Advertisement

Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

Oxidative removal of metronidazole from aqueous solution by thermally activated persulfate process: kinetics and mechanisms

Abstract

Metronidazole (MNZ) is widely used in clinical applications and animal feed as an antibiotic agent and additive, respectively. Widespread occurrence of MNZ in wastewater treatment and hospital effluents has been reported. In this study, the mechanism of MNZ degradation in aqueous solutions via thermally activated persulfate (TAP) process was established under different conditions. The kinetic model was derived for MNZ degradation and followed pseudo-first-order reaction kinetics and was consistent with the model fitted by experimental data (R 2 > 98.8%). The rate constant increased with the initial dosage of persulfate, as well as the temperature, and the yielding apparent activation energy was 23.9 kcal mol−1. The pH of the solutions did not have significant effect on MNZ degradation. The degradation efficiency of MNZ reached 96.6% within 180 min for an initial MNZ concentration of 100 mg L−1 under the optional condition of [PS]0 = 20 mM, T = 60 °C, and unadjusted pH. \( {SO}_4^{\cdotp -} \) and HO · were confirmed using electron paramagnetic resonance (EPR) spectra during TAP process. Radical quenching study revealed that \( {SO}_4^{\cdotp -} \) was mainly responsible for MNZ degradation at an unadjusted pH. MNZ mineralization evaluation showed that the removal efficiency of total organic carbon (TOC) reached more than 97.2%.

This is a preview of subscription content, log in to check access.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

References

  1. Ammar HB (2016) Sono-Fenton process for metronidazole degradation in aqueous solution: effect of acoustic cavitation and peroxydisulfate anion. Ultrason Sonochem 33:164–169

  2. Anipsitakis GP, Dionysiou DD (2004) Radical generation by the interaction of transition metals with common oxidants. Environ Sci Technol 38:3705–3712

  3. Antoniou MG, de la Cruz AA, Dionysiou DD (2010) Degradation of microcystin-LR using sulfate radicals generated through photolysis, thermolysis and e transfer mechanisms. Appl Catal B Environ 96:290–298. https://doi.org/10.1016/j.apcatb.2010.02.013

  4. Azam A, Siraji F, Amran M, Islam J, Amjad F, Hossain M (2011) In vitro interaction of metronidazole and mebendazole with copper (II) and chromium (III) in aqueous media. J Sci Res 4:173–181

  5. Chen J et al (2012) Removal mechanism of antibiotic metronidazole from aquatic solutions by using nanoscale zero-valent iron particles. Chem Eng J 181-182:113–119. https://doi.org/10.1016/j.cej.2011.11.037

  6. Chen J, Qian Y, Liu H, Huang T (2016) Oxidative degradation of diclofenac by thermally activated persulfate: implication for ISCO. Environ Sci Pollut Res 23:3824–3833. https://doi.org/10.1007/s11356-015-5630-0

  7. Cheng W, Yang M, Xie Y, Liang B, Fang Z, Tsang EP (2013) Enhancement of mineralization of metronidazole by the electro-Fenton process with a Ce/SnO2–Sb coated titanium anode. Chem Eng J 220:214–220. https://doi.org/10.1016/j.cej.2013.01.055

  8. Deng J, Shao Y, Gao N, Deng Y, Zhou S, Hu X (2013) Thermally activated persulfate (TAP) oxidation of antiepileptic drug carbamazepine in water. Chem Eng J 228:765–771

  9. Fan Y, Ji Y, Kong D, Lu J, Zhou Q (2015) Kinetic and mechanistic investigations of the degradation of sulfamethazine in heat-activated persulfate oxidation process. J Hazard Mater 300:39–47. https://doi.org/10.1016/j.jhazmat.2015.06.058

  10. Fang Z, Qiu X, Chen J, Qiu X (2010) Degradation of metronidazole by nanoscale zero-valent metal prepared from steel pickling waste liquor. Appl Catal B Environ 100:221–228. https://doi.org/10.1016/j.apcatb.2010.07.035

  11. Fang Z, Chen J, Qiu X, Qiu X, Cheng W, Zhu L (2011) Effective removal of antibiotic metronidazole from water by nanoscale zero-valent iron particles. Desalination 268:60–67. https://doi.org/10.1016/j.desal.2010.09.051

  12. Farzadkia M, Bazrafshan E, Esrafili A, Yang J-K, Shirzad-Siboni M (2015) Photocatalytic degradation of metronidazole with illuminated TiO2 nanoparticles. J Environ. Health Sci Eng 13:35

  13. Furman OS, Teel AL, Watts RJ (2010) Mechanism of base activation of persulfate. Environ Sci Technol 44:6423–6428

  14. Gao H, Chen J, Zhang Y, Zhou X (2016) Sulfate radicals induced degradation of triclosan in thermally activated persulfate system. Chem Eng J 306:522–530. https://doi.org/10.1016/j.cej.2016.07.080

  15. Ghauch A, Tuqan AM, Kibbi N (2012) Ibuprofen removal by heated persulfate in aqueous solution: a kinetics study. Chem Eng J 197:483–492

  16. Gómez MJ, Petrović M, Fernández-Alba AR, Barceló D (2006) Determination of pharmaceuticals of various therapeutic classes by solid-phase extraction and liquid chromatography–tandem mass spectrometry analysis in hospital effluent wastewaters. J Chromatogr A 1114:224–233

  17. Gómez MJ, Malato O, Ferrer I, Agüera A, Fernández-Alba AR (2007) Solid-phase extraction followed by liquid chromatography–time-of-flight–mass spectrometry to evaluate pharmaceuticals in effluents. A pilot monitoring study. J Environ Monit 9:718–729

  18. Gu X, Lu S, Li L, Qiu Z, Sui Q, Lin K, Luo Q (2011) Oxidation of 1,1,1-trichloroethane stimulated by thermally activated persulfate. Ind Eng Chem Res 50:11029–11036

  19. House DA (1962) Kinetics and mechanism of oxidations by peroxydisulfate. Chem Rev 62:185–203

  20. Hussain I, Zhang Y, Huang S (2014) Degradation of aniline with zero-valent iron as an activator of persulfate in aqueous solution. RSC Adv 4:3502–3511

  21. Ingerslev F, Toräng L, Loke M-L, Halling-Sørensen B, Nyholm N (2001) Primary biodegradation of veterinary antibiotics in aerobic and anaerobic surface water simulation systems. Chemosphere 44:865–872. https://doi.org/10.1016/s0045-6535(00)00479-3

  22. Ji Y, Dong C, Kong D, Lu J, Zhou Q (2015) Heat-activated persulfate oxidation of atrazine: implications for remediation of groundwater contaminated by herbicides. Chem Eng J 263:45–54

  23. Kmmerer K (2001) Drugs in the environment: emission of drugs, diagnostic aids and disinfectants into wastewater by hospitals in relation to other sources—a review. Chemosphere 45:957–969

  24. Kolthoff I, Miller I (1951) The chemistry of persulfate. I. The kinetics and mechanism of the decomposition of the persulfate ion in aqueous medium. J Am Chem Soc 73:3055–3059

  25. Kümmerer K, Al-Ahmad A, Mersch-Sundermann V (2000) Biodegradability of some antibiotics, elimination of the genotoxicity and affection of wastewater bacteria in a simple test. Chemosphere 40:701–710

  26. Lee Y-C, Lo S-L, Kuo J, Lin Y-L (2012) Persulfate oxidation of perfluorooctanoic acid under the temperatures of 20–40 °C. Chem Eng J 198:27–32

  27. Liang C, Wang ZS, Bruell CJ (2007) Influence of pH on persulfate oxidation of TCE at ambient temperatures. Chemosphere 66:106–113. https://doi.org/10.1016/j.chemosphere.2006.05.026

  28. Liang C, Huang C-F, Mohanty N, Kurakalva RM (2008) A rapid spectrophotometric determination of persulfate anion in ISCO. Chemosphere 73:1540–1543

  29. Mahdi Ahmed M, Barbati S, Doumenq P, Chiron S (2012) Sulfate radical anion oxidation of diclofenac and sulfamethoxazole for water decontamination. Chem Eng J 197:440–447. https://doi.org/10.1016/j.cej.2012.05.040

  30. McCallum JE, Madison SA, Alkan S, Depinto RL, Rojas Wahl RU (2000) Analytical studies on the oxidative degradation of the reactive textile dye Uniblue A. Environ Sci Technol 34:5157–5164

  31. Mendez-Diaz JD, Prados-Joya G, Rivera-Utrilla J, Leyva-Ramos R, Sanchez-Polo M, Ferro-Garcia MA, Medellin-Castillo NA (2010) Kinetic study of the adsorption of nitroimidazole antibiotics on activated carbons in aqueous phase. J Colloid Interface Sci 345:481–490. https://doi.org/10.1016/j.jcis.2010.01.089

  32. Nie M, Yang Y, Zhang Z, Yan C, Wang X, Li H, Dong W (2014) Degradation of chloramphenicol by thermally activated persulfate in aqueous solution. Chem Eng J 246:373–382. https://doi.org/10.1016/j.cej.2014.02.047

  33. Olmez-Hanci T, Arslan-Alaton I, Genc B (2013) Bisphenol A treatment by the hot persulfate process: oxidation products and acute toxicity. J Hazard Mater 263:283–290

  34. Padmaja S, Alfassi Z, Neta P, Huie R (1993) Rate constants for reactions of radicals in acetonitrile. In J Chem Kinet 25:193–198

  35. Peyton GR (1993) The free-radical chemistry of persulfate-based total organic carbon analyzers. Mar Chem 41:91–103

  36. Pignatello JJ, Oliveros E, MacKay A (2006) Advanced oxidation processes for organic contaminant destruction based on the Fenton reaction and related chemistry. Crit Rev Environ Sci Technol 36:1–84

  37. Rivera-Utrilla J, Prados-Joya G, Sanchez-Polo M, Ferro-Garcia MA, Bautista-Toledo I (2009) Removal of nitroimidazole antibiotics from aqueous solution by adsorption/bioadsorption on activated carbon. J Hazard Mater 170:298–305. https://doi.org/10.1016/j.jhazmat.2009.04.096

  38. Rosal R et al (2010) Occurrence of emerging pollutants in urban wastewater and their removal through biological treatment followed by ozonation. Water Res 44:578–588. https://doi.org/10.1016/j.watres.2009.07.004

  39. Saidi I, Soutrel I, Floner D, Fourcade F, Bellakhal N, Amrane A, Geneste F (2014) Indirect electroreduction as pretreatment to enhance biodegradability of metronidazole. J Hazard Mater 278:172–179

  40. Sanchez-Polo M, Rivera-Utrilla J, Prados-Joya G, Ferro-Garcia MA, Bautista-Toledo I (2008) Removal of pharmaceutical compounds, nitroimidazoles, from waters by using the ozone/carbon system. Water Res 42:4163–4171. https://doi.org/10.1016/j.watres.2008.05.034

  41. Shemer H, Kunukcu YK, Linden KG (2006) Degradation of the pharmaceutical metronidazole via UV, Fenton and photo-Fenton processes. Chemosphere 63:269–276. https://doi.org/10.1016/j.chemosphere.2005.07.029

  42. Singh UC, Venkatarao K (1976) Decomposition of peroxodisulphate in aqueous alkaline solution. J Inorg and Nuclear Chem 38:541–543

  43. Szente V, Baska F, Zelkó R, Süvegh K (2011) Prediction of the drug release stability of different polymeric matrix tablets containing metronidazole. J Pharm Biomed Anal 54:730–734

  44. Tan C, Gao N, Deng Y, An N, Deng J (2012) Heat-activated persulfate oxidation of diuron in water. Chem Eng J 203:294–300

  45. Tsitonaki A, Smets BF, Bjerg PL (2008) Effects of heat-activated persulfate oxidation on soil microorganisms.Water Res 42(4):1013–1022

  46. Tsitonaki A, Petri B, Crimi M, Mosbæk H, Siegrist RL, Bjerg PL (2010) In situ chemical oxidation of contaminated soil and groundwater using persulfate: a review. Crit Rev Environ Sci Technol 40:55–91

  47. Wang X, Wang L, Li J, Qiu J, Cai C, Zhang H (2014) Degradation of Acid Orange 7 by persulfate activated with zero valent iron in the presence of ultrasonic irradiation. Sep Purif Technol 122:41–46

  48. Weng CH, Tsai KL (2016) Ultrasound and heat enhanced persulfate oxidation activated with Fe0 aggregate for the decolorization of C.I. Direct Red 23. Ultrason Sonochem 29:11–18. https://doi.org/10.1016/j.ultsonch.2015.08.012

  49. Xiao JC, Xie LF, Zhao L, Fang SL, Lun ZR (2008) The presence of Mycoplasma hominis in isolates of Trichomonas vaginalis impacts significantly on DNA fingerprinting results. Parasitol Res 102:613–619. https://doi.org/10.1007/s00436-007-0796-0

  50. Yan J, Lei M, Zhu L, Anjum MN, Zou J, Tang H (2011) Degradation of sulfamonomethoxine with Fe3O4 magnetic nanoparticles as heterogeneous activator of persulfate. J Hazard Mater 186:1398–1404. https://doi.org/10.1016/j.jhazmat.2010.12.017

  51. Yan J, Zhu L, Luo Z, Huang Y, Tang H, Chen M (2013) Oxidative decomposition of organic pollutants by using persulfate with ferrous hydroxide colloids as efficient heterogeneous activator. Sep Purif Technol 106:8–14. https://doi.org/10.1016/j.seppur.2012.12.012

  52. Yifei C, Shaojin C (2008) Reduction of methyl and chloro substituted nitrobenzenes in soils by zero-valent iron. J Environ Sci Manag 11:017

Download references

Acknowledgements

This work was supported by the National Nature Science Foundation of China (Grant No. 41302184), Scientific Frontier and Interdisciplinary Research Project of Jilin University, Outstanding Youth Cultivation Plan of Jilin University, and Key Laboratory of Groundwater Resources and Environmental of Ministry of Education (Jilin University).

Author information

Correspondence to Hejun Ren.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Ethical statement

This article does not contain any studies with human participants or animals performed by any of the authors.

Additional information

Responsible editor: Santiago V. Luis

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Zhou, R., Li, T., Su, Y. et al. Oxidative removal of metronidazole from aqueous solution by thermally activated persulfate process: kinetics and mechanisms. Environ Sci Pollut Res 25, 2466–2475 (2018). https://doi.org/10.1007/s11356-017-0518-9

Download citation

Keywords

  • Metronidazole
  • Thermal activation
  • Persulfate
  • Degradation
  • Kinetics
  • Sulfate radicals