Degradation of carbon tetrachloride in thermally activated persulfate system in the presence of formic acid

Abstract

The thermally activated persulfate (PS) degradation of carbon tetrachloride (CT) in the presence of formic acid (FA) was investigated. The results indicated that CT degradation followed a zero order kinetic model, and \mathrm{C}{\mathrm{O}}_{\mathrm{2}}^{-}· was responsible for the degradation of CT confirmed by radical scavenger tests. CT degradation rate increased with increasing PS or FA dosage, and the initial CT had no effect on CT degradation rate. However, the initial solution pH had effect on the degradation of CT, and the best CT degradation occurred at initial pH 6. Cl^- had a negative effect on CT degradation, and high concentration of Cl^- displayed much strong inhibition. Ten mmol·L^-1\mathrm{H}\mathrm{C}{\mathrm{O}}_{\mathrm{3}}^{-} promoted CT degradation, while 100 mmol·L^-1\mathrm{N}{\mathrm{O}}_{\mathrm{3}}^{-} inhibited the degradation of CT, but \mathrm{S}{\mathrm{O}}_{\mathrm{4}}^{\mathrm{2}-} promoted CT degradation in the presence of FA. The measured Cl^- concentration released into solution along with CT degradation was 75.8% of the total theoretical dechlorination yield, but no chlorinated intermediates were detected. The split of C-Cl was proposed as the possible reaction pathways in CT degradation. In conclusion, this study strongly demonstrated that the thermally activated PS system in the presence of FA is a promising technique in in situ chemical oxidation (ISCO) remediation for CT contaminated site.

Keywords

persulfate / carbon tetrachloride / thermal activation / formic acid / carbon dioxide radical anion

References

[1] Choi J, Choi K, Lee W. Effects of transition metal and sulfide on the reductive dechlorination of carbon tetrachloride and 1,1,1-trichloroethane by FeS. Journal of Hazardous Materials, 2009, 162(2-3): 1151-1158

[2] TÁmara M L, Butler E C. Effects of iron purity and groundwater characteristics on rates and products in the degradation of carbon tetrachloride by iron metal. Environmental Science & Technology, 2004, 38(6): 1866-1876

[3] Buxton G V, Greenstock C L, Helman W P, Ross A B. Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (•OH/•O^-) in aqueous solution. Journal of Physical and Chemical Reference Data, 1988, 17(2): 513-886

[4] Gu X G, Lu S G, Li L, Qiu Z F, Sui Q, Lin K F, Luo Q S. Oxidation of 1,1,1-trichloroethane stimulated by thermally activated persulfate. Industrial & Engineering Chemistry Research, 2011, 50(19): 11029-11036

[5] Liang C, Bruell C J, Marley M C, Sperry K L. Persulfate oxidation for in situ remediation of TCE. I. Activated by ferrous ion with and without a persulfate-thiosulfate redox couple. Chemosphere, 2004, 55(9): 1213-1223

[6] Fang G D, Dionysiou D D, Al-Abed S R, Zhou D M. Superoxide radical driving the activation of persulfate by magnetite nanoparticles: implications for the degradation of PCBs. Applied Catalysis B: Environmental, 2013, 129(2): 325-332

[7] Fang G, Gao J, Dionysiou D D, Liu C, Zhou D. Activation of persulfate by quinones: free radical reactions and implication for the degradation of PCBs. Environmental Science & Technology, 2013, 47(9): 4605-4611

[8] Ahmad M, Teel A L, Watts R J. Mechanism of persulfate activation by phenols. Environmental Science & Technology, 2013, 47(11): 5864-5871

[9] Zhao J Y, Zhang Y B, Quan X, Chen S. Enhanced oxidation of 4-chlorophenol using sulfate radicals generated from zero-valent iron and peroxydisulfate at ambient temperature. Separation and Purification Technology, 2010, 71(3): 302-307

[10] House D A. Kinetics and mechanism of oxidations by peroxydisulfate. Chemical Reviews, 1962, 62(3): 185-203

[11] Pennington D E, Haim A. Stoichiometry and mechanism of the chromium(II)—peroxydisulfate reaction. Journal of the American Chemical Society, 2002, 90(14): 3700-3704

[12] Peyton G R. The free-radical chemistry of persulfate-based total organic carbon analyzers. Marine Chemistry, 1993, 41(1-3): 91-103

[13] Kolthoff I M, Miller I K. The chemistry of persulfate. I. The kinetics and mechanism of the decomposition of the persulfate ion in aqueous medium1. Journal of the American Chemical Society, 1951, 73(7): 3055-3059

[14] Watts R J, Bottenberg B C, HessT F, Jensen M D, Teel A L. Role of reductants in the enhanced desorption and transformation of chloroaliphatic compounds by modified Fenton’s reactions. Environmental Science & Technology, 1999, 33(19): 3432-3437

[15] Bielski B H, Cabelli D E, Arudi R L, Ross A B. Reactivity of HO₂/O2- radicals in aqueous solution. Journal of Physical and Chemical Reference Data, 1985, 14(4): 1041-1100

[16] Liang C J, Bruell C J, Marley M C, Sperry K L. Thermally activated persulfate oxidation of trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA) in aqueous systems and soil slurries. Soil & Sediment Contamination, 2003, 12(2): 207-228

[17] Mora V C, Rosso J A, Carrillo Le Roux G, Mártire D O, Gonzalez M C. Thermally activated peroxydisulfate in the presence of additives: a clean method for the degradation of pollutants. Chemosphere, 2009, 75(10): 1405-1409

[18] Lin M Z, Katsumura Y, Muroya Y, He H, Miyazaki T, Hiroishi D. Pluse radiolysis of sodium formate aqueous solution up to 400°C: absorption spectra, kinetics and yield of carboxyl radical CO2-·. Radiation Physics and Chemistry, 2008, 77(10-12): 1208-1212

[19] Liang C, Huang C F, Mohanty N, Kurakalva R M. A rapid spectrophotometric determination of persulfate anion in ISCO. Chemosphere, 2008, 73(9): 1540-1543

[20] Xu M, Gu X, Lu S, Qiu Z, Sui Q, Miao Z, Zang X, Wu X. Degradation of carbon tetrachloride in aqueous solution in the thermally activated persulfate system. Journal of Hazardous Materials, 2015, 286: 7-14

[21] Neta P, Huie R E, Ross A B. Rate constants for reactions of inorganic radicals in aqueous solution. Journal of Physical and Chemical Reference Data, 1988, 17(3): 1027-1284

[22] Mulazzani Q G, D’Angelantonio M, Venturi M, Hoffman M Z, Rodgers M A. Interaction of formate and oxalate ions with radiation-generated radicals in aqueous solution. Methylviologen as a mechanistic probe. Journal of Physical Chemistry, 1986, 90(21): 5347-5352

[23] Berkovic A M, Gonzalez M C, Russo N, Michelini M C, Pis Diez R, Mártire D O. Reduction of mercury(II) by the carbon dioxide radical anion: a theoretical and experimental investigation. Journal of Physical Chemistry A, 2010, 114(49): 12845-12850

[24] Das T N, Ghanty T K, Pal H. Reactions of methyl viologen dication (MV²⁺) with H atoms in aqueous solution: mechanism derived from pulse radiolysis measurements and ab initio mo calculations. Journal of Physical Chemistry A, 2003, 107(31): 5998-6006

[25] Gonzalez M C, Le Roux G C, Rosso J A, Braun A M. Mineralization of CCl₄ by the UVC-photolysis of hydrogen peroxide in the presence of methanol. Chemosphere, 2007, 69(8): 1238-1244

[26] Cooper W J, Cramer C J, Martin N H, Mezyk S P, O’Shea K E, von Sonntag C. Free radical mechanisms for the treatment of methyl tert-butyl ether (MTBE) via advanced oxidation/reductive processes in aqueous solutions. Chemical Reviews, 2009, 109(3): 1302-1345

[27] Flyunt R, Schuchmann M N, von Sonntag C. A common carbanion intermediate in the recombination and proton-catalysed disproportionation of the carboxyl radical anion, CO2-·, in aqueous solution. Chemistry (Weinheim an der Bergstrasse, Germany), 2001, 7(4): 796-799

[28] Morkovinik A F, Okhlobystin O Y. Inorganic radical-ions and their organic reactions. Russian Chemical Reviews, 1979, 48(11): 1055-1075

[29] Buxton G V, Bydder M, Salmon G A. The reactivity of chlorine atoms in aqueous solution, Part II. The reactivity of chlorine atoms in aqueous solution II: The equilibrium SO4-· + Cl^- ↔SO42- + Cl•. Physical Chemistry Chemical Physics, 1999, 1(2): 269-273

[30] Regino C A, Richardson D E. Bicarbonate-catalyzed hydrogen peroxide oxidation of cysteine and related thiols. Inorganica Chimica Acta, 2007, 360(14): 3971-3977

[31] Draganić Z D, Negrón-Mendoza A, Sehested K, Vujošević S I, Navarro-Gonzáles R, Albarrán-SanchezM G, Draganić I G. Radiolysis of aqueous solutions of ammonium bicarbonate over a large dose range. International Journal of Radiation Applications and Instrumentation Part C Radiation Physics and Chemistry, 1991, 38(3): 317-321

[32] Padmaja S, Neta P, Huie R E. Rate constants for some reactions of inorganic radicals with inorganic ions. Temperature and solvent dependence. International Journal of Chemical Kinetics, 1993, 25(6): 445-455

[33] Neta P, Grodkowsk J, Ross A B. Rate constants for reactions of aliphatic carbon-centered radicals in aqueous solution. Journal of Physical and Chemical Reference Data, 1996, 25(3): 709-1050

[34] McCormick M L, Adriaens P. Carbon tetrachloride transformation on the surface of nanoscale biogenic magnetite particles. Environmental Science & Technology, 2004, 38(4): 1045-1053

[35] McCormick M L, Bouwer E J, Adriaens P. Carbon tetrachloride transformation in a model iron-reducing culture: relative kinetics of biotic and abiotic reactions. Environmental Science & Technology, 2002, 36(3): 403-410

Acknowledgements

This study was financially supported by a grant from the National Natural Science Foundation of China (Grant Nos. 41373094 and 51208199).

RIGHTS & PERMISSIONS

2014 Higher Education Press and Springer-Verlag Berlin Heidelberg