本研究探討過硫酸鹽(Persulfate)對水中三氯乙烯(TCE)在不同氧化劑濃度 (Persulfate/TCE = 20及60)、離子強度及離子種類等熱催化氧化之動力。過硫酸鹽的分解反應乃遵循一階衰減，其在無磷酸緩衝溶液條件下的自解之反應速率約為0.0030 hr-1，比其在磷酸緩衝溶液條件下的自解0.0011 hr-1來得快。此項差異可以歸諸於在緩衝溶液條件下，因為pH值變化固定於6.6，因此酸催化作用不明顯，以及離子強度增加之緣故。TCE在40oC及pH6.6 的氧化動力顯示其去除率與 P/T 莫耳比呈正相關，然過硫酸鹽的消耗對不同的P/T 莫耳比卻無顯著差異。研究中並提出三項模式，以模擬過硫酸鹽與TCE之反應動力數據。其中模式3考量過硫酸鹽自解、甲醇氧化及TCE氧化等三個機制，可以合理模擬所有觀測到的數據。該模式所得到之最佳化參數(0.016 M-1s-1、0.023 M-1s-1 TCE，及0.034 hr-1、0.050 hr-1 過硫酸鹽)在不同環境條件下相當接近，顯示可以跨系統使用。TCE的降解會受到水中離子濃度及種類影響。由於硝酸根離子屬最高氧化態，若與氯離子及溴離子比較，其對TCE氧化之影響則最小，僅止於離子濃度效應，相對而言，鹵素離子(如氯離子及溴離子)，除離子濃度效應外，因為是自由基的攜帶者，會降低過硫酸鹽的自解速率，同時亦降低TCE的去除。然而，在非常高濃度的氯存在下，反應經過20小時後，TCE的去除卻大幅提升，此可能因高濃度的氯離子反應後產生的Cl2-•會繼續與污染物起反應並去除之。由簡化模式(模式2)模擬的結果得知，模式與實驗結果相當吻合。TCE的降解速率(k3)與無三種離子狀況下比較(k3 = 0.023 M-1s-1)，在氯離子為0.01 M、0.1M及0.5M情況下，降低為0.0044 M-1s-1, 0.0004 M-1s-1及0.0006 M-1s-1。在溴離子及硝酸鹽為0.5M情況下，降低為0.0003 M-1s-1及 0.009 M-1s-1。雖然這些k3在不同條件下不同，但是可以提供在不同陰離子條件下之氧化動力參考數值。

　The kinetics on heat-assisted persufate oxidation of trichloroethene (TCE) in aqueous solutions at various oxidant concentrations (persulfate/TCE ratio = 20 and 60), ionic strength and ionic kinds was studied. The decomposition of persulfate was found to follow a first-order decay kinetic model in deionized water, and the rate constant was larger in unbuffered condition of at around 0.0030 hr-1 than that in buffered condition at 0.0011 hr-1. The difference may be attributed to that no acid-catalyzed reaction was present in the buffered condition as the pH remained always constant at 6.6, and higher ionic strength in the condition. A higher persulfate/TCE molar ratio in the oxidation experiments resulted higher efficiencies of TCE destruction by persulfate at 40 C. Three models were proposed to simulate the kinetic data of both persulfate and TCE. Model 3, which considered the effect of persulfate decomposition, methanol oxidation, and TCE degradation, was able to simulate all the experimental data to a reasonable degree. The determined rate constants (0.016 M-1s-1 and 0.023 M-1s-1 for TCE, and 0.034 hr-1 and 0.050 hr-1 for persulfate), were close in different experimental conditions, indicating that the model and the extracted parameters may be appropriate for extrapolating into other systems. The oxidation of TCE by persulfate was influenced at different degree by the presence of three anions, nitrate, chloride, and bromide. For nitrate, the influence is the smallest and may be attributed to the effect of increasing ionic strength. For both chloride and bromide, in addition to the ionic strength effect, it is speculated that the two anions were radical scavengers that caused additional reduction of reaction rates. A simplified model (model 2) was employed to simulate the kinetics of both persulfate and TCE concentration changes with the presence of the three anions in the systems. Excellent model fits to the experimental data was obtained in this study. Compared to the case without the presence of the three anions (k3 = 0.023 M-1s-1), the rate constants for TCE degradation were much smaller at 0.0044 M-1s-1, 0.0004 M-1s-1 and 0.0006 M-1s-1 for chloride cases at 0.01, 0.1, and 0.5 M, respectively, and were 0.0003 M-1s-1 and 0.009 M-1s-1, for bromide and nitrate cases at 0.5M, respectively. Although the rate constants are different under different experimental conditions, the determined rate constants may provide basis for estimating the reaction rate under the influence of different anions.

Alexander A., and Eli K., 2001. Solubilities and vapour pressures of saturated aqueous solutions of sodium peroxydisulfate and potassium peroxydisulfate. J. Chemical Thermodynamics, 33, 61-69.

Amarante D., 2000. Applying in situ chemical oxidation. Pollution Engineering, 32(2), 40-42.

Behrman E.J., and Dean D.H., 1999. Sodium peroxydisulfate is a stable and cheap substitute for ammonium peroxydisulfate (Persulfate) in polyacrylamide gel electrophoresis. J. Chromatography. B, 723, 325-326.

Berlin Ad. A., 1986. Kinetics of radical-chain decomposition of persulfate in aqueous solutions of organic compounds. Kinetics and Catalysis, 27, 34-39.

Brown R.A., Robinson D., Skladany G., and Loeper J., 2003. Response to naturally occurring organic material: Permanganate versus persulfate. Proceedings of ConSoil, 2003-8th International FZK/TNO Conference on Contaminated Soil, 1692-1698, May 12-16, Gent, Belgium.

Dijkshoorn P., 2003. In-situ chemical oxidation of chlorinated solvents with potassium permanganate on a site in Belgium. Proceedings of ConSoil, 2003-8th International FZK/TNO Conference on Contaminated Soil, 1686-1691, May 12-16, Gent, Belgium.

Dogliotti L. and Hayon E., 1967. Flash photolysis of persulfate ions in aqueous solutions. Study of the sulfate and ozonide redical anions. J. Physical Chemistry, 71(8), 2511-2516.

Edwards J.O., 1980. Thermal decomposition of peroxodisulphate ions. Reviews in Inorganic Chemistry, 2(3), 179-206.

Environmental Security Technology Certification Program (ESTCP), 1999. Technology Status Review: In-Situ Oxidation, Http://www.estcp.gov/.

Gareth J.P. and Andrew A.C., 1996. Polymer communications: sonochemical acceleration of persulfate decomposition. Polymer, 37(17), 3971-3973.

Gates, D.D., and Siegrist, R.L., 1995. In situ chemical oxidation of trichloroethylene using hydrogen peroxide. J. Environmental Engineering, 121, 639-644.

Gates-Anderson, D.D., Siegrist, R.L., and S.R. Cline, 2001. Comparixon of potassium permanganate and hydrogen peroxide as chemical oxidants for organically contaminated soils. J. Environmental Engineering, 127(4): 337-347.

Goulden P.D. and Anthony D.H.J., 1978. Kinetics of uncatalyzed peroxydisulfate oxidation of organic material in fresh water. Analytical Chemistry, 50(7), 953-958.

Halogenated Solvents Industry Alliance, Inc., 2001. Trichloroethylene, HSIA white paper, February.

Hayon E., and McGarvey J.J., 1967. Flash photolysis in the vacuum ultraviolet region of SO42-, CO32- and OH- ions in aqueous solutions. J. Physical Chemistry, 71, 1472-1477.

Hayon E., Treinin A., and Wilf A., 1972. Electron spectra, photochemistry and qutooxidation mechanism of the sulfite-bisulfite-pyrosulfite systems. J. America Chemistry Society, 94, 47-57.

Hoag, G.E., Chheda, V., Woody, B.A., and Dobbs, G.M., 2000. Chemical oxidation of volatile organic compounds. U.S. Patent no.6, 019, 548.

House D.A., 1962. Kinetics and mechanism of oxidations by peroxydisulfate. Chemical Reviews, 62, 185-203.

Huang K.C., Couttenye R.A., Hoag G.E., 2002. Kinetics of heat-assisted persulfate oxidation of Methyl tert-Butyl Ether (MTBE). Chemoshpere, 49, 413-420

International Technology and Regulatory Cooperation (ITRC), 2002. In situ chemical oxidation. ITRC Training Course for SRP, October. Http://www.itrcweb.org/

Kelly K.L., Marley, M.C., Sperry, K.L., 2002. In situ chemical oxidation on MTBE. Proceedings of 2002 Joint CSCE/EWRI of ASCE International Conference on Environmental Engineering, July 21-24, Niagara Falls, Ontario, Canada.

Kislenko V.N., Berlin A.A., and Litovchnko N.V., 1995. Kinetics of oxidation of glucose by persulfate ions in the presence of Mn(II) ions. Kinetics and Catalysis, 38(3), 359-364.

Kolthoff I.M. and Miller I.K., 1951. The chemistry of persulfate. I. The kinetics and mechanism of the decomposition of the persulfate ion in aqueous medium. J. American Chemical Society, 73, 3055-3059.

Leung, S.W., Watts R.J. and Miller G.C., 1992. Degradation of erchloroethylene by Fenton’s reagent: speciation and pathway. J. Environmental Quality, 21, 377-381.

Lewis R.W., 2002. Key factor for a successful ISCO application with permanganate. Teleconference of In Situ Treatment of Groundwater Contaminated with Non-Aqueous Phase Liquids, Dec 10-11, 2002, Chicago, IL. Http://www.clu-in.org/.

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-Trichlorothane (TCA) in aqueous systems and soil slurries. Soil and Sediment Contamination, 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. Acivated by ferrous ion with and without a persulfate-thiosulfate recox couple. Chemosphere, 55, 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. Acivated by chelated ferrous ion. Chemosphere, 55, 1225-1233.

Lin T.F. (2002) Current status of physico-chemical and thermal treatment technologies for soil and ground water remediation, Environmental Protection Monthly 9, 87-99, 2002. (In Chinese)

Lowe K.S., Gardner F.G., Siegrist R.L., and Houk T.C., 2000. Field pilot test of in situ chemical oxidation through recirculation using vertical wells at the Portsmouth gaseous diffusion plant. EPA/625/R-99/012. U.S. EPA ORD, Washington, DC., 42-49.

MacKinnon, L.K., and Thomson, N.R., 2002. Laboratory-scale in situ chemical oxidation of a perchloroethylele pool using permanganate, J. Contaminant Hydrology, 56, 49-74.

Neta P., Robert E. H., and Alberta B. R., 1988. Rate constants for reactions of inorganic radical in aqueous solution. J. Physical Chemistry Reference Data, 17 (3), 1027-1262.

Peter J. Palko, P.E., CHMM, Chuck Elmendorf, Kevin D.Dyson, and EIT (Panther Technologies), 2004. Ex-situ remediation of PCE and TCE in soils using a proprietary, persulfate-based oxidation technology. Http://www.panthertech.com/

Peyton G.R., 1993. The free-radical chemistry of persulfate-based total organic carbon analyzers. Marine Chemistry, 41, 91-103.

Peyton G.R., 1998. Effect of bicarbonate alkalinity on performance of advanced oxidation processes, chapter 3, 13-15.

Pugh, J.R., 1999. In situ remediation of soils containing organic contaminants using the electromigration of peroxysulfate ions. U.S. Patent 597348.
Richard A.B., David R., George S., Joseph L., 2002. Response to naturally occurring organic material: permanganate versus pesulfate. USEPA, Solid Waste and Emergency Response, EPA 542-N-02-002, 43, 1692-1698.

Riggs J.P. and Rodriguez F., 1967. Polymerization of acrylamide initiated by the persulfate-thiosulfate redox couple. J. polymer science: part A-1, 5, 3167-3181.

Schnarr M., Traux C., Farquhar G., Hood E., Gonullu T., and Stickney B. (1998) Laboratory and controlled field experiments using potassium permanganate to remediate Trichloroethylene and Perchloroethylene DNAPLs in porous media. J. Contaminant Hydrology, 29, 205-224.

Schroth, M.H., Oostrom, M., Wietsma, T.W., and Istok, J.D. (2001) In-situ oxidation of Trichloroethylene by permanganate: effects on porous medium hydraulic properties, J. Contaminant Hydrology, 50, 79-98.

Siegrist R.L., 2002. Fundamentals of in situ chemical oxidation (ISCO). Teleconference of In Situ Treatment of Groundwater Contaminated With Non-Aqueous Phase Liquids, Dec 10-11, 2002, Chicago, IL. Http://www.clu-in.org/.

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.

Siegrist R.L, Lowe K.S., Murdoch L.C., Slack W.W., and Houk T.C., 1998a. X-231A demonstration of in situ remediation of DNAPL compounds in low permeability media by soil fracturing with thermally enhanced mass recovery or reactive barrier destruction. Oak Ridge National Laboratory report. ORNL/TM-13534.

Siegrist R.L, Lowe K.S., Murdoch L.C., Case T.L., Pickering D.A., and Houk T.C., 1998b. Horizontal treatment barriers of fracture-emplaced iron and permanganate particles. NATO/CCMS pilot study special session on treatment walls and permeable reactive barriers. EPA 542-R-98-003. May 1998, 77-82.
Siegrist R.L, Lowe K.S., Murdoch L.C., Case T.L., and Pickering D.A., 1999. In situ oxidation by fracture emplaced reactive solids. J. Environmental Engineering. 125(5), 429-440.

Struse A.M. and Siegrist R.L., 2000. Permanganate transport and matrix interactions in silty clay soils. In: Wickramanayake, G.B., A.R. Gavaskar, and A.S.C. Chen (ed.). Chemical Oxidation and Reactive Barriers. Battelle Press, Columbus, OH. 67-74.

Susan P., and Monice Z.F., 2001. Final report on the safety assessment of ammonium, potassium, and sodium persulfate. Internation Journal of Toxicology. 20(3), 7-21.

Tieckelmann, R.H., Thorp, D.S., Gagliardi, C., and Downey, G.D., 1998. Use of persulfate to destroy haloform. U.S. Patent 5, 849, 985.

Urynowicz M.N., and Siegrist R.L., 2000. Chemical degradation of TCE DNAPL by permanganate. In: Wickramanayake, G.B., A.R. Gavaskar, and A.S.C. Chen (ed.). Chemical Oxidation and Reactive Barriers. Battelle Press, Columbus, OH. 75-82.

U.S. Department of Energy, 1999. In situ chemical oxidation using potassium permanganate. Innovative Technology Summary Report.

U.S. Department of Energy, 2000. Permanganate treatment of DNAPLs in reactive barriers and source zone flooding schemes. Final Report.

U.S. Environmental Protection Agency (USEPA), 2004. How to Evaluate Alternative Cleanup Technologies for Underground Storage Tank Sites: A Guide for Corrective Action Plan Reviewers, EPA 510-R-04-002.

Vella P.A., Deshinsky G., Boll J.E., Munder J., and Joyce W.M., 1990. Treatment of low level phenols with potassium permanganate. Research journal of the Water Pollution Control Federation, 62(7), 907-914.

Vella, P.A. and Veronda B., 1994. Oxidation of Trichloroethylene: A comparison of potassium permanganate and Fenton’s reagent. 3rd Intern. Symposium on chemical oxidation. In: In situ chemical oxidation for the nineties. Vol. 3. Technomic Publishing Co., Inc. Lancaster, PA. 62-73.

Von S.C., 1989. The chemical basis of radiation biology. Taylor and Francis, New York, 515.

Vorsina I.A., Grishakova T.E., and Mikhailov Y.I., 1995. Thermal decomposition of ammonium persulfate studied by raman spectroscopy. Inorganic Materials, 31(11), 1321-1324.

Vorsina I.A., 1997. Initial stage in the thermal decomposition of persulfates. Inorganic Materials, 33(6), 639-640.

West O.R., Cline S.R., Holden W.L., Gardner F.G., Schlosser B.M., Thate J.E., Pickering, D.A. and Houk T.C., 1998a. A full-scale field demonstration of in situ chemical oxidation through recrculation at the X-701B site. Oak Ridge National Laboratory Report, ORNL/TM-13556.

West O.R., Cline, S.R., Siegrist R.L., Houk T.C., Holden W.L., Gardner F.G., and Schlosser B.M., 1998b. A field-scale test of in situ chemical oxidation through recirculation. Proc. Spectrum ’98 International Conference on Nuclear and hazardous Waste Management. Denver, Colorado, Set. 13-18, 1051-1057.

Yan Y.E. and Schwartz F. W., 1996. Oxidation of chlorinated solvents by permanganate. Proc. Intern. Conf. on Remediation of Chlorinated and Recalcitrant Compounds, Ohio: Battelle Press., 403-408.

Yan Y.E. and Schwartz F. W., 1999. Oxidative degradation and kinetics of chlorinated ethylenes by potassium permanganate. J. Contaminant Hydrology 37, 343-365.

Yan Y.E. and Schwartz F. W., 2000. Kinetics and mechanisms for TCE oxidation by permanganate. Environmental science & technology, 34, 2535-2541.

Yang C.C., 2003 Oxidation of MTBE in Water, Master Thesis, Depatment of Environmental Engineering, National Cheng Kung University, Tainan City, Taiwan (ROC). (In Chinese)

Yu X.Y., Bao Z.C., and John R.B., 2004. Free radical reaction involving Cl‧, Cl2-‧, and SO4-‧ in the 248 nm photolysis of aqueous solutions containing S2O82- ad Cl-. J. Physical Chemistry A, 108, 295-308.