Application of permanganate in the oxidation of micropollutants: a mini review

Abstract

As a green oxidant, permanganate has received considerable attention for the removal of micropollutants in drinking water treatment. To provide a better understanding of the oxidation of organic micropollutants with permanganate, the oxidation kinetics of 32 micropollutants were compiled. The pollutants include algal toxins, endocrine disrupting chemicals (EDCs), and pharmaceuticals. The oxidation kinetics of micropollutants by permanganate were found to be first order with respect to both contaminant and permanganate concentrations from which second-order rate constants (k″) were obtained. Permanganate oxidized the heterocyclic aromatics with vinyl moiety (i.e., microcystins, carbamazepine, and dichlorvos) by the addition of double bonds. For the polycyclic aromatic hydrocarbons (PAHs) with alkyl groups, permanganate attacked the benzylic C-H through abstraction of hydrogen. The mechanism for the oxidation of phenolic EDCs by permanganate was a single electron transfer and aromatic ring cleavage. The presence of background matrices could enhance the oxidation of some phenolic EDCs by permanganate, including phenol, chlorinated phenols, bisphenol A, and trichlosan. The toxicity of dichlorvos solution increased after permanganate oxidation, and the estrogenic activity of bisphnol A/estrone increased significantly at the beginning of permanganate oxidation. Therefore, the toxicity of degradation products or intermediates should be determined in the permanganate oxidation processes to better evaluate the applicability of permanganate. The influence of background ions on the permanganate oxidation process is far from clear and should be elucidated in the future studies to better predict the performance of permanganate oxidation of micropollutants. Moreover, methods should be employed to catalyze the permanganate oxidation process to achieve better removal of micropollutants.

Keywords

pharmaceuticals / endocrine disrupting chemicals (EDCs) / algal toxins / permanganate / oxidation

References

[1] Kolpin D W, Furlong E T, Meyer M T, Thurman E M, Zaugg S D, Barber L B, Buxton H T. Pharmaceuticals, hormones, and other organic wastewater contaminants in U.S. streams, 1999-2000: a national reconnaissance. Environmental Science & Technology, 2002, 36(6): 1202–1211

[2] Snyder S A, Westerhoff P, Yoon Y, Sedlak D L. Pharmaceuticals, personal care products, and endocrine disruptors in water: implications for the water industry. Environmental Engineering Science, 2003, 20(5): 449–469

[3] Jobling S, Nolan M, Tyler C R, Brighty G, Sumpter J P. Widespread sexual disruption in wild fish. Environmental Science & Technology, 1998, 32(17): 2498–2506

[4] Ohe T, Watanabe T, Wakabayashi K. Mutagens in surface waters: a review. Mutation Research, 2004, 567(2-3): 109–149

[5] Zhang T C, Emary S C. Jar tests for evaluation of atrazine removal at drinking water treatment plants. Environmental Engineering Science, 1999, 16(6): 417–432

[6] Petrovic M, Eljarrat E, de Alda M J L, Barcelo D. Analysis and environmental levels of endocrine-disrupting compounds in freshwater sediments. TrAC Trends in Analytical Chemistry, 2001, 20: 637–648

[7] Ternes T A, Meisenheimer M, McDowell D, Sacher F, Brauch H J, Haist-Gulde B, Preuss G, Wilme U, Zulei-Seibert N. Removal of pharmaceuticals during drinking water treatment. Environmental Science & Technology, 2002, 36(17): 3855–3863

[8] Westerhoff P, Yoon Y, Snyder S, Wert E. Fate of endocrine-disruptor, pharmaceutical, and personal care product chemicals during simulated drinking water treatment processes. Environmental Science & Technology, 2005, 39(17): 6649–6663

[9] Vongunten U. Ozonation of drinking water: part I. Oxidation kinetics and product formation. Water Research, 2003, 37(7): 1443–1467

[10] Gallard H, von G U. Chlorination of natural organic matter: kinetics of chlorination and of THM formation. Water Research, 2002, 36(1): 65–74

[11] Vongunten U. Ozonation of drinking water: part II. Disinfection and by-product formation in presence of bromide, iodide or chlorine. Water Research, 2003, 37(7): 1469–1487

[12] Hoigné J, Bader H. Kinetics of reactions of chlorine dioxide (OClO) in water -I. Rate constants for inorganic and organic compounds. Water Research, 1994, 28(1): 45–55

[13] Krasner S W, Weinberg H S, Richardson S D, Pastor S J, Chinn R, Sclimenti M J, Onstad G D, Thruston A D Jr. Occurrence of a new generation of disinfection byproducts. Environmental Science & Technology, 2006, 40(23): 7175–7185

[14] Jiang J Q, Lloyd B. Progress in the development and use of ferrate(VI) salt as an oxidant and coagulant for water and wastewater treatment. Water Research, 2002, 36(6): 1397–1408

[15] Stewart R. Oxidation Mechanisms. New York: W A Benjamin Inc., 1964

[16] Waldemer R H, Tratnyek P G. Kinetics of contaminant degradation by permanganate. Environmental Science & Technology, 2006, 40(3): 1055–1061

[17] Rodríguez E, Majado M E, Meriluoto J, Acero J L. Oxidation of microcystins by permanganate: reaction kinetics and implications for water treatment. Water Research, 2007, 41(1): 102–110

[18] Ma J, Graham N, Li G. Effects of permanganate preoxidation in enhancing the coagulation of surface waters–Laboratory case studies. Journal of Water Supply Research and Technology-AQUA, 1997, 46: 1–10

[19] Rodríguez E, Sordo A, Metcalf J S, Acero J L. Kinetics of the oxidation of cylindrospermopsin and anatoxin-a with chlorine, monochloramine and permanganate. Water Research, 2007, 41(9): 2048–2056

[20] Hu L, Martin H M, Arce-Bulted O, Sugihara M N, Keating K A, Strathmann T I. Oxidation of carbamazepine by Mn(VII) and Fe(VI): reaction kinetics and mechanism. Environmental Science & Technology, 2009, 43(2): 509–515

[21] Liu C, Qiang Z, Adams C, Tian F, Zhang T. Kinetics and mechanism for degradation of dichlorvos by permanganate in drinking water treatment. Water Research, 2009, 43(14): 3435–3442

[22] Kao C M, Huang K D, Wang J Y, Chen T Y, Chien H Y. Application of potassium permanganate as an oxidant for in situ oxidation of trichloroethylene-contaminated groundwater: a laboratory and kinetics study. Journal of Hazardous Materials, 2008, 153(3): 919–927

[23] Tixier C, Singer H P, Oellers S, Müller S R. Occurrence and fate of carbamazepine, clofibric acid, diclofenac, ibuprofen, ketoprofen, and naproxen in surface waters. Environmental Science & Technology, 2003, 37(6): 1061–1068

[24] Pomati F, Castiglioni S, Zuccato E, Fanelli R, Vigetti D, Rossetti C, Calamari D. Effects of a complex mixture of therapeutic drugs at environmental levels on human embryonic cells. Environmental Science & Technology, 2006, 40(7): 2442–2447

[25] Cooper R L, Kavlock R J. Endocrine disruptors and reproductive development: a weight-of-evidence overview. The Journal of Endocrinology, 1997, 152(2): 159–166

[26] Richards S M, Wilson C J, Johnson D J, Castle D M, Lam M, Mabury S A, Sibley P K, Solomon K R. Effects of pharmaceutical mixtures in aquatic microcosms. Environmental Toxicology and Chemistry, 2004, 23(4): 1035–1042

[27] Huber M M, Canonica S, Park G Y, von Gunten U. Oxidation of pharmaceuticals during ozonation and advanced oxidation processes. Environmental Science & Technology, 2003, 37(5): 1016–1024

[28] Zhang H, Yamada H, Tsuno H. Removal of endocrine-disrupting chemicals during ozonation of municipal sewage with brominated byproducts control. Environmental Science & Technology, 2008, 42(9): 3375–3380

[29] Deborde M, von Gunten U. Reactions of chlorine with inorganic and organic compounds during water treatment-Kinetics and mechanisms: a critical review. Water Research, 2008, 42(1-2): 13–51

[30] Rule K L, Ebbett V R, Vikesland P J. Formation of chloroform and chlorinated organics by free-chlorine-mediated oxidation of triclosan. Environmental Science & Technology, 2005, 39(9): 3176–3185

[31] Sharma V K, Li X Z, Graham N, Doong R A. Ferrate(VI) oxidation of endocrine disruptors and antimicrobials in water. Journal of Water Supply Research and Technology -AQUA, 2008, 57(6): 419–426

[32] Jiang J Q, Yin Q, Zhou J L, Pearce P. Occurrence and treatment trials of endocrine disrupting chemicals (EDCs) in wastewaters. Chemosphere, 2005, 61(4): 544–550

[33] Lee Y, Yoon J, von Gunten U. Kinetics of the oxidation of phenols and phenolic endocrine disruptors during water treatment with ferrate (Fe(VI)). Environmental Science & Technology, 2005, 39(22): 8978–8984

[34] Sharma V K, Mishra S K, Ray A K. Kinetic assessment of the potassium ferrate(VI) oxidation of antibacterial drug sulfamethoxazole. Chemosphere, 2006, 62(1): 128–134

[35] Shao X L, Ma J, Wen G, Yang J J. Oxidation of estrone by permanganate: Reaction kinetics and estrogenicity removal. Chinese Science Bulletin, 2010, 55(9): 802–808

[36] Jiang J, Pang S Y, Ma J. Oxidation of triclosan by permanganate (Mn(VII)): importance of ligands and in situ formed manganese oxides. Environmental Science & Technology, 2009, 43(21): 8326–8331

[37] Yang J J. Determination of trace permanganate and oxidation of bisphenol A by permanganate. Dissertation for the Master Degree, Harbin: Harbin Institute of Technology, 2008, 32–35(in Chinese).

[38] Zhang J, Li G B, Jun M A. Effects of chlorine content and position of chlorinated phenols on their oxidation kinetics by potassium permanganate. Journal of Environmental Sciences (China), 2003, 15(3): 342–345

[39] Radhakrishnamurti P S, Sahu S N. Kinetics and mechanism of oxidation of nitrophenols and nitroanilines by potassium permanganate. Journal of the Indian Chemical Society, 1976, 53: 1154–1155

[40] Forsey S P. In situ chemical oxidation of creosote/coal tar residuals: experimental and numerical investigation. Dissertation for the Doctoral Degree. Waterloo: University of Waterloo, 2004

[41] Huang K C, Hoag G E, Chheda P, Woody B A, Dobbs G M. Oxidation of chlorinated ethenes by potassium permanganate: a kinetics study. Journal of Hazardous Materials, 2001, 87(1-3): 155–169

[42] Schnarr M, Truax C, Farquhar G, Hood E, Gonullu T, Stickney B. Laboratory and controlled field experiments using potassium permanganate to remediate trichloroethylene and perchloroethylene DNAPLs in porous media. Journal of Contaminant Hydrology, 1998, 29(3): 205–224

[43] Huber M M, Korhonen S, Ternes T A, von Gunten U. Oxidation of pharmaceuticals during water treatment with chlorine dioxide. Water Research, 2005, 39(15): 3607–3617

[44] Westerhoff P, Aiken G, Amy G, Debroux J. Relationships between the structure of natural organic matter and its reactivity towards molecular ozone and hydroxyl radicals. Water Research, 1999, 33(10): 2265–2276

[45] Yan Y E, Schwartz F W. Kinetics and mechanisms for TCE oxidation by permanganate. Environmental Science & Technology, 2000, 34(12): 2535–2541

[46] Lee D G, Sebastian C F. The oxidation of phenol and chlorophenols by alkaline permanganate. Canadian Journal of Chemistry, 1981, 59(18): 2776–2779

[47] Jiang J, Pang S Y, Ma J. Role of ligands in permanganate oxidation of organics. Environmental Science & Technology, 2010, 44(11): 4270–4275

[48] Abe Y, Takigami M, Sugino K, Taguchi M, Kojima T, Umemura T, Tsunoda K. Decomposition of phenolic endocrine disrupting chemicals by potassium permanganate and -ray irradiation. Bulletin of the Chemical Society of Japan, 2003, 76(8): 1681–1685

[49] Rudakov E S, Lobachev V L. The kinetics, kinetic isotope effects, and substrate selectivity of alkylbenzene oxidation in aqueous permanganate solutions. 2. Reaction with HMnO₄. Kinetics and Catalysis, 1994, 35: 180–187

[50] Rudakov E S, Lobachev V L. The first step of oxidation of alkylbenzenes by permanganates in acidic aqueous solutions. Russian Chemical Bulletin, 2000, 49(5): 761–777

[51] Gugger M, Lenoir S, Berger C, Ledreux A, Druart J C, Humbert J F, Guette C, Bernard C. First report in a river in France of the benthic cyanobacterium Phormidium favosum producing anatoxin-a associated with dog neurotoxicosis. Toxicon, 2005, 45(7): 919–928

[52] Rodríguez E, Onstad G D, Kull T P J, Metcalf J S, Acero J L, von Gunten U. Oxidative elimination of cyanotoxins: comparison of ozone, chlorine, chlorine dioxide and permanganate. Water Research, 2007, 41(15): 3381–3393

[53] WHO. Guidelines for Drinking Water Quality, Vol. 1, 3rd ed. Geneva: WHO, 2004

[54] Falconer I R. Cyanobacterial Toxins of Drinking Water Supplies: Cylindrospermopsins and Microcystins. Boca Raton: CRC Press, 2005

[55] Edwards C, Beattie K A, Scrimgeour C M, Codd G A. Identification of anatoxin-A in benthic cyanobacteria (blue-green algae) and in associated dog poisonings at Loch Insh, Scotland. Toxicon, 1992, 30(10): 1165–1175

[56] Himberg K, Keijola A M, Hiisvirta L, Pyysalo H, Sivonen K. The effect of water treatment processes on the removal of hepotoxins from Microcystis and Oscillatoria cyanobacteria: A laboratory study. Water Research, 1989, 23(8): 979–984

[57] Rositano J, Newcombe G, Nicholson B, Sztajnbok P. Ozonation of NOM and algal toxins in four treated waters. Water Research, 2001, 35(1): 23–32

[58] Nicholson B, Rositano J, Burch M D. Destruction of cyanobacterial peptide hepatotoxins by chlorine and chloramine. Water Research, 1994, 28(6): 1297–1303

[59] Liu I, Lawton L A, Robertson P K. Mechanistic studies of the photocatalytic oxidation of microcystin-LR: an investigation of byproducts of the decomposition process. Environmental Science & Technology, 2003, 37(14): 3214–3219

[60] Kull T P J, Backlund P H, Karlsson K M, Meriluoto J A O. Oxidation of the cyanobacterial hepatotoxin microcystin-LR by chlorine dioxide: reaction kinetics, characterization, and toxicity of reaction products. Environmental Science & Technology, 2004, 38(22): 6025–6031

[61] Bellar T A, Lichtenberg J J, Kroner R C. The occurrence of organohalides in chlorinated drinking waters. Journal American Water Works Association, 1974, 66(12): 703–706

[62] Kronberg L, Vartiainen T. Ames mutagenicity and concentration of the strong mutagen 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone and its geometric isomer E-chloro-3-(dichloromethyl)-4-oxobutenoic acid in tap waters. Mutation Research & Genetic Toxicology, 1988, 206(2): 177–182

[63] Hall T, Hart J, Croll B, Gregory P. Laboratory-scale investigations of algal toxin removal by water treatment. Journal of the Chartered Institution of Water and Environmental Management, 2000, 14(2): 143–149

[64] Rositano J. The destruction of cyanobacterial peptide toxins by oxidants used in water treatment. Urban Water Research Association of Australia, Report 110. 1996

[65] Pietsch J, Bornmann K, Schmidt W. Relevance of intra- and extracellular cyanotoxins for drinking water treatment. Acta Hydrochimica et Hydrobiologica, 2002, 30(1): 7–15

[66] Drikas M, Chow C W K, House J, Burch M D. Using coagulation, flocculation, and settling to remove toxic cyanobacteria. Journal American Water Works Association, 2001, 93(2): 100–111

[67] Chen J J, Yeh H H. The mechanisms of potassium permanganate on algae removal. Water Research, 2005, 39(18): 4420–4428

[68] Hou C R, Jia R B, Hu W R. Study on the removal of algae and algal toxin with permanganate enhanced coagulation. Overseas Construction Material Technology, 2006, 27(3): 27–29 (in Chinese)

[69] Lawton L A, Robertson P K J. Physico-chemical treatment methods for the removal of microcystins (cyanobacterial hepatotoxins) from potable waters. Chemical Society Reviews, 1999, 28(4): 217–224

[70] He D, Guan X H, Ma J, Yu M. Influence of different nominal molecular weight fractions of humic acids on phenol oxidation by permanganate. Environmental Science & Technology, 2009, 43(21): 8332–8337

[71] He D, Guan X H, Ma J, Yang X, Cui C W. Influence of humic acids of different origins on oxidation of phenol and chlorophenols by permanganate. Journal of Hazardous Materials, 2010, 182(1-3): 681–688

[72] Rodríguez E M, Acero J L, Spoof L, Meriluoto J. Oxidation of MC-LR and -RR with chlorine and potassium permanganate: toxicity of the reaction products. Water Research, 2008, 42(6-7): 1744–1752

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