Effect of Basicity on Persulfate Reactivity
Publication: Journal of Environmental Engineering
Volume 137, Issue 4
Abstract
The generation of reactive species in activated persulfate systems under different conditions of basicity was investigated using three probe compounds. Anisole was used to detect both sulfate radical and hydroxyl radical. Nitrobenzene was used to detect hydroxyl radical, and hexachloroethane was used as a reductant probe. Minimal probe compound degradation occurred in persulfate reactions conducted at , demonstrating that a low flux of reactants is generated at acidic, neutral, and slightly basic pH regimes. In persulfate reactions at pH 12, sulfate and hydroxyl radical were generated but minimal reductants were produced. Scavenging studies showed that the dominant reactive species at basic pH was hydroxyl radical. The generation of reductants increased at high molar ratios of base to persulfate; however, hydroxyl radical generation rates increased only when molar ratios of base to persulfate were . The results of this research demonstrate that the hydroxyl radical is the dominant reactive oxygen species in base-activated persulfate formulations and that overall reactivity increases with increasing base:persulfate ratios.
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Acknowledgments
Funding for this research was provided by the Strategic Environmental Research and Development Program (SERDP) through Grant No. UNSPECIFIEDER-1489.
References
Afanassiev, A. M., Okazaki, K., and Freeman, G. R. (1979). “Effect of solvation energy on electron reaction rates in hydroxylic solvents.” J. Phys. Chem., 83(10), 1244–1249.
Block, P. A. (2004). “Comparison of activators for the destruction of organic compounds of concern by sodium persulfate.” 3rd Int. Conf. on Oxidative and Reductive Technologies for Environmental Remediation, Redox Technologies, Inc., San Diego.
Block, P. A., Brown, R. A., and Robinson, D. (2004). “Novel activation technologies for sodium persulfate in situ chemical oxidation.” 4th Int. Conf. on the Remediation of Chlorinated and Recalcitrant Compounds, Battelle, Monterey, CA.
Buxton, G. V., Greenstock, C. L., Helman, W. P., and Ross, A. B. (1988). “Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals () in aqueous solution.” J. Phys. Chem. Ref. Data, 17(2), 513–780.
Clifton, C. L., and Huie, R. E. (1989). “Rate constants for hydrogen abstraction reactions of the sulfate radical, . Alcohols.” Int. J. Chem. Kinet., 21(8), 677–687.
Furman, O., et al. (2009). “Enhanced reactivity of superoxide in water-solid matrices.” Environ. Sci. Technol., 43(5), 1528–1533.
Haag, W. R., and Yao, C. C. D. (1992). “Rate constants for reaction of hydroxyl radicals with several drinking water contaminants.” Environ. Sci. Technol., 26(6), 1005–1013.
Hakoila, E. (1963). Annales universitatis Turkuensis series A I, Vol. 66, Univ. of Turku, Turku, Finland, 51.
House, D. A. (1962). “Kinetics and mechanism of oxidations by peroxydisulfate.” Chem. Rev., 62(3), 185–203.
Huang, K. C., Couttenye, R. A., and Hoag, G. H. (2002). “Kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE).” Chemosphere, 49(6), 413–420.
Huang, K. C., Zhao, Z., Hoag, G. E., Dahmani, A., and Block, P. A. (2005). “Degradation of volatile organic compounds with thermally activated persulfate oxidation.” Chemosphere, 61(4), 551–560.
Kolthoff, I. M., and Miller, J. K. (1951). “The chemistry of persulfate: I. The kinetics and mechanism of the decomposition of the persulfate ion in aqueous medium.” J. Am. Chem. Soc., 73(7), 3055–3059.
Larson, R. A., and Weber, E. J. (1994). Reaction mechanisms in environmental organic chemistry, Lewis Publishers, Chelsea, MI.
Liang, C. J., and Bruell, C. J. (2008). “Thermally activated persulfate oxidation of trichloroethylene: Experimental investigation of reaction orders.” Ind. Eng. Chem. Res., 47(9), 2912–2918.
Liang, C. J., Bruell, C. J., Marley, M. C., and Sperry, K. L. (2003). “Thermally activated persulfate oxidation of trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA) in aqueous systems and soil slurries.” Soil Sediment Contam., 12(2), 207–228.
Liang, C. J., Bruell, C. J., Marley, M. C., and Sperry, K. L. (2004a). “Persulfate oxidation for in situ remediation of TCE. I. Activated by ferrous ion with and without a persulfate-thiosulfate redox couple.” Chemosphere, 55(9), 1213–1223.
Liang, C. J., Bruell, C. J., Marley, M. C., and Sperry, K. L. (2004b). “Persulfate oxidation for in situ remediation of TCE. II. Activated by chelated ferrous ion.” Chemosphere, 55(9), 1225–1233.
Liang, C. J., Liang, C.-P., and Chen, C.-C. (2009). “pH dependence of persulfate activation by EDTA/Fe(III) for degradation of trichloroethylene.” J. Contam. Hydrol., 106(3–4), 173–182.
Liang, C. J., and Su, H.-W. (2009). “Identification of sulfate and hydroxyl radicals in thermally activated persulfate.” Ind. Eng. Chem. Res., 48(11), 5558–5562.
Neta, P., Madhavan, V., Zemel, H., and Fessenden, R. W. (1977). “Rate constants and mechanism of reaction of with aromatic compounds.” J. Am. Chem. Soc., 99(1), 163–164.
O’Neill, P., Steenken, S., and Schulte-Frohlinde, D. (1975). “Formation of radical cations of methoxylated benzenes by reaction with OH radicals, , , and in aqueous solution. An optical and conductometric pulse radiolysis and in situ radiolysis electron spin resonance study.” J. Phys. Chem., 79(25), 2773–2779.
Quan, H. N., Teel, A. L., and Watts, R. J. (2003). “Effect of contaminant hydrophobicity on H2O2 dosage requirements in the Fenton-like treatment of soils.” J. Hazard. Mater., 102(2–3), 277–289.
SAS. (2003). “The SAS system for Windows.” Release 9.1., SAS Institute, Cary, NC.
Siegrist, R. L., Urynowicz, M. A., West, O. R., Crimi, M. L., and Lowe, K. S. (2001). Principles and practices of in situ chemical oxidation using permanganate, Battelle Press, Columbus, OH.
Smith, B. A., Teel, A. L., and Watts, R. J. (2004). “Identification of the reactive oxygen species responsible for carbon tetrachloride degradation in modified Fenton’s systems.” Environ. Sci. Technol., 38(20), 5465–5469.
Smith, B. A., Teel, A. L., and Watts, R. J. (2006). “Mechanism for the destruction of carbon tetrachloride and chloroform DNAPLs by modified Fenton’s reagent.” J. Contam. Hydrol., 85(3–4), 229–246.
Watts, R. J., Finn, D. D., Cutler, L. M., Schmidt, J. T., and Teel, A. L. (2007). “Enhanced stability of hydrogen peroxide in the presence of subsurface solids.” J. Contam. Hydrol., 91(3–4), 312–326.
Watts, R. J., and Teel, A. L. (2006). “Treatment of contaminated soils and groundwater using in situ chemical oxidation.” Pract. Period. Hazard. Toxic Radioact. Waste Manage., 10(1), 2–9.
Information & Authors
Information
Published In
Journal of Environmental Engineering
Volume 137 • Issue 4 • April 2011
Pages: 241 - 247
Copyright
© 2011 American Society of Civil Engineers.
History
Received: Oct 30, 2009
Accepted: Oct 24, 2010
Published online: Nov 5, 2010
Published in print: Apr 1, 2011
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