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Environmental Science and Pollution Research

, Volume 25, Issue 34, pp 34164–34180 | Cite as

Effective reduction of metronidazole over the cryptomelane-type manganese oxide octahedral molecular sieve (K-OMS-2) catalyst: facile synthesis, experimental design and modeling, statistical analysis, and identification of by-products

  • Ebrahim Mohammadi Kalhori
  • Esmaeil Ghahramani
  • Tariq J. Al-Musawi
  • Hossien Najafi Saleh
  • Mohammad Noori Sepehr
  • Mansur Zarrabi
Research Article
  • 58 Downloads

Abstract

High concentrations of antibiotic compounds within pharmaceutical wastewater have hazardous impacts toward environment and human health. Therefore, there is an immediate requirement of efficient treatment method for removal of antibiotics from aquatic environment. In the present study, the cryptomelane catalyst-type manganese oxide octahedral molecular sieve (K-OMS-2) was synthesized in the presence of benzyl alcohol as a reducing agent and cetyltrimethylammonium bromide as a structure-directing agent and then utilized to reduce the metronidazole. The central composite design method was the experimental design adopted. The FESEM analysis revealed that the K-OMS-2 surface contained many uniformly cylindrical aggregates less than about 40 nm in diameter and about 80–100 nm in length. Besides, a high specific surface area of 129 m2/g and average pore size of 45.47 nm were recorded. According to the TGA/DTA analysis, the prepared catalyst revealed high thermal stability. The maximum metronidazole degradation (95.36%) was evident at conditions of pH = 3, catalyst mass = 0.97 g/L, contact time = 200 min, and metronidazole concentration = 20 mg/L. Metronidazole did not form a complex with nitrate, fluoride, sulfate, or hardness. These ions exerted a negligible effect on metronidazole reduction using the K-OMS-2 catalyst, except for hardness, which reduced the removal efficiency of metronidazole by 17%. The FTIR and LC-MS revealed a complex mechanism involved in the metronidazole degradation by the K-OMS-2 involving the formation of an amino group, a hydroxyelated compound via N-denitration, and hydrogenation process on the K-OMS-2 catalyst surface.

Keywords

K-OMS-2 catalyst Pharmaceuticals removal Wastewater Central composite design Interfering ions 

Notes

Funding information

The authors are grateful to the Alborz University of Medical Sciences for the financial support made available to them for this research.

References

  1. Abecassis-Wolfovich M, Jothiramalingam R, Landau MV, Herskowitz M, Viswanathan B, Varadarajan TK (2005) Cerium incorporated ordered manganese oxide OMS-2 materials: improved catalysts for wet oxidation of phenol compounds. Appl Catal B Environ 59:91–98CrossRefGoogle Scholar
  2. Ahmed MJ, Theydan SK (2013) Microporous activated carbon from Siris seed pods by microwave-induced KOH activation for metronidazole adsorption. J Anal Appl Pyrolysis 99:101–109CrossRefGoogle Scholar
  3. Al-Musawi TJ, Brouers F, Zarrabi M (2017) Kinetic modeling of antibiotic adsorption onto different nanomaterials using the Brouers–Sotolongo fractal equation. Environ Sci Pollut Res 24:4048–4057CrossRefGoogle Scholar
  4. Barhoumi N, Olvera-Vargas H, Oturan N, Huguenot D, Gadri A, Ammar S, Brillas E, Oturan MA (2017) Kinetics of oxidative degradation/mineralization pathways of the antibiotic tetracycline by the novel heterogeneous electro-Fenton process with solid catalyst chalcopyrite. Appl Catal B Environ 209:637–647CrossRefGoogle Scholar
  5. Calabrese I, Cavallaro G, Scialabba C, Licciardi M, Merli M, Sciascia L, Liveri MLT (2013) Montmorillonite nanodevices for the colon metronidazole delivery. Int J Pharm 457:224–236CrossRefGoogle Scholar
  6. Carrales-Alvarado DH, Ocampo-Pérez R, Leyva-Ramos R, Rivera-Utrilla J (2014) Removal of the antibiotic metronidazole by adsorption on various carbon materials from aqueous phase. J Colloid Interface Sci 436:276–285CrossRefGoogle Scholar
  7. Chen J, Qiu X, Fang Z, Yang M, Pokeung T, Fenglong G, Cheng W, Lan B (2012) Removal mechanism of antibiotic metronidazole from aquatic solutions by using nanoscale zero-valent iron particles. Chem Eng J:113, 181–119, 182Google Scholar
  8. Chien YW, Lambert HJ, Sanvordeker DR (1975) Interaction of metronidazole with metallic ions of biological importance. J Pharm Sci 64:957–960CrossRefGoogle Scholar
  9. Daughton CG (2014) Eco-directed sustainable prescribing: feasibility for reducing water contamination by drugs. Sci Total Environ 493:392–404CrossRefGoogle Scholar
  10. Derikvandi H, Nezamzadeh-Ejhieh A (2017) Designing of experiments for evaluating the interactions of influencing factors on the photocatalytic activity of NiS and SnS2: focus on coupling, supporting and nanoparticles. J Colloid Interface Sci 490:628–641CrossRefGoogle Scholar
  11. Destrieux D, Laurent F, Budzinski H, Pedelucq J, Vervier P, Gerino M (2017) Drug residues in urban water: a database for ecotoxicological risk management. Sci Total Environ 609:927–941CrossRefGoogle Scholar
  12. Dharmarathna S, King’ondu CK, Pahalagedara L, Kuo C-H, Zhang Y, Suib SL (2014) Manganese octahedral molecular sieve (OMS-2) catalysts for selective aerobic oxidation of thiols to disulfides. Appl Catal B Environ 147:124–131CrossRefGoogle Scholar
  13. Duan L, Sun B, Wei M, Luo S, Pan F, Xu A, Li X (2015) Catalytic degradation of Acid Orange 7 by manganese oxide octahedral molecular sieves with peroxymonosulfate under visible light irradiation. J Hazard Mater 285:356–365CrossRefGoogle Scholar
  14. El-Sawy AM, Kingondu CK, Kuo C-H, Kriz DA, Guild CJ, Meng Y, Frueh SJ, Dharmarathna S, Ehrlich SN, Suib SL (2014) X-ray absorption spectroscopic study of a highly thermally stable manganese oxide octahedral molecular sieve (OMS-2) with high oxygen reduction reaction activity. Chem Mater 26:5752–−5760CrossRefGoogle Scholar
  15. Fang Z, Qiu X, Chen J, Qiu X (2010) Degradation of metronidazole by nanoscale zero-valent metal prepared from steel pickling waste liquor. Appl Catalysis B: Environ 100:221–228CrossRefGoogle Scholar
  16. Gao T, Glerup M, Krumeich F, Nesper R, Fjellvag H, Norby P (2008) Microstructures and spectroscopic properties of cryptomelane-type manganese dioxide nanofibers. J Phys Chem C 112:13134–13140CrossRefGoogle Scholar
  17. Gao Q, Li H-T, Ling Y, Han B, Xia K-S, Zhou C-G (2017) Synthesis of MnSiO3 decorated hollow mesoporous silica spheres and its promising application in environmental remediation. Microporous Mesoporous Mater 241:409–417CrossRefGoogle Scholar
  18. Habib MJ, Asker AF (1989) Complex formation of metronidazole and sodium urate: effect on photodegradation of metronidazole. Pharm Res 6:58–61CrossRefGoogle Scholar
  19. Hamaguchi T, Tanaka T, Takahashi N, Tsukamoto Y, Takagi N, Shinjoh H (2016) Low-temperature NO-adsorption properties of manganese oxide octahedral molecular sieves with different potassium content. Appl Catal B Environ 193:234–239CrossRefGoogle Scholar
  20. Hou J, Liu L, Li Y, Mao M, Lv H, Zhao X (2013) Tuning the K+ concentration in the tunnel of OMS-2 nanorods leads to a significant enhancement of the catalytic activity for benzene oxidation. Environ Sci Technol 47:13730–13736CrossRefGoogle Scholar
  21. Hou J, Luo J, Hu Z, Li Y, Mao M, Song S, Liao Q, Li Q (2016) Tremendous effect of oxygen vacancy defects on the oxidation of arsenite to arsenate on cryptomelane-type manganese oxide. Chem Eng J 306:597–606CrossRefGoogle Scholar
  22. Hu B, Chen C-h, Frueh SJ, Jin L, Joesten R, Suib SL (2010) Removal of aqueous phenol by adsorption and oxidation with doped hydrophobic cryptomelane-type manganese oxide (K-OMS-2) nanofibers. J Phys Chem A 114:9835–9844Google Scholar
  23. Kalhori EM, Al-Musawi TJ, Ghahramani E, Kazemian H, Zarrabi M (2017) Enhancement of the adsorption capacity of the light-weight expanded clay aggregate surface for the metronidazole antibiotic by coating with MgO nanoparticles: studies on the kinetic, isotherm, and effects of environmental parameters. Chemosphere 175:8–20CrossRefGoogle Scholar
  24. Khataee A, Kıran M, Karaca S, Sheydaei M (2017) Photocatalytic ozonation of metronidazole by synthesized zinc oxide nanoparticles immobilized on montmorillonite. Journal of the Taiwan Institute of Chemical Engineers 0 0(0):1–9Google Scholar
  25. Liu J, Son Y-C, Cai J, Shen X, Suib SL, Aindow M, Control S (2004) Metal substitution, and catalytic application of cryptomelane nanomaterials prepared using cross-linking reagents. Chem Mater 16:276–285CrossRefGoogle Scholar
  26. Liu H-Q, Lamb JCW, Li W-W, Yu H-Q, Lam PKS (2017) Spatial distribution and removal performance of pharmaceuticals in municipal wastewater treatment plants in China. Sci Total Environ 586:1162–1169CrossRefGoogle Scholar
  27. Luo S, Duan L, Sun B, Wei M, Li X, Xu A (2015) Manganese oxide octahedral molecular sieve (OMS-2) as an effective catalyst for degradation of organic dyes in aqueous solutions in the presence of peroxymonosulfate. Appl Catal B Environ 164:92–99CrossRefGoogle Scholar
  28. Mohseni-Bandpi A, Al-Musawi TJ, Ghahramani E, Zarrabi M, Mohebi S, Vahed SA (2016) Improvement of zeolite adsorption capacity for cephalexin by coating with magnetic Fe3O4 nanoparticles. J Molecular Liquids 218:615–624CrossRefGoogle Scholar
  29. Pakarinen J, Koivula R, Laatikainen M, Laatikainen K, Paatero E, Harjula R (2010) Nanoporous manganese oxides as environmental protective materials—effect of Ca and Mg on metals sorption. J Hazard Mater 180:234–240CrossRefGoogle Scholar
  30. Pan F, Xu A, Xia D, Yu Y, Guo C, Meyer M, Zhao D, Huang C-H, Wu Q, Jie F (2015) Effects of octahedral molecular sieve on treatment performance, microbial metabolism, and microbial community in expanded granular sludge bed reactor. Water Res 87:127–136CrossRefGoogle Scholar
  31. Samarghandi MR, Al-Musawi TJ, Mohseni-Bandpi A, Zarrabi M (2015) Adsorption of cephalexin from aqueous solution using natural zeolite and zeolite coated with manganese oxide nanoparticles. J of Molecular Liquids 211:431–441CrossRefGoogle Scholar
  32. Sanchez-Polo M, Rivera-Utrilla J, Prados-Joya G, Ferro-Garcıa MA, Bautista-Toledo I (2008) Removal of pharmaceutical compounds, nitroimidazoles, from waters by using the ozone/carbon system. Water Research 42:4163–4171CrossRefGoogle Scholar
  33. Santana DR, Espino-Estevez MR, Santiago DE, Ortega Mendez JA, Gonzalez-Dıaz O, Dona-Rodrıguez JM (2017) Treatment of aquaculture wastewater contaminated with metronidazole by advanced oxidation techniques. Environmental Nanotechnology, Monitoring & Management 8:11–24CrossRefGoogle Scholar
  34. Sing KSW, Everett DH, Haul RAW, Moscou L, Pierotti RA, Rouquerol J, Siemieniewska T (1985) Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity. Pure Appl Chemistry 57:603–619CrossRefGoogle Scholar
  35. Soori MM, Ghahramani E, Kazemian H, Al-Musawi TJ, Zarrabi M (2016) Intercalation of tetracycline in nano sheet layered double hydroxide: an insight into UV/VIS spectra analysis. J Taiwan Inst Chem Eng 63:271–285CrossRefGoogle Scholar
  36. Sulaymon AH, Mohammed AA, Al-Musawi TJ (2014) Comparative study of removal of cadmium (II) and chromium (III) ions from aqueous solution using low-cost biosorbent. Int J Chem Reac Eng 12:1–10Google Scholar
  37. Tian H, He J, Zhang X, Zhou L, Wang D (2011) Facile synthesis of porous manganese oxide K-OMS-2 materials and their catalytic activity for formaldehyde oxidation. Microporous Mesoporous Mater 138:118–122CrossRefGoogle Scholar
  38. Trivedi MK, Patil S, Shettigar H, Bairwa K, Jana S (2015) Spectroscopic characterization of biofield treated metronidazole and tinidazole. Med Chem 5:340–344Google Scholar
  39. Wang X, Liu P, Ma J, Liu H (2016a) Preparation of novel composites based on hydrophilized and functionalized polyacrylonitrile membrane-immobilized NZVI for reductive transformation of metronidazole. Appl Surf Sci 396:841–850CrossRefGoogle Scholar
  40. Wang X, Yi D, Ma J (2016b) Novel synthesis of carbon spheres supported nanoscale zero-valentiron for removal of metronidazole. Appl Surf Sci 390:50–59CrossRefGoogle Scholar
  41. Xiao X, Sun S-P, McBride MB, Lemley AT (2013) Degradation of ciprofloxacin by cryptomelane-type manganese(III/IV) oxides. Environ Sci Pollut Res 20:10–21CrossRefGoogle Scholar
  42. Xu W, Deng Z, Li G (2012) Facile preparation of nanocryptomelane and its application in the treatment of aqueous solutions containing basic fuchsin. Industrial Engineering Chemistry Res 51:16188–16195CrossRefGoogle Scholar
  43. Yang J, Wang X, Zhu M, Liu H, Ma J (2014) Investigation of PAA/PVDF–NZVI hybrids for metronidazole removal: synthesis, characterization, and reactivity characteristics. J Hazard Mater 264:269–277CrossRefGoogle Scholar
  44. Yang J, Zhu M, Wang X, Alvarez PJJ, Liu K (2015) Poly(vinylidenefluoride) membrane supported nano zero valent iron for metronidazole removal: influences of calcium and bicarbonate ions. J Taiwan Inst Chem Eng 49:113–118CrossRefGoogle Scholar
  45. Yang Y, Ok YS, Kim K-H, Kwon EE, Tsang YF (2017) Occurrences and removal of pharmaceuticals and personal care products (PPCPs) in drinking water and water/sewage treatment plants: a review. Sci Total Environ 596–597:303–320CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Ebrahim Mohammadi Kalhori
    • 1
  • Esmaeil Ghahramani
    • 2
  • Tariq J. Al-Musawi
    • 3
  • Hossien Najafi Saleh
    • 4
  • Mohammad Noori Sepehr
    • 1
  • Mansur Zarrabi
    • 1
  1. 1.Department of Environmental Health Engineering, Research Center for Health, Safety and Environment, Faculty of HealthAlborz University of Medical SciencesKarajIran
  2. 2.Environmental Health Research Center, Research Institute for Health DevelopmentKurdistan University of Medical SciencesSanandajIran
  3. 3.Department of Civil Engineering, Faculty of EngineeringIsra UniversityAmmanJordan
  4. 4.Department of Environmental Health Engineering, School of HealthTorbat Heydariyeh University of Medical SciencesTorbat HeydariehIran

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