Battery grade γ-MnO<sub>2</sub> powder was investigated as an oxidant and an adsorbent in combination with Fe/Al coagulants for removal of arsenic from contaminated water. Simultaneous oxidation of As(III) and removal by coprecipitation/adsorption (one step process) was compared with pre-oxidation and subsequent removal by coprecipitation/adsorption (two step process). The rate of As(III) oxidation with MnO<sub>2</sub> is completed in two stages: rapid initially followed by a first order reaction. As(III) is oxidised to As(V) by the MnO<sub>2</sub> with a release of approximately 1:1 molar Mn(II) into the solution. No significant pH effect on oxidation of As(III) was observed in the pH range 4 - 6. The rate showed a decreasing trend above pH 6. The removal of As(V) by adsorption on the MnO2 decreased significantly with increasing pH from 4 to 8. The adsorption capacity of the γ-MnO<sub>2</sub> with particle size 90% passing 10 µm was determined to be 1.5 mg/g at pH 7. MnO<sub>2</sub> was found to be more effective as an oxidant for As(III) in the two step process than in the one step process.
KeywordsManganese OxidesIron HydroxidesArsenic RemediationFe/Al CoagulantsContaminated Water
G. H. Khoe, M. T. Emett, M. Zaw and P. Prasad, “Arsenic Removal from Tubewell Water in Bangladesh, Report,” Australian Nuclear Science & Technology Organisation CRC for Waste Management & Pollution Control ANSTO/C585, CRC/1956R, August 1999.
W. Driehaus and M. Jekel, “Oxidation Process for Trivalent Arsenic,” DVGW-Schriftenr., Wasser, Vol. 82, 1993, pp. 55-69.
T. Phommavong, T. Viraraghavan and K. S. Subramanian, “Removal of Arsenic with KMnO4. Oxidation and Manganese Greensand Filtration,” Proceedings of the Annual Conference on West Canadian Water Wastewater Association, 48th, 1996.
Y. Li, M. Xi, F. L. Kong and C. Y. Yu, “Experimental Study on the Removal of Arsenic in Waste Water from Semiconductor Manufacturing,” Journal of Water Resource and Protection, Vol. 1, 2009, pp. 48-51.
T. Nishimura and Y. Umetsu, “Removal of As(III), Arsenic(V) with Manganese from Aqueous Solution by Ozonation,” Impurity Control and Disposal in Hydrometallurgical Processes, Toronto, Ontario, Canada, 21-24 August 1994, pp. 91-100.
M. Pettine and F. J. Millero, “Effect of Metals on the Oxidation of As(III) with H2O2,” Marine Chemistry, Vol. 70, No. 1-3, 2000, pp. 223-234. doi:10.1016/S0304-4203(00)00028-1
T. Chen, S. J. Kang, K. P. Olmstead, M. D. Rathsack and J. R. Porter, “Removal of Arsenic from BTEX-Contami- nated Groundwater,” Water Environment Federation Technical Conference 1996 (WEFTEC’96), 69th Annual Conference & Exposition, 1996.
E. Nieminski and D. Evans, “Pilot Testing of Trace Metals Removal with Ozone at Snowbird Ski Resort,” Ozone: Science & Engineering, Vol. 17, 1995, pp. 297-309.
Gaid, I. Raguenes and P. Ravarini, “Arsenic Removal at Baudricourt (Vosges, France) Drinkable Water Plant,” Industry Water Pollution, Vol. 205, 1997, pp. 54-58.
S. P. Pande, L. S. Deshpande, P. M. Patni and S. L. Lutade, “Arsenic Removal Studies in Some Groundwaters of West Bengal, India,” Journal of Environmental Science and Health, Part A: Toxic / Hazardous Substances and Environmental Engineering, Vol. A32, No. 7, 1997, pp. 1981-1987.
R. K. Sinha, A. M. Bandyopadhyaya, B. Roy, G. Poddar, I. Chakravarty, A. Majumdar and K. J. Nath, “Use of Some Iron Salts on Total Removal of Arsenic from Arsenical Tubewell Water of West Bengal,” Journal of the Institution of Chemists, Vol. 65, No. 1, 1993, pp. 30-31.
K. Sano and S. Hosudo, “Removal of Arsenic from Water,” Jpn. Kokai Tokkyo Koho., Kotobuki Kakoki Kk, Japan. 1995, p. 5.
H. Naito, “Apparatus and Method for Removing Tace Arsenic from Groundwater or Pond Water,” Jpn. Kokai Tokkyo Koho, NBL K. K., Japan, 1997, 6 Pages.
W. Zhang, P. Singh and D. M. Muir, “Kinetics of Oxidation of As(III) with SO2/O2 and UV Light,” In: C. A. Young, Ed., Proceedings of Minor Elements 2000: Processing and environmental aspects of As, Sb, Se, Te, and Bi, SME, Littleton CO, 2000, pp. 333-343.
T. Nishimura, Q. Wang and Y. Umetsu, “Removal of Arsenic from Process Liquors by Oxidation of Iron(II), Arsenic(III) and Sulfur(IV) with Oxygen,” In: J. E. Dutrizac and G. B. Harris, Eds., Iron Control and Disposal, CIM, Montreal Quebec, 1996, pp. 535-548.
J. Bednar, J. F. Ranville, T. R. Wildeman, J. R. Garbarino, P. J. Lamothe and K. S. Smith, “Remediation Approaches Using Photooxidation of Inorganic and Organic Arsenic Species,” ACS National Meeting, American Chemical Society, Division Environmental Chemistry, Vol. 41, 2001, pp. 253-256.
M. T. Emett and G. H. Khoe, “Photochemical Oxidation of Arsenic by Oxygen and Iron in Acidic Solutions,” Water Research, Vol. 35, No. 3, 2001, pp. 649-656. doi:10.1016/S0043-1354(00)00294-3
G. H. Khoe, M. Zaw, P. S. Prasad and M. T. Emett, “Photo-Assisted Oxidation of Inorganic Species in Aqueous Solutions,” PCT Int. Appl. Wo, CRC for Waste Management & Pollution Control Limited, Australia; Australian Nuclear Science and Technology Organisation, 1999, 30 p.
S. J. Hug, L. Canonica, M. Wegelin, D. Gechter and U. von Gunten, “Solar Oxidation and Removal of Arsenic at Circumneutral pH in Iron Containing Waters,” Environmental Science & Technology, Vol. 35, No. 10, 2001, pp. 2114-2121. doi:10.1021/es001551s
L. Carlson and U. Schwertmann, “Iron and Manganese Oxides in Finnish Ground Water Treatment Plants,” Water Research, Vol. 21, No. 2, 1987, pp. 165-170. doi:10.1016/0043-1354(87)90045-5
M. Ogawa, M. Kato, T. Okuyama and T. Saito, “Removal of As from Water by Manganese Dioxide,” Shigen Kankyo Taisaku, Vol. 37, 2001, pp. 1459-1468.
T. Takamatsu, M. Kawashima and M. Koyama, “The Role of Manganese(2+)-Rich Hydrous Manganese Oxide in the Accumulation of Arsenic in Lake Sediments,” Water Research, Vol. 19, No. 8, 1985, pp. 1029-1032. doi:10.1016/0043-1354(85)90372-0
D. W. Oscarson, P. M. Huang, C. Defosse and A. Herbillon, “Oxidative Power of Manganese(IV) and Iron(III) Oxides with Respect to Arsenic(III) in Terrestrial and Aquatic Environments,” Nature, Vol. 291, No. 5810, 1981, pp. 50-51.
B. A. Manning, S. E. Fendorf and D. L. Suarez, “Arsenic(III) Complexation and Oxidation Reactions on Environmental Surfaces,” Environmental Science & Technology, Vol. 36, No. 5, 2002, pp. 976-981.
B. A. Manning, S. E. Fendorf and D. L. Suarez, “Arsenic(III) Complexation and Oxidation Reactions on Soil,” ACS Symposium Series, Vol. 835, 2003, pp. 55-69
B. A. Manning, E. Fendorf Scott, B. Bostick, and L. Suarez Donald, “Arsenic(III) Oxidation and Arsenic(V) Adsorption Reactions on Synthetic Birnessite,” Environmental Science & Technology, Vol. 36, 2002, pp. 976- 981.
D. W. Oscarson, P. M. Huang, W. K. Liaw and U. T. Hammer, “Kinetics of Oxidation of Arsenite by Various Manganese Dioxides,” Soil Science Society of America Journal, Vol. 47, 1983, pp. 644-648. doi:10.2136/sssaj1983.03615995004700040007x
H. Chen and S. Fang, “Study on Oxidation of As(III) to As(V) by MnO2 in wastewater,” Gaoxiao Huaxue Gongcheng Xuebao, Vol. 14, 2000, pp. 48-52.
M. J. Scott and J. J. Morgan, “Reactions at Oxide Surfaces. 1. Oxidation of As(III) by Synthetic Birnessite,” Environmental Science and Technology, Vol. 29, 1995, pp. 1898-1905. doi:10.1021/es00008a006
V. Q. Chiu and J. G. Hering, “Oxidation State of Arsenic on Manganite (.Gamma.-MnOOH) Surfaces,” 217th ACS National Meeting, Anaheim, 21-25 March 1999.
H. W. Nesbitt, G. W. Canning and G. M. Bancroft, “XPS Study of Reductive Dissolution of 7 A-Birnessite by H 3 AsO 3 , with Constraints on Reaction Mechanism,” Geochimica et Cosmochimica Acta, Vol. 62, No. 12, 1998, pp. 2097-2110.
S. Ouvrard, M.-O. Simonnot and M. Sardin, “Reactive Behavior of Natural Manganese Oxides toward the Adsorption of Phosphate and Arsenate,” Industrial & Engineering Chemistry Research, Vol. 41, No. 11, 2002, pp. 2785-2791.
S. Chakravarty, V. Dureja, G. Bhattacharyya, S. Maity and S. Bhattacharjee, “Removal of Arsenic from Groundwater Using Low Cost Ferruginous Manganese Ore,” Water Research, Vol. 36, No. 3, 2002, pp. 625-632. doi:10.1016/S0043-1354(01)00234-2
S. Bajpai and M. Chaudhuri, “Removal of Arsenic from Ground Water by Manganese Dioxide-Coated Sand,” Journal of Environmental Engineering, Vol. 125, No. 8, 1999, pp. 782-784.
T. Kasai, H. Koyanaka, J. Aizawa and Y. Fujimoto, “Removal of Arsenic Ion from Aqueous Solution with Manganese Oxide,” Nippon Bunri Daigaku Kiyo, Vol. 28, No. 2, 2000, pp. 81-86.
T. Kasai and H. Koyanaka, “Removal of Arsenic Ion with Manganese Oxide Compounds,” Transactions of the Materials Research Society of Japan, Vol. 27, 2002, pp. 463- 466.
J. J. Wen and L. H. Odell, “Case Studies on Concurrent Arsenic Removal in Pyrolusite Iron and Manganese Treatment,” Proceedings—Water Quality Technology Conference, 1999, pp. TU11.5.1-TU11.5.14.
A. Vogel, “Text Book of Quantitative Inorganic Analysis,” 3rd Edition, Longman, London, 1961.
S. B. Kanungo and D. M. Mahapatra, “Interfacial Properties of Some Hydrous Manganese Dioxides in 1-1 Electrolyte Solution,” Journal of Colloid and Interface Science, Vol. 131, 1989, pp. 103-111. doi:10.1016/0021-9797(89)90150-1
S. Ardizzone and S. Trasatti, “Interfacial Properties of Oxides with Technological Impact in Electrochemistry,” Advances in Colloid and Interface Science, Vol. 64, 1996, pp. 173-251. doi:10.1016/0001-8686(95)00286-3
P. Thanabalasingam and W. F. Pickering, “Effect of pH on Interaction between Arsenic(III) or Arsenic(V) and Manganese(IV) Oxide,” Water, Air, and Soil Pollution, Vol. 29, No. 2, 1986, pp. 205-216. doi:10.1007/BF00208409