Chemical Oxidation of Chlorinated Solvents in Contaminated Groundwater: Review
Publication: Practice Periodical of Hazardous, Toxic, and Radioactive Waste Management
Volume 12, Issue 2
Abstract
The groundwater contaminated with chlorinated solvents poses daunting challenges for environmental remediation. Conventional treatment technologies such as pump-and-treat and bioremediation are costly and may require lengthy treatment periods. In situ chemical oxidation can be cost competitive with conventional treatment technologies and can destroy the contaminants rather than transferring them to another media. Four oxidants including hydrogen peroxide (Fenton’s reagent and Fenton-like), permanganate, persulfate, and ozone commonly employed in the chemical oxidation process are evaluated in this paper. The applicability of various oxidizing agents in subsurface contaminant remediation is also reviewed. Chemical oxidation technologies are effective and inexpensive alternatives. The merits also include that oxidation is relatively unaffected by contaminant characteristics and concentration. Future development-related chemical oxidation technology including a treatment train system, application of zero-valent iron nanoparticles in chemical oxidation processes, and solubilizer enhanced chemical oxidation are depicted. The summaries of this review paper regarding the chemical oxidation are applicable for designing in situ chemical oxidation systems.
Get full access to this article
View all available purchase options and get full access to this article.
References
Alexander, A., and Eli, K. (2001). “Solubilities and vapour pressures of saturated aqueous solutions of sodium peroxydisulfate and potassium peroxydisulfate.” J. Chem. Thermodyn., 33, 61–69.
Amarante, D. (2000). “Applying in situ chemical oxidation.” Pollut. Eng., February, 3–23.
Amiri, A. S. (2001). “ Treatment of methyl-tert-butyl ether (MTBE) in contaminated water.” Water Res., 35(15), 3706–3714.
Arizona Department of Environmental Quality (ADEQ). (2003). “Superfund programs section site information.” July, 21–38.
Azbar, N., Yonar, T., and Kestioglu, K. (2004). “Comparison of various oxidation processes and chemical treatment methods for COD and color removal from polyster and acetate fiber dyeing effluent.” Chemosphere, 55, 35–43.
Baciocchi, R., Boni, M. R., and April, L. D. (2003). “Hydrogen peroxide lifetime as an indicator of the efficiency of 3-chlorophenol Fenton’s and Fenton-like oxidation in soils.” J. Hazard. Mater., B96, 305–329.
Baciocchi, R., Boni, M. R., and D’Aprile, L. (2004). “Application of lifetime as an indicator of TCE Fenton-like oxidation in soils.” J. Hazard. Mater., B107, 97–102.
Basel, M. D. (2000). “Overview of in situ chemical oxidation: Status and lessons learned.” Proc., 2nd Int. Conf. on Remediation of Chlorinated and Recalcitrant Compounds, G. B. Wickramanayake, A. R. Gavaskar, and N. Gupta, eds., Monterey, Calif., 117–119.
Brewster, M. E., and Loftsson, T. (2007). “Cyclodextrins as pharmaceutical solubilizers.” Adv. Drug Delivery Rev., 59, 645–666.
Brown, G. S., Barton, L. L., and Thomson, B. M. (2003). “Permanganate oxidation of sorbed polycyclic aromatic hydrocarbons.” Waste Manage., 23, 737–740.
Chapman, S. W., Parker, B. L., Cherry, J. A., Aravena, R., and Hunkeler, D. (2007). “Groundwater—Surface water interaction and its role on TCE groundwater plume attenuation.” J. Contam. Hydrol., 91, 203–232.
Chen, G., Hoag, G. E., Chedda, P., Nadim, F., Woody, B. A., and Dobbs, G. M. (2001). “The mechanism and applicability of in situ oxidation of trichloroethylene with Fenton’s reagent.” J. Hazard. Mater., B87, 171–186.
Childs, J. D., Acosta, E., Knox, R., Harwell, J. H., and Sabatini, D. A. (2004). “Improving the extraction of tetrachloroethylene from soil columns using surfactant gradient systems.” J. Contam. Hydrol., 71, 27–45.
Chu, W., and Kwan, C. Y. (2003). “Remediation of contaminated soil by a solvent/surfactant system.” Chemosphere, 53, 9–15.
Chung, H. H., Jung, J., Yoon, J. H., and Lee, M. J. (2002). “Catalytic ozonation of PCE by clay from tidal flat sediments.” Catal. Lett., 78(1–4), 77–79.
Conrad, S. H., Glass, R. J., and Peplinski, W. J. (2002). “Bench-scale visualization of DNAPLs remediation processes in analog heterogeneous aquifers: Surfactant floods and in situ oxidation using permanganate.” J. Contam. Hydrol., 58, 13–49.
DeHghi, B., Hodges, A., and Feng, T. H. (2002). “Post-treatment evaluation of Fenton’s reagent in situ chemical oxidation.” Proc., 3rd Int. Conf. on Remediation of Chlorinated and Recalcitrant Compounds, Battelle Press, Monterey, Calif., 1195–1204.
Dijkshoorn, P. (2003). “In-situ chemical oxidation of chlorinated solvents with potassium permanganate on a site in Belgium.” Proc., ConSoil, 2003—8th Int. FZK/TNO Conf. on Contaminated Soil, Gent, Belgium, 1686–1691.
Dong, X., Shen, W., Zhu, Y., Xiong, L., Gu, J., and Shi, J. (2005). “Investigation on Mn-loaded mesoporous silica MCM-41 prepared via reducing with in situ surfactant.” Microporous Mesoporous Mater., 81, 235–240.
Fenton, H. J. H. (1894). “Oxidation of tartaric acid in presence of iron.” J. Chem. Soc., 65, 899–910.
Ferraz, W., Oliverira, L. C. A., Dallago, R., and Conceicao, L. D. (2007). “Effect of organic acid to enhance the oxidative power of the Fenton-like system: Computational and empirical evidences.” Catal. Commun., 8, 131–134.
Fountain, J. C. (1998). Technologies for dense non-aqueous phase liquid source zone remediation, Ground-Water Remediation Technologies Analysis Center (GWRTAC), Pittsburgh.
Gibbs, G. F., Kermasha, S., Alli, I., and Mulligan, C. N. (1999). “Encapsulation in the food industry: A review.” Int. J. Food Sci. Nutr., 50, 213–225.
Hanna, K., de Brauer, C., and Germain, P. (2004). “Cyclodextrin-enhanced solubilization of pentachlorophenol in water.” J. Environ. Manage., 71, 1–8.
Hao, X., Zhou, M., Xin, Q., and Lei, L. (2007). “Pulsed discharge plasma induced Fenton-like reactions for the enhancement of the degradation of 4-chlorophenol in water.” Chemosphere, 66, 2185–2192.
Harwell, J. H., Sabatini, D. A., and Knox, R. C. (1999). “Surfactants for groundwater remediation.” Colloids Surf., A, 141, 255–268.
He, Y., Li, P., and Yalkowsky, S. H. (2003). “Solubilization of fluasterone in cosolvent/cyclodextrin combinations.” Int. J. Pharm., 264, 25–34.
Huang, K. C., Couttenye, R. A., and Hoag, G. E. (2002). “Kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE).” Chemosphere, 49, 413–420.
Huling, S. G., and Pivetz, B. E. (2006). “In-situ chemical oxidation.” EPA/600/R-06/072, U.S. Environmental Protection Agency, Office of Research and Development, National Risk Management Research Laboratory, Washington, D.C.
Interstate Technology and Regulatory Council (ITRC). (2001). Technical and regulatory guidance for in situ chemical oxidation of contaminated soil and groundwater, Washington, D.C.
Interstate Technology and Regulatory Council (ITRC). (2002a). DNAPL source reduction: Facing the challenge, Washington, D.C.
Interstate Technology and Regulatory Council (ITRC). (2002b). Technical and regulatory guidance for surfactant/cosolvent flushing of DNAPL source zones, Washington, D.C.
Interstate Technology and Regulatory Council (ITRC). (2003). Technology overview: An introduction to characterizing sites contaminated with DNAPLs, Washington, D.C.
Interstate Technology Regulatory Council (ITRC). (2005). Technical and regulatory guidance for in situ chemical oxidation of contaminated soil and groundwater, Washington, D.C.
Jafvert, C. T. (1996). “Report: Surfactant/co-solvent.” Rep. to Ground-Water Remediation Technologies Analysis Center, Document TE-96-02.
Jerome, K. (1997). “In situ oxidation destruction of DNAPL.” EPA ground water currents, Developments in innovative ground-water treatment, EPA/542/-N-97/004, EPA Washington D.C.
Kasprzyk-Hordern, B., Zio’ek, M., and Nawrocki, J. (2003). “Catalytic ozonation and methods of enhancing molecular ozone reactions in water treatment.” Appl. Catal., B, B46, 639–669.
Kawakami, K., Miyoshi, K., and Ida, Y. (2004). “Solubilization behavior of poorly soluble drugs with combined use of Gelucire 44/14 and cosolvent.” J. Pharm. Sci., 93, 1471–1479.
Kawakami, K., Oda, N., Miyoshi, K., Funaki, T., and Ida, Y. (2006). “Solubilization behavior of a poorly soluble drug under combined use of surfactants and cosolvents.” Eur. J. Pharm. Sci., 28, 7–14.
Kislenko, V. N., Berlin, A. A., and Litovchenko, N. V. (1995). “Kinetics of glucose oxidation with persulfate ions, catalyzed by iron salts.” Russian J. Gen. Chem. Part 2, 65(7), 96–1092.
Krishna, G., Chen, K. J., Lin, C. C., and Nomeir, A. A. (2001). “Permeability of lipophilic compounds in drug discovery using in-vitro human absorption model Caco-2.” Int. J. Pharm., 222, 77–89.
Kulik, N., Goi, A., Trapido, M., and Tuhkanen, T. (2006). “Degradation of polycyclic aromatic hydrocarbons by combined chemical pre-oxidation and bioremediation in creosote contaminated soil.” J. Environ. Manage., 78, 382–391.
Langlais, B., Reckhow, D., and Brink, D. (1991). Ozone in water treatment, Lewis, Chelsea, Mich.
Lee, E. S., and Schwartz, F. W. (2007). “Characteristics and applications of controlled-release for groundwater remediation.” Chemosphere, 66, 2058–2066.
Leung, S. W., Watts, R. J., and Miller, G. C. (1992). “Degradation of perchloroethylene by Fenton’s reagent: Speciation and pathway.” J. Environ. Qual., 21, 377–381.
Levin, R., Kellar, E., Wilson, J., Ware, L., Findley, J., and Baehr, J. (2000). “Full-scale soil remediation of chlorinated solvents by in situ chemical oxidation.” Proc., 2nd Int. Conf. on Remediation of Chlorinated and Recalcitrant Compounds, Monterey, Calif., G. B. Wickramanayake, A. R. Gavaskar, and A. S. C. Chen, eds., 153–159.
Li, Z. (2004). “Surfactant-enhanced oxidation of trichloroethylene by permanganate—Proof of concept.” Chemosphere, 54, 419–423.
Li, X. D., and Schwartz, F. W. (2004a). “DNAPL remediation with in situ chemical oxidation using potassium permanganate. I: Mineralogy of Mn oxide and its dissolution in organic acids.” J. Contam. Hydrol., 68, 39–53.
Li, X. D., and Schwartz, F. W. (2004b). “DNAPL remediation with in situ chemical oxidation using potassium permanganate. II: Increasing removal efficiency by dissolving Mn oxide precipitates.” J. Contam. Hydrol., 68, 269–287.
Li, P., Tabibi, S. E., and Yalkowsky, S. H. (1999). “Solubilization of ionized and un-ionized avopiridol by ethanol and polysorbate 20.” J. Pharm. Sci., 88, 507–509.
Liang, C., 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., Bruell, C. J., Marley, M. C., and Sperry, K. L. (2004). “Persulfate oxidation for in situ remediation of TCE: Activated by ferrous ion with and without a persulfate–thiosulfate redox couple.” Chemosphere, 55, 1213–1223.
Liang, C., Wang, Z. S., and Bruell, C. J. (2007). “Influence of pH on persulfate oxidation of TCE at ambient temperatures.” Chemosphere, 66, 106–113.
Lien, H. L., and Zhang, W. X. (2001). “Nanoscale iron particles for complete reduction of chlorinated ethenes.” Colloids Surf., A, 191, 97–105.
Lindsey, M. E., Xu, G., Lu, J., and Tarr, M. A. (2003). “Enhanced Fenton degradation of hydrophobic organics by simultaneous iron and pollutant complexation with cyclodextrins.” Sci. Total Environ., 307, 215–229.
Liu, L., and Guo, Q. X. (2002). “The driving forces in the inclusion complexation of cyclodextrins.” J. Inclusion Phenom. Mol. Recognit. Chem., 42, 1–8.
Lunn, S. R. D., and Kueper, B. H. (1999). “Manipulation of density and viscosity for the optimization of DNAPL recovery by alcohol flooding.” J. Contam. Hydrol., 38, 427–445.
MacKinnon, L. K., and Thomson, N. R. (2002). “Laboratory-scale in situ chemical oxidation of a perchloroethylene pool using permanganate.” J. Contam. Hydrol., 56, 49–74.
Masten, S., and Hoigne, J. (1992). “Comparison of ozone and hydroxyl radical-induced oxidation of chlorinated hydrocarbons in water.” Ozone: Sci. Eng., 14, 197–214.
Mayer, A., and Endres, K. L. (2007). “Simultaneous optimization of dense non-aqueous phase liquid (DNAPL) source and contaminant plume remediation.” J. Contam. Hydrol., 91, 288–311.
Melero, J. A., Calleja, G., Martinez, F., Molina, R., and Pariente, M. I. (2007). “Nanocomposite : An efficient and stable catalyst for the catalytic wet peroxidation of phenolic aqueous solutions.” Chem. Eng. J., 131, 245–256.
Mitani, M. M., Keller, A. A., Bunton, C. A., Rinker, R. G., and Sandall, O. C. (2002). “Kinetics and products of reactions of MTBE with ozone and ozone/hydrogen peroxide in water.” J. Hazard. Mater., B89, 197–212.
Mulligan, C. N. (2005). “Environmental applications for biosurfactants.” Environ. Pollut., 133, 183–198.
Nelson, C., and R. Brown. (1994). “Adapting ozonation for soil and groundwater cleanup.” Chemosphere, 28, EE18–EE22.
Nema, S., Washkuhn, R. J., and Brendel, R. J. (1997). “Excipients and their use in injectable products PDA.” J. Pharm. Sci. Technol., 51, 166–171.
Neyens, E., and Baeyens, J. (2003). “A review of classic Fenton’s peroxidation as an advanced oxidation technique.” J. Hazard. Mater., 98, 33–50.
Nimmer, M., Wayner, B., and Morr, A. (2000). “In situ ozonation of contaminated groundwater.” Environ. Prog., 19(3), 183–196.
Oostrom, M., Hofstee, C., Walker, R. C., and Dane, J. H. (1999). “Movement and remediation of trichloroethylene in a saturated, heterogeneous porous medium 2. Pump-and-treat and surfactant flushing.” J. Contam. Hydrol., 37, 179–197.
Pan, L., Ho, Q., Tsutsui, K., and Takahashi, L. (2001). “Comparison of chromatographic and spectroscopic methods used to rank compounds for aqueous solubility.” J. Pharm. Sci., 90, 521–529.
Qin X. S., Huang, G. H., Chakma, A., Chen, B., and Zeng, G. M. (2007). “Simulation-based process optimization for surfactant-enhanced aquifer remediation at heterogeneous DNAPL-contaminated sites.” Sci. Total Environ., 381, 17–37.
Rivas, F. J. (2006). “Polycyclic aromatic hydrocarbons sorbed on soils: A short review of chemical oxidation based treatments.” J. Hazard. Mater., 138(2), 234–251.
Ross, C., Murdoch, L. C., Freedman, D. L., and Siegrist, R. L. (2005). “Characteristics of potassium permanganate encapsulated in polymer.” J. Environ. Eng., 131, 1203–1211.
Schaerlaekens, J., and Feyen, J. (2004). “Effect of scale and dimensionality on the surfactant-enhanced solubilization of a residual DNAPL contamination.” J. Contam. Hydrol., 71, 283–306.
Schwarzenbach, R. P., Gschwend, P. M., and Imboden, D. M. (2002) Environmental organic chemistry, Wiley, New York.
Siegrist, R. L., Urynowicz, M. A., West, O. R., Crimi, M. L., and Lowe, K. S. (2001). Principle and practices of in situ chemical oxidation using permanganate, Battelle Press, Columbus, Ohio.
Singh, N., and Lee, D. G. (2001). “Permanganate: A green and versatile industrial oxidant.” Org. Process Res. Dev., 5(6), 599–603.
Sperry, K. L., Marley, M. C., Bruell, C. J., Liang, C., and Hochreiter, J. (2002). “Iron-catalyzed persulfate oxidation of chlorinated solvents.” Remediation and Recalcitrant Compounds–2002, A. R. Gavaskar, and A. S. C. Chen, eds., Battelle Press, Columbus, Ohio, 1158–1165.
Strickley, R. G. (2004). “Solubilizing excipients in oral and injectable formulations.” Pharm. Res., 21, 201–230.
Susan, P., and Monice, Z. F. (2001). “Final report on the safety assessment of ammonium, potassium, and sodium persulfate.” Int. J. Toxicology, 20(3), 7–21.
Sutherland, J., Adams, C., and Kekobad, J. (2004). “Treatment of MTBE by air stripping, carbon adsorption, and advanced oxidation: Technical and economic comparison for five groundwaters.” Water Res., 38, 193–205.
Szejtli, J. (1982). Cyclodextrins and their inclusion complexes, Akademiai Kiado, Budapest, Hungary, 100–109.
Tantak, N. P., and Chaudhari, S. (2006). “Degradation of azo dyes by sequential Fenton’s oxidation and aerobic biological treatment.” J. Hazard. Mater., B136, 698–705.
Tyrovola, K., and Diamadopoulos, E. (2005). “Bromate formation during ozonation of groundwater in coastal areas in Greece.” Desalination, 176, 201–209.
USEPA. (2001). Treatment technologies for site cleanup annual status report, 10th Ed. EPA-542-R-01-004, Washington, D.C.
USEPA. (2004). Treatment technologies for site cleanup annual status report, 11th Ed. EPA-542-R-03-009, Washington, D.C.
Wakimoto, K. (2004). “Review: Utilization advantages of controlled release nitrogen fertilizer on paddy rice cultivation.” JARQ-Jpn. Agr. Res. Q., 38, 15–20.
Watts, R. J., and Dilly, S. E. (1996). “Evaluation of iron catalysis for the Fenton-like remediation of diesel-contaminated soils.” J. Hazard. Mater., 51, 209–224.
Watts, R. J., Stanton, P. C., Howsawkeng, J., and Teel, A. L. (2002). “Mineralization of a sorbed polycyclic aromatic hydrocarbon in two soils using catalyzed hydrogen peroxide.” Water Res., 36(17), 4283–4292.
Weeks, K. R., Bruell, C. J., and Mohanty, N. R. (2000). “Use of Fenton’s reagent for the degradation of TCE in aqueous systems and soil slurries.” Soil Sediment Contam., 9(4), 331.
Yaghmur, A., Aserin, A., and Garti, N. (2002). “Phase behavior of microemulsions based on food-grade nonionic surfactants: Effect of polyols and short-chain alcohols.” Colloids Surf., A, 209, 71–81.
Yan, Y. E., and Schwartz, F. W. (2000). “Kinetics and mechanisms for TCE oxidation by permanganate.” Environ. Sci. Technol., 34, 2535–2541.
Yang, J. S., Baek, K., Kwon, T. S., and Yang, J. W. (2006). “Competitive immobilization of multiple component chlorinated solvents by cyclodextrin derivatives.” J. Hazard. Mater., B137, 1866–1869.
Yeh, C. K. J., Kao, Y. A., and Chen, C. P. (2002). “Oxidation of chlorophenols in soil at natural pH by catalyzed hydrogen: The effect of soil organic matter.” Chemosphere, 46, 67–73.
Yeh, C. K. J., Wu, H. M., and Chen, T. C. (2003). “Chemical oxidation of chlorinated non-aqueous phase liquids by hydrogen peroxide in natural sand systems.” J. Hazard. Mater., 96, 29–51.
Yin, Y., and Allen, H. E. (1999). “In situ chemical treatment.” Technology Evaluation Rep., Groundwater Remediation Technologies Analysis Center, Pittsburgh, 3–6.
Zhai, X., Hua, I., Rao, P. S. C., and Lee, L. S. (2006). “Cosolvent-enhanced chemical oxidation of perchloroethylene by potassium permanganate.” J. Contam. Hydrol., 82, 61–74.
Zhang, W. X. (2003). “Nanoscale iron particles for environmental remediation: An overview.” J. Nanopart. Res., 5, 323–332.
Information & Authors
Information
Published In
Practice Periodical of Hazardous, Toxic, and Radioactive Waste Management
Volume 12 • Issue 2 • April 2008
Pages: 116 - 126
Copyright
© 2008 ASCE.
History
Received: Oct 1, 2007
Accepted: Oct 1, 2007
Published online: Apr 1, 2008
Published in print: Apr 2008
Authors
Metrics & Citations
Metrics
Citations
Download citation
If you have the appropriate software installed, you can download article citation data to the citation manager of your choice. Simply select your manager software from the list below and click Download.