Enhanced Degradation of Methyl Parathion in the Ligand Stabilized Soluble Mn(III)-Sulfite System

  • Caixiang ZhangEmail author
  • Xiaoping Liao
  • You Lü
  • Chao Nan


The ligand-stabilized soluble Mn(III) recognized as active intermediate can potentially mediate the attenuation of contaminants. In this study, the abiotic degradation behaviors of methyl parathion in the ligand stabilized Mn(III)-sulfite system were investigated. The results showed that the yield of soluble Mn(III) produced from the redox reaction of MnO2 and oxalic acid was dependent linearly on the dosage of MnO2 and caused the decomposition of methyl parathion up to 50.1% in Mn(III)-sulfite system after 30 minutes. The fitted pseudo-first-order reaction constants of methyl parathion degradation increased with the increasing of the amount of produced Mn(III) but was not effected linearly by the addition of sulfite. Other ligands, including pyrophosphate and oxalic acid, acted as effective complexing agents to stabilize soluble Mn(III), and exhibited competitive effect on methyl parathion degradation with sulfite. The formation of Mn(III)-sulfite complexes is the critical step in the system to produce abundant reactive oxygen species identified as SO3- to facilitate methyl parathion degradation. The hydrolysis and oxidation of methyl parathion were acknowledged as two primary transformation mechanisms in Mn(III)-sulfite system. These findings indicate that naturally ligands-stabilized soluble Mn(III) can be generated and could oxidatively decompose organophosphate pesticides such as methyl parathion.

Key Words

soluble Mn(III) sulfite methyl parathion degradation mechanism 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.



This study was supported by the National Natural Science Foundation of China (Nos. 41772251, 41702267 and 41521001), the State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology (No. FSKLCCA1511), China Postdoctoral Science Foundation (No. 2017M612536), and the “111” Project of the Ministry of Education of China. The final publication is available at Springer via

Supplementary material

12583_2018_889_MOESM1_ESM.docx (3.3 mb)
Supplementary material, approximately 118 KB.


  1. Ahmad, T., Ramanujachary, K. V., Lofland, S. E., et al., 2004. Nanorods of Manganese Oxalate: A Single Source Precursor to Different Manganese Oxide Nanoparticles (MnO, Mn2O3, Mn3O4). Journal of Materials Chemistry, 14(23): 3406. Google Scholar
  2. Babu, V., Unnikrishnan, P., Anu, G., et al., 2011. Distribution of Organophosphorus Pesticides in the Bed Sediments of a Backwater System Located in an Agricultural Watershed: Influence of Seasonal Intrusion of Seawater. Archives of Environmental Contamination and Toxicology, 60(4): 597–609. CrossRefGoogle Scholar
  3. Boonchom, B., Baitahe, R., 2009. Synthesis and Characterization of Nanocrystalline Manganese Pyrophosphate Mn2P2O7. Materials Letters, 63(26): 2218–2220. CrossRefGoogle Scholar
  4. Buxton, G. V., Greenstock, C. L., Helman, W. P., et al., 1988. 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, 17(2): 513–886. CrossRefGoogle Scholar
  5. Ccanccapa, A., Masiá, A., Navarro-Ortega, A., et al., 2016. Pesticides in the Ebro River Basin: Occurrence and Risk Assessment. Environmental Pollution, 211: 414–424. CrossRefGoogle Scholar
  6. Chen, W. R., Huang, C. H., 2009. Transformation of Tetracyclines Mediated by Mn(II) and Cu(II) Ions in the Presence of Oxygen. Environmental Science & Technology, 43(2): 401–407. CrossRefGoogle Scholar
  7. Chen, W. R., Liu, C., Boyd, S. A., et al., 2013. Reduction of Carbadox Mediated by Reaction of Mn(III) with Oxalic Acid. Environmental Science & Technology, 47(3): 1357–1364. CrossRefGoogle Scholar
  8. Das, T. N., Huie, R. E., Neta, P., 1999. Reduction Potentials of SO3•-, SO5•-, and S4O6•3-Radicals in Aqueous Solution. The Journal of Physical Chemistry A, 103(18): 3581–3588. CrossRefGoogle Scholar
  9. Davies, G., 1969. Some Aspects of the Chemistry of Manganese(III) in Aqueous Solution. Coordination Chemistry Reviews, 4(2): 199–224. CrossRefGoogle Scholar
  10. Duckworth, O. W., Sposito, G., 2005. Siderophore-Manganese(III) Interactions. I. Air-Oxidation of Manganese(II) Promoted by Desferrioxamine B. Environmental Science & Technology, 39(16): 6037–6044. Google Scholar
  11. Ehlert, K., Mikutta, C., Kretzschmar, R., 2016. Effects of Manganese Oxide on Arsenic Reduction and Leaching from Contaminated Floodplain Soil. Environmental Science & Technology, 50(17): 9251–9261. CrossRefGoogle Scholar
  12. Ehrlich, H. L., 1987. Manganese Oxide Reduction as a Form of Anaerobic Respiration. Geomicrobiology Journal, 5(3/4): 423–431. CrossRefGoogle Scholar
  13. Gao, Y., Jiang, J., Zhou, Y., et al., 2017. Unrecognized Role of Bisulfite as Mn(III) Stabilizing Agent in Activating Permanganate (Mn(VII)) for Enhanced Degradation of Organic Contaminants. Chemical Engineering Journal, 327: 418–422. CrossRefGoogle Scholar
  14. Guo, X. F., Jans, U., 2006. Kinetics and Mechanism of the Degradation of Methyl Parathion in Aqueous Hydrogen Sulfide Solution: Investigation of Natural Organic Matter Effects. Environmental Science & Technology, 40(3): 900–906. CrossRefGoogle Scholar
  15. Harrington, J. M., Parker, D. L., Bargar, J. R., et al., 2012. Structural Dependence of Mn Complexation by Siderophores: Donor Group Dependence on Complex Stability and Reactivity. Geochimica et Cosmochimica Acta, 88: 106–119. CrossRefGoogle Scholar
  16. Hayon, E., Treinin, A., Wilf, J., 1972. Electronic Spectra, Photochemistry, and Autoxidation Mechanism of the Sulfite-Bisulfite-Pyrosulfite Systems. SO2-, SO3-, SO4-, and SO5- Radicals. Journal of the American Chemical Society, 94(1): 47–57. CrossRefGoogle Scholar
  17. Hu, E. D., Zhang, Y., Wu, S. Y., et al., 2017. Role of Dissolved Mn(III) in Transformation of Organic Contaminants: Non-Oxidative Versus Oxidative Mechanisms. Water Research, 111: 234–243. CrossRefGoogle Scholar
  18. Huang, T. Y., Fang, C., Qian, Y. J., et al., 2017. Insight into Mn(II)-Mediated Transformation of Β-Lactam Antibiotics: The Overlooked Hydrolysis. Chemical Engineering Journal, 321: 662–668. CrossRefGoogle Scholar
  19. Jiang, B., Liu, Y. K., Zheng, J. T., et al., 2015. Synergetic Transformations of Multiple Pollutants Driven by Cr(VI)–Sulfite Reactions. Environmental Science & Technology, 49(20): 12363–12371. CrossRefGoogle Scholar
  20. Jurado, A., Vàzquez-Suñé, E., Carrera, J., et al., 2012. Emerging Organic Contaminants in Groundwater in Spain: A Review of Sources, Recent Occurrence and Fate in a European Context. Science of The Total Environment, 440: 82–94. CrossRefGoogle Scholar
  21. Kim, M., Liu, Q. C., Gabbaï, F. P., 2004. Use of an Organometallic Palladium Oxazoline Catalyst for the Hydrolysis of Methylparathion. Organometallics, 23(23): 5560–5564. CrossRefGoogle Scholar
  22. Klewicki, J. K., Morgan, J. J., 1998. Kinetic Behavior of Mn(III) Complexes of Pyrophosphate, EDTA, and Citrate. Environmental Science & Technology, 32(19): 2916–2922. CrossRefGoogle Scholar
  23. Klewicki, J. K., Morgan, J. J., 1999. Dissolution of Β-MnOOH Particles by Ligands: Pyrophosphate, Ethylenediaminetetraacetate, and Citrate. Geochimica et Cosmochimica Acta, 63(19/20): 3017–3024. CrossRefGoogle Scholar
  24. Liao, X. P., Zhang, C. X., Liu, Y., et al., 2016. Abiotic Degradation of Methyl Parathion by Manganese Dioxide: Kinetics and Transformation Pathway. Chemosphere, 150: 90–96. CrossRefGoogle Scholar
  25. Liao, X. P., Zhang, C. X., Wang, Y. X., et al., 2017. The Abiotic Degradation of Methyl Parathion in Anoxic Sulfur-Containing System Mediated by Natural Organic Matter. Chemosphere, 176: 288–295. CrossRefGoogle Scholar
  26. Liu, Y., 2016. The Study of Hydrolysis Behavior of Methyl Parathion: [Dissertation]. China University of Geosciences, Wuhan (in Chinese with English Abstract)Google Scholar
  27. Madison, A. S., Tebo, B. M., Mucci, A., et al., 2013. Abundant Porewater Mn(III) is a Major Component of the Sedimentary Redox System. Science, 341(6148): 875–878. CrossRefGoogle Scholar
  28. Neta, P., Huie, R. E., Ross, A. B., 1988. Rate Constants for Reactions of Inorganic Radicals in Aqueous Solution. Journal of Physical and Chemical Reference Data, 17(3): 1027–1284. CrossRefGoogle Scholar
  29. Oldham, V. E., Mucci, A., Tebo, B. M., et al., 2017. Soluble Mn(III)–L Complexes are Abundant in Oxygenated Waters and Stabilized by Humic Ligands. Geochimica et Cosmochimica Acta, 199: 238–246. CrossRefGoogle Scholar
  30. Peña, J., Duckworth, O. W., Bargar, J. R., et al., 2007. Dissolution of Hausmannite (Mn3O4) in the Presence of the Trihydroxamate Siderophore Desferrioxamine B. Geochimica et Cosmochimica Acta, 71(23): 5661–5671. CrossRefGoogle Scholar
  31. Pino, N., Peñuela, G., 2011. Simultaneous Degradation of the Pesticides Methyl Parathion and Chlorpyrifos by an Isolated Bacterial Consortium from a Contaminated Site. International Biodeterioration & Biodegradation, 65(6): 827–831. CrossRefGoogle Scholar
  32. Pryor, W. A., 1960. The Kinetics of the Disproportionation of Sodium Thiosulfate to Sodium Sulfide and Sulfate. Journal of the American Chemical Society, 82(18): 4794–4797. CrossRefGoogle Scholar
  33. Sheng, G. D., Xu, C., Xu, L., et al., 2009. Abiotic Oxidation of 17β-Estradiol by Soil Manganese Oxides. Environmental Pollution, 157(10): 2710–2715. CrossRefGoogle Scholar
  34. Straus, D. L., Schlenk, D., Chambers, J. E., 2000. Hepatic Microsomal Desulfuration and Dearylation of Chlorpyrifos and Parathion in Fingerling Channel Catfish: Lack of Effect from Aroclor 1254. Aquatic Toxicology, 50(1/2): 141–151. CrossRefGoogle Scholar
  35. Sun, B., Guan, X. H., Fang, J. Y., et al., 2015. Activation of Manganese Oxidants with Bisulfite for Enhanced Oxidation of Organic Contaminants: The Involvement of Mn(III). Environmental Science & Technology, 49(20): 12414–12421. CrossRefGoogle Scholar
  36. Sun, D. L., Wei, Y. L., Li, H. Z., et al., 2016. Insecticides in Sediment Cores from a Rural and a Suburban Area in South China: A Reflection of Shift in Application Patterns. Science of the Total Environment, 568: 11–18. CrossRefGoogle Scholar
  37. Sun, S. F., Pang, S. Y., Jiang, J., et al., 2018. The Combination of Ferrate(VI) and Sulfite as a Novel Advanced Oxidation Process for Enhanced Degradation of Organic Contaminants. Chemical Engineering Journal, 333: 11–19. CrossRefGoogle Scholar
  38. Taube, H., 1947. Catalysis of the Reaction of Chlorine and Oxalic Acid. Complexes of Trivalent Manganese in Solutions Containing Oxalic Acid. Journal of the American Chemical Society, 69(6): 1418–1428. Google Scholar
  39. Trouwborst, R. E., Clement, B. G., Tebo, B. M., et al., 2006. Soluble Mn(III) in Suboxic Zones. Science, 313(5795): 1955–1957. CrossRefGoogle Scholar
  40. Van Aken, B., Agathos, S. N., 2002. Implication of Manganese (III), Oxalate, and Oxygen in the Degradation of Nitroaromatic Compounds by Manganese Peroxidase (MnP). Applied Microbiology and Biotechnology, 58(3): 345–351. CrossRefGoogle Scholar
  41. Wang, Y., Stone, A. T., 2006. Reaction of MnIII,IV (Hydr)Oxides with Oxalic Acid, Glyoxylic Acid, Phosphonoformic Acid, and Structurally-Related Organic Compounds. Geochimica et Cosmochimica Acta, 70(17): 4477–4490. CrossRefGoogle Scholar
  42. Wang, Z. M., Tebo, B. M., Giammar, D. E., 2014a. Effects of Mn(II) on UO2 Dissolution under Anoxic and Oxic Conditions. Environmental Science & Technology, 48(10): 5546–5554. CrossRefGoogle Scholar
  43. Wang, Z. M., Xiong, W., Tebo, B. M., et al., 2014b. Oxidative UO2 Dissolution Induced by Soluble Mn(III). Environmental Science & Technology, 48(1): 289–298. CrossRefGoogle Scholar
  44. Zamora, P. L., Villamena, F. A., 2012. Theoretical and Experimental Studies of the Spin Trapping of Inorganic Radicals by 5,5-Dimethyl- 1-Pyrroline N-Oxide (DMPO). 3. Sulfur Dioxide, Sulfite, and Sulfate Radical Anions. The Journal of Physical Chemistry A, 116(26): 7210–7218. Google Scholar

Copyright information

© China University of Geosciences and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.State Key Laboratory of Biogeology and Environmental GeologyChina University of GeosciencesWuhanChina
  2. 2.Central South China Center for Geoscience InnovationWuhanChina

Personalised recommendations