molar ratio. In an aqueous system a chelate/Fe2+ molar ratio of 1/5 (e.g., S2O8(2)-/chelate/Fe2+/TCE ratio of 20/2/10/1) was found to be the lowest acceptable ratio to maintain sufficient quantities of Fe2+ activator in solution resulting in nearly complete TCE destruction after only 20 min. The availability of Fe2+ appeared to be controlled by adjusting the molar ratio of chelate/Fe2+. In general, high levels of chelated ferrous ion concentrations resulted in faster TCE degradation and more persulfate decomposition. However, if initial ferrous ion contents are relatively low, sufficient quantities of chelate must be provided to ensure the chelation of a greater percentage of the limited ferrous ion present. Citric acid chelated ferrous ion appeared effective for TCE degradation within soil slurries but required longer reaction times. Additionally, the use of citric acid without the addition of supplemental Fe2+ in soil slurries, where the citric acid apparently extracted native metals from the soil, appeared to be somewhat effective at enhancing persulfate oxidation of TCE over extended reaction times. A comparison of different chelating agents revealed that citric acid was the most effective.
authors.affiliation: Department of Civil and Environmental Engineering, University of Massachusetts, One University Avenue, Lowell, MA 01854, USA. chenju_liang@uml.edu
authors.forename: Chenju
authors.initials: C
authors.lastname: Liang
authors.forename: Clifford J
authors.initials: CJ
authors.lastname: Bruell
authors.forename: Michael C
authors.initials: MC
authors.lastname: Marley
authors.forename: Kenneth L
authors.initials: KL
authors.lastname: Sperry
mesh_terms: D002614:Chelating Agents / Q000737:chemistry*; D019343:Citric Acid / Q000737:chemistry*; D005296:Ferrous Compounds / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D010084:Oxidation-Reduction; D012987:Soil / Q000032:analysis; D013431:Sulfates / Q000737:chemistry*; D013457:Sulfur Compounds / Q000737:chemistry; D014241:Trichloroethylene / Q000737:chemistry*; D014874:Water Pollutants, Chemical
chemical_list: D002614:Chelating Agents; D005296:Ferrous Compounds; D005609:Free Radicals; D012987:Soil; D013431:Sulfates; D013457:Sulfur Compounds; D014874:Water Pollutants, Chemical; C069025:sulfate radical; D014241:Trichloroethylene; D019343:Citric Acid