Advertisement

Environmental Science and Pollution Research

, Volume 25, Issue 21, pp 20363–20373 | Cite as

Electro-Fenton oxidation of para-aminosalicylic acid: degradation kinetics and mineralization pathway using Pt/carbon-felt and BDD/carbon-felt cells

  • Nihal Oturan
  • Charuvila T. Aravindakumar
  • Hugo Olvera-Vargas
  • Mathew M. Sunil Paul
  • Mehmet A. OturanEmail author
Water: From Pollution to Purification
First Online:

Abstract

Degradation of a widely used antibiotic, the para-aminosalicylic acid (PAS), and mineralization of its aqueous solution was investigated by electro-Fenton process using Pt/carbon-felt and boron-doped diamond (BDD)/carbon-felt cells with applied currents in the range of 50–1000 mA. This process produces the highly oxidizing species, the hydroxyl radical (•OH), which is mainly responsible for the oxidative degradation of PAS. An absolute rate constant of 4.17 × 109 M−1 s−1 for the oxidation of PAS by ●OH was determined from the competition kinetics method. Degradation rate of PAS increased with current reaching an optimal value of 500 mA with complete disappearance of 0.1 mM PAS at 7 min using Pt/carbon-felt cell. The optimum degradation rate was reached at 300 mA for BDD/carbon-felt. The latter cell was found more efficient in total organic carbon (TOC) removal where a complete mineralization was achieved within 240 min. A multi-step mineralization process was observed with the formation of a number of aromatic intermediates, short-chain carboxylic acids, and inorganic ions. Eight aromatic intermediate products were identified using both LC-Q-ToF-MS and GC-MS techniques. These products were the result of hydroxylation of PAS followed by multiple additions of hydroxyl radicals to form polyhydroxylated derivatives. HPLC and GC/MS analyses demonstrated that extended oxidation of these intermediate products conducted to the formation of various short-chain carboxylic acids. Prolonged electrolysis resulted in a complete mineralization of PAS with the evolution of inorganic ions such as NO3 − and NH4 +. Based on the identified intermediates, carboxylic acids and inorganic ions, a plausible mineralization pathway is also deduced. The remarkably high degree of mineralization (100%) achieved by the present EF process highlights the potential application of this technique to the complete removal of salicylic acid-based pharmaceuticals from contaminated water.

Keywords

Pharmaceuticals and personal care products Para-aminosalicylic acid Electro-Fenton Hydroxyl radical Mineralization 
This is a preview of subscription content, log in to check access.

Notes

Acknowledgements

C.T. Aravindakumar is thankful to Université Paris-Est Marne-la-Vallée for a visiting professorship position.

References

  1. Bocos E, Oturan N, Pazos M, Sanromán MÁ, Oturan MA (2016) Elimination of radiocontrast agent diatrizoic acid by photo-Fenton process and enhanced treatment by coupling with electro-Fenton process. Environ Sci Pollut Res 23(19):19134–19144CrossRefGoogle Scholar
  2. Brillas E, Sirés I, Oturan MA (2009) Electro-Fenton process and related electrochemical technologies based on Fenton’s reaction chemistry. Chem Rev 109:6570–6631Google Scholar
  3. Buxton GV, Greenstock CL, Helman WP, Ross AB (1988) Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (•OH/•O−) in aqueous solutions. J Phys Chem Ref Data 17:513–886CrossRefGoogle Scholar
  4. Cruz-González K, Torres-López O, García-León A, Guzmán-Mar JL, Reyes LH, Hernández-Ramírez A, Peralta-Hernández JM (2010) Determination of optimum operating parameters for acid yellow 36 decolorization by electro-Fenton process using BDD cathode. Chem Eng J 160:199–206CrossRefGoogle Scholar
  5. De Araújo DM, Cañizares P, Martínez-Huitle CA, Rodrigo MA (2014) Electrochemical conversion/combustion of a model organic pollutant on BDD anode: role of sp3/sp2 ratio. Electrochem Commun 47:37–40CrossRefGoogle Scholar
  6. De Heredia JB, Torregrosa J, Dominguez JR, Peres JA (2001) Kinetic model for phenolic compound oxidation by Fenton’s reagent. Chemosphere 45:85–90CrossRefGoogle Scholar
  7. Dirany A, Aaron SE, Oturan N, Sires I, Oturan MA, Aaron JJ (2011) Study of the toxicity of sulfamethoxazole and its degradation products in water by a bioluminescence method during application of the electro-Fenton treatment. Anal Bioanal Chem 400:353–360CrossRefGoogle Scholar
  8. El-Ghenymy A, Rodriguez RM, Brillas E, Oturan N, Oturan MA (2014) Electro-Fenton degradation of the antibiotic sulfanilamide with Pt/carbon-felt and BDD/carbon-felt cells. Kinetics, reaction intermediates, and toxicity assessment. Environ Sci Pollut Res 21:8368–8378CrossRefGoogle Scholar
  9. Feng L, van Hullebusch ED, Rodrigo MA, Esposito G, Oturan MA (2013) Removal of residual anti-inflammatory and analgesic pharmaceuticals from aqueous systems by electrochemical advanced oxidation processes. A review. Chem Eng J 228:944–964CrossRefGoogle Scholar
  10. Florenza X, Garcia-Segura S, Centellas F, Brillas E (2016) Comparative electrochemical degradation of salicylic and aminosalicylic acids: influence of functional groups on decay kinetics and mineralization. Chemosphere 154:171–178CrossRefGoogle Scholar
  11. Ganzenko O, Oturan N, Huguenot D, van Hullebusch ED, Esposito G, Oturan MA (2015) Removal of psychoactive pharmaceutical caffeine from water by electro-Fenton process using BDD anode: effects of operating parameters on removal efficiency. Sep Purif Technol 156:987–995CrossRefGoogle Scholar
  12. Garcia-Segura S, Brillas E (2011) Mineralization of the recalcitrant oxalic and oxamic acids by electrochemical advanced oxidation processes using a boron-doped diamond anode. Water Res 45:2975–2984CrossRefGoogle Scholar
  13. Garcia-Segura S, Brillas E (2017) Applied photoelectrocatalysis on the degradation of organic pollutants in wastewaters. J Photoch Photobio C: Photochem Rev 31:1–35CrossRefGoogle Scholar
  14. Garcia-Segura S, Mostafa E, Baltruschat E (2017) Could NOx be released during mineralization of pollutants containing nitrogen by hydroxyl radical? Ascertaining the release of N-volatile species. Appl Catal B Environ 207:376–384CrossRefGoogle Scholar
  15. Gros M, Petrovic M, Barcelo D (2007) Wastewater treatment plants as a pathway for aquatic contamination by pharmaceuticals in the Ebro river basin (northeast Spain). Environ Toxicol Chem 26:1553–1562CrossRefGoogle Scholar
  16. Guinea E, Brillas E, Centellas F, Canizares P, Rodrigo MA, Saez C (2009) Oxidation of enrofloxacin with conductive-diamond electrochemical oxidation, ozonation and Fenton oxidation. A comparison. Water Res 43:2131–2138CrossRefGoogle Scholar
  17. Houtman CJ, Kroesbergen J, Lekkerkerker-Teunissen K, van der Hoek JP (2014) Human health risk assessment of the mixture of pharmaceuticals in Dutch drinking water and its sources based on frequent monitoring data. Sci Total Environ 496:54–62CrossRefGoogle Scholar
  18. Komesli OT, Muz M, Ak MS, Bakırdere S, Gokcay CF (2015) Occurrence, fate and removal of endocrine disrupting compounds (EDCs) in Turkish wastewater treatment plants. Chem Eng J 277:202–208CrossRefGoogle Scholar
  19. Lan H, He W, Wang A, Liu R, Liu H, Qu J, Huang CP (2016) An activated carbon fiber cathode for the degradation of glyphosate in aqueous solutions by the electro-Fenton mode: optimal operational conditions and the deposition of iron on cathode on electrode reusability. Water Res 105:575–582CrossRefGoogle Scholar
  20. Lin H, Wu J, Oturan N, Zhang H, Oturan MA (2016) Degradation of artificial sweetener saccharin in aqueous medium by electrochemically generated hydroxyl radicals. Environ Sc Pollut Res 23:4442–4453CrossRefGoogle Scholar
  21. Lin H, Oturan N, Wu J, Zhang H, Oturan MA (2017) Cold incineration of sucralose in aqueous solution by electro-Fenton process. Separ Purif Technol 173:218–225CrossRefGoogle Scholar
  22. Martínez-Huitle CA, Rodrigo MA, Sirés I, Scialdone O (2015) Single and coupled electrochemical processes and reactors for the abatement of organic water pollutants: a critical review. Cheml Rev 115:13362–13407CrossRefGoogle Scholar
  23. Moreira FC, Garcia-Segura S, Boaventura RAR, Brillas E, Vilar VJP (2014) Degradation of the antibiotic trimethoprim by electrochemical advanced oxidation processes using a carbon-PTFE air-diffusion cathode and a boron-doped diamond or platinum anode. Appl Catal B Environ 160-161:492–505CrossRefGoogle Scholar
  24. Nidheesh PV, Gandhimathi R (2014) Removal of rhodamine B from aqueous solution using graphite-graphite electro-Fenton system. Desal Water Treat 52:1872–1877CrossRefGoogle Scholar
  25. Olvera-Vargas H, Oturan N, Aravindakumar CT, Paul MMS, Sharma VK, Oturan MA (2014a) Electro-oxidation of the dye azure B: kinetics, mechanism, and by-products. Environ Sci Pollut Res 21:8379–8386CrossRefGoogle Scholar
  26. Olvera-Vargas H, Oturan N, Brillas E, Buisson D, Esposito G, Oturan MA (2014b) Electrochemical advanced oxidation for cold incineration of the pharmaceutical ranitidine: mineralization pathway and toxicity evolution. Chemosphere 117:644–651CrossRefGoogle Scholar
  27. Olvera-Vargas H, Cocerva T, Oturan N, Buisson D, Oturan MA (2016) Bioelectro-Fenton: a sustainable integrated process for removal of organic pollutants from water: application to mineralization of metoprolol. J Hazard Mater 319:13–23CrossRefGoogle Scholar
  28. Oturan MA (2000) An ecologically effective water treatment technique using electrochemically generated hydroxyl radicals for in situ destruction of organic pollutants. Application to herbicide 2,4-D. J Appl Electrochem 30:477–482CrossRefGoogle Scholar
  29. Oturan MA (2014) Electrochemical advanced oxidation technologies for removal of organic pollutants from water. Environ Sci Poll Res 21:8333–8335CrossRefGoogle Scholar
  30. Oturan MA, Aaron JJ (2014) Advanced oxidation processes in water/wastewater treatment: principles and applications. A review. Crit Rev Env Sci Technol 44:2577–2641CrossRefGoogle Scholar
  31. Oturan N, Brillas E, Oturan MA (2012) Unprecedented total mineralization of atrazine and cyanuric acid by anodic oxidation and electro-Fenton with a boron-doped diamond anode. Environ Chem Lett 10:165–170CrossRefGoogle Scholar
  32. Oturan N, Wu J, Zhang H, Sharma VK, Oturan MA (2013) Electrocatalytic destruction of the antibiotic tetracycline in aqueous medium by electrochemical advanced oxidation processes: effect of electrode materials. Appl Catal B Environ 140-141:92–97CrossRefGoogle Scholar
  33. Oturan N, van Hullebusch ED, Zhang H, Mazeas L, Budzinski H, Le Menach K, Oturan MA (2015) Occurrence and of removal organic micropollutants in landfill leachates treated by electrochemical advanced oxidation processes. Environ Sci Technol 49:12187–12196CrossRefGoogle Scholar
  34. Özcan A, Sahin Y, Oturan MA (2008a) Removal of propham from water by using electro-Fenton technology: kinetics and mechanism. Chemosphere 73:737–744CrossRefGoogle Scholar
  35. Özcan A, Şahin Y, Koparal AS, Oturan MA (2008b) Carbon sponge as a new cathode material for the electro-Fenton process. Comparison with carbon felt cathode and application to degradation of synthetic dye basic blue 3 in aqueous medium. J Electroanal Chem 616:71–78CrossRefGoogle Scholar
  36. Panizza M, Cerisola G (2009) Direct and mediated anodic oxidation of organic pollutants. Chem Rev 109:6541–6569CrossRefGoogle Scholar
  37. Panizza M, Brillas E, Comninellis C (2008) Application of boron-doped diamond electrodes for wastewater treatment. J Environ Eng Manage 18:139–153Google Scholar
  38. Randazzo S, Scialdone O, Brillas E, Sirés I (2011) Comparative electrochemical treatments of two chlorinated aliphatic hydrocarbons. Time course of the main reaction by-products. J Hazard Mater 192:1555–1564CrossRefGoogle Scholar
  39. Rodrigo MA, Cañizares P, Sánchez-Carretero A, Sáez C (2010) Use of conductive diamond electrochemical oxidation for wastewater treatment. Catal Today 151:173–177CrossRefGoogle Scholar
  40. Rodrigo MA, Oturan N, Oturan MA (2014) Electrochemically assisted remediation of pesticides in soils and water: a review. Chem Rev 114:8720–8745CrossRefGoogle Scholar
  41. Sales Solano AM, Costa de Araujo CK, de Melo JV, Peralta-Hernandez JM, da Silva DR, Martinez-Huitle CA (2013) Decontamination of real textile industrial effluent by strong oxidant species electrogenerated on diamond electrode: viability and disadvantages of this electrochemical technology. Appl Catal B Environ 130:112–120CrossRefGoogle Scholar
  42. Shukla S, Oturan MA (2015) Dye removal via electrochemistry and oxidation using semiconductor oxides nanotubes. Environ Chem Lett 13:157–172CrossRefGoogle Scholar
  43. Simazaki D, Kubota R, Suzuki T, Akiba M, Nishimura T, Kunikane S (2015) Occurrence of selected pharmaceuticals at drinking water purification plants in Japan and implications for human health. Water Res 76:187–200CrossRefGoogle Scholar
  44. Sirés I, Brillas E (2012) Remediation of water pollution caused by pharmaceutical residues based on electrochemical separation and degradation technologies: a review. Environ Int 40:212–229CrossRefGoogle Scholar
  45. Sirés I, Brillas E, Oturan MA, Rodrigo MA, Panizza M (2014) Electrochemical advanced oxidation processes: today and tomorrow. A review. Environ Sci Pollut Res 21:8336–8367CrossRefGoogle Scholar
  46. Soltani RDC, Rezaee A, Khataee AR, Godini H (2013) Electrochemical generation of hydrogen peroxide using carbon black-, carbon nanotube-, and carbon black/carbon nanotube-coated gas-diffusion cathodes: effect of operational parameters and decolorization study. Res Chem Intermed 39:4277–4286CrossRefGoogle Scholar
  47. Sopaj F, Rodrigo MA, Oturan N, Podvorica F, Pinson J, Oturan MA (2015) Influence of the anode materials on the electrochemical oxidation efficiency. Application to oxidative degradation of the pharmaceutical amoxicillin. Chem Eng J 262:286–294CrossRefGoogle Scholar
  48. Sopaj F, Oturan N, Pinson J, Podvorica F, Oturan MA (2016) Effect of the anode materials on the efficiency of the electro-Fenton process for the mineralization of the antibiotic sulfamethazine. Appl Catal B Environ 199:331–341CrossRefGoogle Scholar
  49. Vasudevan S, Oturan MA (2014) Electrochemistry as cause and cure in water pollution. An overview. Environ Chem Lett 12:97–108CrossRefGoogle Scholar
  50. Yahya MS, Oturan N, El Kacemi K, El Karbane M, Aravindakumar CT, Oturan MA (2014) Oxidative degradation study on antimicrobial agent ciprofloxacin by electro-fenton process: kinetics and oxidation products. Chemosphere 117:447–454CrossRefGoogle Scholar
  51. Yahya MS, Karbane M, Oturan N, El Kacemi K, Oturan MA (2016) Mineralization of the antibiotic levofloxacin in aqueous medium by electro-Fenton process: kinetics and intermediates products analysis. Environ Technol 37:1276–1287CrossRefGoogle Scholar
  52. Yu X, Zhou M, Hu Y, Groenen Serrano K, Yu F (2014) Recent updates on electrochemical degradation of bio-refractory organic pollutants using BDD anode: a mini review. Environ Sci Pollut Res 21:8417–8431CrossRefGoogle Scholar
  53. Zaleska-Radziwill M, Affek K, Rybak J (2014) Ecotoxicity of chosen pharmaceuticals in relation to micro-organisms-risk assessment. Desalin Water Treat 52:3908–3917CrossRefGoogle Scholar
  54. Zazou H, Oturan N, Zhang H, Hamdani M, Oturan MA (2017) Comparative study of electrochemical oxidation of herbicide 2,4,5-T: kinetics, parametric optimization and mineralization pathway. Sust Environ Res 27:15–23Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2017

Authors and Affiliations

  • Nihal Oturan
    • 1
  • Charuvila T. Aravindakumar
    • 2
  • Hugo Olvera-Vargas
    • 1
  • Mathew M. Sunil Paul
    • 2
  • Mehmet A. Oturan
    • 1
    Email author
  1. 1.Laboratoire Géomatériaux et Environnement (LGE)Université Paris-EstMarne-la-ValléeFrance
  2. 2.School of Environmental SciencesMahatma Gandhi UniversityKottayamIndia

Personalised recommendations

Cite article

Buy options